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WO2015169002A1 - 一种树脂组合物及其在高频电路板中的应用 - Google Patents

一种树脂组合物及其在高频电路板中的应用 Download PDF

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Publication number
WO2015169002A1
WO2015169002A1 PCT/CN2014/084109 CN2014084109W WO2015169002A1 WO 2015169002 A1 WO2015169002 A1 WO 2015169002A1 CN 2014084109 W CN2014084109 W CN 2014084109W WO 2015169002 A1 WO2015169002 A1 WO 2015169002A1
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Prior art keywords
weight
resin composition
unit
resin
parts
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PCT/CN2014/084109
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English (en)
French (fr)
Inventor
陈广兵
曾宪平
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Priority to EP14891459.1A priority Critical patent/EP3056544B1/en
Priority to US15/027,365 priority patent/US10308806B2/en
Priority to JP2016516616A priority patent/JP6216043B2/ja
Priority to KR1020167022064A priority patent/KR101965940B1/ko
Publication of WO2015169002A1 publication Critical patent/WO2015169002A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08K5/14—Peroxides
    • 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
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • 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
    • 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
    • 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
    • H05K1/038—Textiles
    • 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

Definitions

  • the present invention relates to a resin composition, and in particular to a resin composition and its use in a high frequency circuit substrate.
  • the relationship between the signal transmission rate of the insulating material is a dielectric constant D k: the lower the dielectric constant D k dielectric material, the faster the transmission rate of the signal. Therefore, in order to increase the speed of the 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 signal in the substrate can no longer be ignored.
  • the relationship between the signal loss and the frequency, the dielectric constant D k , and the dielectric loss factor D f is as follows: The smaller the dielectric constant D k of the substrate is, the smaller the dielectric loss factor D f is, and the smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D k and a low dielectric loss factor D f 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 number of benzene ring structures 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 have achieved certain results.
  • a reactive group is introduced at the molecular chain end or side chain of the polyphenylene ether to make it a thermosetting resin.
  • the resin has excellent heat resistance, dielectric properties, etc. after heat curing, and becomes a high frequency preparation.
  • the modified polyphenylene ether resin having a reactive chain group at the terminal or side chain of the molecular chain is preferably used in a high-frequency circuit substrate to form a resin composition in combination with a crosslinking agent.
  • the crosslinking agent has a reactive group reactive with the modified polyphenylene ether.
  • commonly used crosslinking agents are polybutadiene, butadiene styrene copolymers and the like.
  • a high frequency circuit substrate is prepared by using a polybutadiene or a butadiene styrene copolymer as a crosslinking agent for a modified polyphenylene ether, as disclosed in CN 101370866A, CN 102161823, and CN 102304264. Although the dielectric properties of the sheet are excellent, the polybutadiene or butadiene styrene copolymer lowers the heat resistance and interlayer adhesion of the sheet.
  • Patent CN 102993683 uses a silicone compound containing an unsaturated double bond to prepare a crosslinking agent as a modified polyphenylene ether.
  • the prepared high frequency circuit substrate has a high glass transition temperature, a high thermal decomposition temperature, and a high interlayer. Adhesion, low dielectric constant and low dielectric loss tangent are ideal for use as circuit boards for high frequency electronic devices.
  • the organosilicon compound structure containing an unsaturated double bond employed in the patent CN 102993683 is a linear or cyclic organosilicon compound.
  • the linear organosilicon compound containing an unsaturated double bond has a good flexibility, and the prepared high-frequency circuit substrate has a low bending strength.
  • the circuit substrate prepared by using an annular organosilicon compound containing an unsaturated double bond has a good overall performance, but due to a small molecular weight, it has a problem of volatilization during the baking process.
  • an object of the present invention is to provide a resin composition, the thermosetting resin composition has a low dielectric constant D k and a low dielectric loss factor D f, heat resistance, interlayer Excellent adhesion performance, etc., meeting the dielectric properties, heat resistance and interlayer of high frequency circuit substrates Performance requirements such as adhesion can be used to prepare high frequency circuit substrates.
  • a resin composition comprising a modified polyphenylene ether resin and a monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond:) and a tetrafunctional siloxane unit: Made of MQ silicone resin.
  • the 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 curing in the presence of a curing initiator to obtain resistance.
  • a thermosetting resin excellent in thermal properties, dimensional stability, low water absorption, and dielectric properties.
  • a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit hydrolytic condensation of MQ silicone resin as a modified polyphenylene
  • the crosslinker of the ether, the resin composition has a high crosslink density after curing, and can provide a high glass transition temperature of the high frequency circuit substrate.
  • the MQ silicone resin obtained by hydrolysis-condensation of a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond is not polar. The group can ensure low water absorption and excellent dielectric properties of the high-frequency circuit substrate.
  • the MQ silicone resin obtained by hydrolysis-condensation of a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit having a three-dimensional network structure having an unsaturated double bond has a high thermal decomposition temperature. Provides excellent heat resistance of high frequency circuit substrates. Further, the prepared high-frequency circuit substrate has high interlayer adhesion and bending strength, and the reliability of the substrate can be improved.
  • the modified polyphenylene ether resin has excellent low dielectric constant and low dielectric loss tangent properties, and adopts a monofunctional siloxane unit (M unit:) and a tetrafunctional group having a three-dimensional network structure containing an unsaturated double bond.
  • the substrate Compared with polybutadiene and styrene-butadiene copolymer as a crosslinking agent, the substrate has higher heat resistance and interlayer adhesion.
  • the substrate has a higher flexural strength than the linear organosiliconization containing unsaturated double bonds as a crosslinker.
  • the MQ silicone resin obtained by hydrolysis condensation does not have the problem of volatilization when the sheet is baked.
  • the modified polyphenylene ether resin has the following structure:
  • M is selected from:
  • N is selected from any one of -0-, -CO-, SO, -SC-, -S0 2 - or -C(CH 3 ) 2 -.
  • R 2 , R 4 , R 6 , R 8 , R u , R 13 , R 15 and R 17 are each independently selected from a substituted or unsubstituted C1-C8 linear fluorenyl group, a substituted or unsubstituted C1-C8 branch. Any one of a chain fluorenyl group or a substituted or unsubstituted phenyl groupkind.
  • Ri, R 5 , R 7 , Ri. , Ri 2 , R 14 and R 16 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 linear fluorenyl group, a substituted or unsubstituted C1-C8 branched fluorenyl group or a substituted or unsubstituted phenyl group. Any of them.
  • R 9 is selected from:
  • A is an arylene group, a carbonyl group, or an anthracene group having 1 to 10 carbon atoms.
  • Z is an integer from 0-10.
  • R 21 , R 22 and R 23 are each independently selected from a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms.
  • the 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 7,000 g/mol.
  • methacrylate-modified polyphenylene ether resin is SA9000.
  • the key has a high thermal decomposition temperature and can improve the heat resistance of the cured product of the resin mixed system.
  • the monofunctional siloxane having a three-dimensional network structure containing an unsaturated double bond is as follows:
  • At least one of Zi, z 2 and z 3 is a group containing an unsaturated double bond, and the other two are independently selected from a substituted or unsubstituted C1-C8 linear fluorenyl group, a substituted or unsubstituted C1-C8 group.
  • MQ silicone resin is DT-2020 (Guangzhou Delta Silicone Technology Development Co., Ltd.).
  • Zl, Z2, and Z3 of DT-2020 are respectively vinyl, methyl, and methyl.
  • MQ silicone resins SY-1 and SY-2 different from DT-2020 we synthesized MQ silicone resins SY-1 and SY-2 different from DT-2020.
  • Zl, Z2, and Z3 of SY-1 are respectively vinyl, vinyl, and vinyl.
  • Zl, Z2, and Z3 of SY-2 are vinyl, phenyl, and phenyl, respectively.
  • the resulting MQ silicone resin has a weight of 10 to 100 parts by weight.
  • the 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 reaction cross-linking between reactive groups in the resin system, and the three-dimensional structure of the formal space Butyl peroxidation: a mixture of n-butyl valerate and t-butyl peroxybenzoate, a mixture of dibenzoyl peroxide and dicumyl peroxide, 4,4-di(tert-butylperoxidation: a mixture of n-butyl valerate and dibenzoyl peroxide, a mixture of tert-butyl peroxybenzoate and dicumyl peroxide, 4,4-di(tert-butylperoxy:) pentanoic acid A mixture of an ester, t-butyl peroxybenzoate and dibenzoyl peroxide.
  • the resin composition of the present invention further comprises a flame retardant.
  • the flame retardant of the present invention is selected from one or a mixture of at least two of a halogen flame retardant, a phosphorus flame retardant or a nitrogen flame retardant; more preferably, the flame retardant is selected One or a mixture of at least two of a bromine-based flame retardant, a phosphorus-based flame retardant, or a nitrogen-based flame retardant.
  • the bromine-based flame retardant is selected from any one or at least two selected from the group consisting of decabromodiphenyl ether, hexabromobenzene, decabromodiphenylacetone, and ethylenebistetrabromophthalimide. mixture.
  • the mixture is, for example, a mixture of decabromodiphenylacetamone and hexabromobenzene, a mixture of decabromodiphenyl ether and ethylene bistetrabromophthalimide, decabromodiphenylacetamidine, hexabromobenzene and ten a mixture of bromodiphenyl ether, a mixture of ethylene bistetrabromophthalimide, decabromodiphenylacetamidine, 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-oxygen Hetero-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl:)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa- One or a mixture of at least two of 10-phosphaphenanthrene-10-oxide.
  • the mixture is, for example, 10-phenyl-9,10-dihydro-9-oxa-10-phosphinophen-10-oxide and 2,6-bis(2,6-dimethylphenyl:)phosphino a mixture of benzene, 10-(2,5-dihydroxyphenyl: )-9,10-dihydro-9-oxa-10-phosphinophen-10-oxide and tris(2,6-dimethylbenzene) Base: a mixture of phosphines, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl) a mixture of phosphinobenzene and 10-(2,5-dihydroxyphenyl:)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethyl Phenyl)phosphine, 10-phenyl-9,
  • the nitrogen-based flame retardant is selected from the group consisting of one or a mixture of at least two of melamine, melamine phosphate, strontium phosphate, strontium carbonate or bismuth sulfamate, such as bismuth sulfamate and cesium carbonate.
  • the 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, aluminum oxide, 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. a mixture of cerium, a mixture of barium titanate and silicon carbide, a mixture of spherical silica, crystalline silica and amorphous silica.
  • the powder filler functions to improve dimensional stability, lower the coefficient of thermal expansion, and lower the cost of the system.
  • the shape and particle diameter of the powder filler are not limited in the present invention, and the particle diameter generally used is 0.2-10 ⁇ m, for example, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 5 ⁇ m, 8 ⁇ m, 9 ⁇ m, for example, the particle diameter can be selected to be 0.2. -10 ⁇ of spherical silica.
  • the resin composition comprises: a methacrylate-modified polyphenylene ether resin and a monofunctional siloxane unit ( ⁇ unit:) and a tetrafunctional silicon having a three-dimensional network structure containing an unsaturated double bond
  • the weight of the MQ silicone resin obtained by hydrolytic condensation of the oxygen unit (Q unit:) is 100 parts by weight, the weight of the radical initiator is 1-3 parts by weight, and the weight of the flame retardant is 5-40 weight. Share.
  • 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, and 2.9 parts by weight. Selecting the content of the radical initiator described in the present invention can obtain an appropriate anti-curing process At a high speed, good curability can be obtained in the curing reaction for manufacturing a prepreg or a high-frequency circuit substrate.
  • the parts by weight of the flame retardant are, for example, 5 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, 39 parts by weight. Parts by weight.
  • the content of the flame retardant is too high, resulting in a decrease in heat resistance and interlayer adhesion.
  • the weight of the flame retardant is from 10 to 150 parts by weight based on 100 parts by weight of the flame retardant.
  • the weight of the powder filler is, for example, 10 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, 120 parts by weight. 130 parts by weight, 140 parts by weight, and 145 parts by weight.
  • composition comprising means that it may include, in addition to the components, other components which impart different characteristics to the resin composition.
  • the resin composition of the present invention may be added with a thermosetting resin.
  • a thermosetting resin include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, a melamine resin, and the like, and these thermosetting resins may be added.
  • a curing agent or a curing agent accelerator include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, a melamine resin, and the like, and these thermosetting resins may be added.
  • a curing agent or a curing agent accelerator include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, a melamine resin, and the like.
  • the resin composition may further contain various additives such as a silicon germanium coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, and lubrication. Agents, etc.
  • additives such as a silicon germanium coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, and lubrication. Agents, etc.
  • additives such as a silicon germanium coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, and lubrication. Agents, etc.
  • the methacrylate-modified polyphenylene ether resin and the three-dimensional network structure containing an unsaturated double bond may be blended, stirred, and mixed by a known method.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing a 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, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and mesitylene, ethoxylate
  • An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide or hydrazine-methyl-2-pyrrolidone.
  • solvents may be used singly or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, butanone, 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 those skilled in the art according to their own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added 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 dipping 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 such as: 7628 fiberglass cloth, 2116 fiberglass cloth.
  • the total weight of the fat, flame retardant and powder filler is 100 parts by weight, and the weight of the glass fiber cloth 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, 220 parts by weight.
  • the drying temperature is 80-220 ° C, such as 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C.
  • the drying time is l-30 min, such as 5 min, 8 min, 13 min, 17 min, 21 min, 24 min, 28 min.
  • a fourth object of the present invention is to provide a method for preparing a high-frequency circuit substrate, wherein: at least one prepreg as described above is overlapped, and copper foil is placed on the upper and lower sides of the overlapping prepreg to perform a layer Prepared by compression molding.
  • the overlap preferably employs an automatic 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 70-120 min, such as 75 min, 80 min, 85 min, 90 min, 95 min, 100 min,
  • the lamination temperature is 180-220 ° C, for example 185 ° C, 190 ° C,
  • the pressure of the lamination is 40-60 kg/cm 2 , for example
  • a fifth object of the present invention is to provide a high-frequency circuit substrate prepared by the above-described production method. According to the method of the present invention, a high-frequency circuit substrate having excellent dielectric properties, heat resistance, low water absorption, high interlayer adhesion, and high bending strength can be obtained.
  • 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 monofunctional silicon having a three-dimensional network structure containing an unsaturated double bond, calculated as 100 parts by weight of the modified polyphenylene ether resin
  • the silicone resin obtained by hydrolyzing and condensing the oxon unit (M unit:) and the tetrafunctional siloxane unit: is 10-90 parts by weight.
  • Modified polyphenylene ether resin and three-dimensional network structure containing unsaturated double bonds The weight of the MQ silicone resin obtained by hydrolytic condensation of a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit:) is 100 parts by weight, and the weight of the radical initiator is 1-3 parts by weight, the weight of the flame retardant is 5-40 parts by weight; a modified polyphenylene ether resin, a monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond (M unit: The weight of the MQ silicone resin and the flame retardant obtained by hydrolytic condensation of a tetrafunctional siloxane unit (Q unit:) is 100-part by weight, and the weight of the powder filler is 10 to 150 parts by weight;
  • At least one prepreg is overlapped, copper foil is placed on both sides of the prepreg, and laminated and cured in a vacuum laminator to obtain a high-frequency circuit substrate.
  • High frequency as used in the present invention means that the frequency is greater than 1 ⁇ .
  • the present invention has the following beneficial effects:
  • the group can ensure low water absorption of high frequency circuit substrate and excellent dielectric properties;
  • a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit: hydrolytic condensation of MQ silicone resin as a modification
  • the cross-linking agent of the polyphenylene ether resin has high adhesion between the layers of the high-frequency circuit substrate and high bending strength, thereby improving the reliability of the substrate.
  • the MQ silicone resin obtained by hydrolysis-condensation of a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond is not volatile, There is no problem of volatilization during the baking process.
  • the high-frequency circuit substrate prepared by the resin has high glass transition temperature, good heat resistance, low water absorption rate, high interlayer adhesion, high bending strength, and excellent dielectric properties, and is very suitable for preparing a circuit board of a high-frequency electronic device.
  • FIG. 1 is a schematic view showing an embodiment of a high frequency circuit substrate according to the present invention.
  • 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 in this embodiment is 9 sheets. 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.
  • Preparation Example 2 A three-necked flask was charged with a mixture of divinyltetraphenylphosphonium oxide, concentrated hydrochloric acid, deionized water and ethanol, and the mechanical stirrer was turned on, and then rapidly added to the orthosilicate under rapid stirring and heating under reflux. The ethyl ester is hydrolyzed and condensed, and after hydrolysis for a certain period of time, toluene is added for extraction, and then the reaction liquid is poured into a separatory funnel, and allowed to stand for stratification. The water layer was separated and the oil layer was washed with water until neutral.
  • St-PPE-1 Styrene-modified polyphenylene ether resin having a molecular weight Mn of 2000. Monofunctional with a three-dimensional network of unsaturated double bonds
  • TD-2020 decondensed MQ silicone resin of which DL-2020 Zl, development limited
  • Z2 and Z3 are respectively vinyl, methyl, methyl, and molecular weight Mn is
  • MQ silicone resin obtained by decomposing SY-1 from a monofunctional siloxane unit (M unit) and a tetrafunctional siloxane unit (Q unit) with a three-dimensional network structure containing an unsaturated double bond Among them, Zl, Z2 and Z3 of SY-1 are respectively vinyl, vinyl and vinyl, and the molecular weight Mn is 10,000.
  • Example 1 90 parts by weight of methacrylate-based modified polyphenylene ether resin powder SA9000, 10 parts by weight of monofunctional silicon having three-dimensional network structure containing unsaturated double bonds MQ silicone resin TD-2020 obtained by hydrolytic condensation of oxyalkyl unit (M unit) with tetrafunctional siloxane unit (Q unit), 1.0 part by weight of free radical initiator dicumyl peroxide (DCP), dissolved 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 through the clamp shaft, and drying in an oven to remove the toluene solvent.
  • Example 2 80 parts by weight of a methacrylate-based modified polyphenylene ether resin powder SA9000, 20 parts by weight of a monofunctional siloxane unit (M unit) having a three-dimensional network structure containing an unsaturated double bond MQ silicone resin TD-2020 obtained by hydrolysis condensation of a tetrafunctional siloxane unit (Q unit), 3.0 parts by weight of a radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of flame retardant
  • M unit monofunctional siloxane unit
  • Q unit tetrafunctional siloxane unit
  • the emulsifier is used for emulsification, and the powder filler and the flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight through 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 provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • a methacrylate-based modified polyphenylene ether resin powder SA9000 30 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond and four MQ silicone resin TD-2020 obtained by hydrolysis and condensation of functional silicon oxide unit (Q unit:), 3.0 parts by weight of a radical initiator benzoyl peroxide (BPO), 170 parts by weight of spherical silica SJS- 0020, 15 parts by weight of flame retardant Exolit OP935 was mixed, dissolved in toluene solvent, and adjusted to a suitable viscosity.
  • M unit: monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond and four MQ silicone resin TD-2020 obtained by hydrolysis and condensation of functional silicon oxide unit (Q unit:), 3.0 parts by weight of a radical initiator benzoyl peroxide (BPO), 170 parts by weight of spherical silica S
  • the emulsifier is used for emulsification, and the powder filler and the flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight through 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 10Z thickness, vacuum laminated 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-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • styrene-based modified polyphenylene ether resin powder St-PPE-1 10 parts by weight of a monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond (M unit:) MQ silicone resin TD-2020 hydrolyzed and condensed with a tetrafunctional siloxane unit (Q unit:), 1.0 part by weight of a free radical initiator dicumyl peroxide (DCP), dissolved in toluene solvent, and Adjust to suit the viscosity.
  • DCP free radical initiator dicumyl peroxide
  • the 2116 prepreg was prepared by infiltrating the resin glue with a 2116 glass fiber cloth, controlling the weight with a pinch shaft, drying in an oven, and removing the toluene solvent.
  • Example 5 Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • a styrene-based modified polyphenylene ether resin powder St-PPE-1 20 parts by weight of a monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond (M unit:) MQ silicone resin TD-2020 obtained by hydrolysis condensation of a tetrafunctional siloxane unit (Q unit:), 3.0 parts by weight of a radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of resistance
  • the fuel agent BT-93W 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 flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight through 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 10Z thickness, vacuum laminated 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-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • a methacrylate-based modified polyphenylene ether resin powder SA9000 20 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond and four MQ silicone resin SY-1 obtained by hydrolysis-condensation of functional silicon oxide unit (Q unit:), 3.0 parts by weight of radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of flame retardant
  • M unit: monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond and four MQ silicone resin SY-1 obtained by hydrolysis-condensation of functional silicon oxide unit (Q unit:), 3.0 parts by weight of radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of flame retardant
  • the BT-93W 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 flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight through 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 provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • Example 7 80 parts by weight of a methacrylate-based modified polyphenylene ether resin powder SA9000, 20 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond and four Methyl silicone resin SY-2 obtained by hydrolysis condensation of functional silicone unit (Q unit:), 3.0 parts by weight of radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of flame retardant
  • M unit: monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond and four Methyl silicone resin SY-2 obtained by hydrolysis condensation of functional silicone unit (Q unit:), 3.0 parts by weight of radical initiator DCP, 60 parts by weight of fused silica 525, 30 parts by weight of flame retardant
  • Q unit: Methyl silicone resin SY-2 obtained by hydrolysis condensation of functional silicone unit (Q unit:)
  • Q unit: 3.0 parts by weight of radical initiator DCP
  • the emulsifier is used for emulsification, and the powder filler and the flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight through 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 provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • the organosilicon compound RH-Vi306 containing an unsaturated double bond was linearly the same as in Example 2. As shown in Table 2, Examples 1-7 and Comparative Examples constitute 1-2 and performance test results.
  • the organosilicon compound WD-V4 having an unsaturated double bond was ring-shaped, and the rest was the same as in Example 2.
  • Examples 1-7 and Comparative Example Composition 1-2 and performance test results are shown. 3 ⁇ 4>
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Performance
  • a monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond a hydrolytic condensation of a tetrafunctional siloxane unit:) with a silicone silicone resin as a crosslinking agent.
  • the high-frequency circuit substrate has a high glass transition temperature, a high thermal decomposition temperature, a low water absorption rate, a high interlayer adhesion, a high bending strength, and an excellent dielectric property, and thus contains an unsaturated double bond.
  • a silicone resin obtained by hydrolysis-condensation of a monofunctional siloxane unit (M unit:) and a tetrafunctional siloxane unit:) having a three-dimensional network structure is an excellent cross-linking agent and can be used for Preparation of a high frequency circuit substrate.
  • the substrate has a higher glass transition temperature than the MQ resin crosslinking agent TD-2020, SY-1 cross-linked SA9000, indicating that increasing the vinyl content can increase the crosslinking density of the substrate.
  • SY-2 cross-links SA9000 which has better compatibility with SA9000, indicating that the resin containing a benzene ring structure can increase the compatibility with the benzene ring-containing structural resin.
  • a methacrylate-modified polyphenylene ether resin 70 parts by weight of a methacrylate-modified polyphenylene ether resin, 30 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional group MQ silicone resin TD-2020 obtained by hydrolysis and condensation of silicon oxide unit (Q unit:), 2 parts by weight of radical initiator 4,4-di(tert-butylperoxy:) n-butyl valerate, 98 weight Parts of silicon carbide, 40 parts by weight of flame retardant tris(2,6-dimethylphenyl)phosphine, dissolved in a mixed solvent of toluene and methyl ethyl ketone, and adjusted to a suitable viscosity to obtain a tree Grease solution.
  • M unit: monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond
  • TD-2020
  • the resin paste was impregnated with 119 parts by weight of 7628 glass fiber cloth, controlled by a pinch shaft to be suitable for a single weight, and dried in an oven to remove the solvent to obtain a 7628 prepreg.
  • Four sheets of 7628 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 10Z 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-frequency circuit substrate.
  • the molecular weight of the methacrylate-modified polyphenylene ether is 10,000 g/mol.
  • a methacrylate-based modified polyphenylene ether resin 40 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional group MQ silicone resin TD-2020 obtained by hydrolysis and condensation of silicon oxide unit (Q unit:), 1.5 parts by weight of a radical initiator dibenzoyl peroxide, 125 parts by weight of aluminum nitride, and 25 parts by weight of decabromo
  • the diphenyl ether is mixed, dissolved in a toluene solvent, and adjusted to a suitable viscosity.
  • 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 2116 prepreg was prepared by impregnating the resin glue with 575 parts by weight of a 2116 glass fiber cloth, controlling it to a single weight by means of a pinch shaft, and drying it in an oven to remove the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the molecular weight of the methacrylate-modified polyphenylene ether resin is 8000 g/mol
  • a styrene-based modified polyphenylene ether resin 50 parts by weight of a styrene-based modified polyphenylene ether resin, 50 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional siloxane Unit unit:) Hydrolyzed and condensed MQ silicone resin TD-2020, 1 part by weight of a free radical initiator dibenzoyl peroxide, 100 parts by weight of alumina, 30 parts by weight of decabromodiphenyl ether, Dissolve in toluene solvent and adjust to a suitable viscosity.
  • M unit monofunctional siloxane unit
  • TD-2020 Hydrolyzed and condensed MQ silicone resin
  • the emulsifier is used for emulsification, and the powder filler and the flame retardant are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 230 parts by weight of a 2116 glass fiber cloth, controlling the weight by a pinch shaft, and baking the sheet 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 10Z thickness, vacuum laminated for 120 minutes in a press, a curing pressure of 40 kg/cm 2 , and a curing temperature of 180 ° C to obtain a high-frequency 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.
  • a styrene-based modified polyphenylene ether resin 40 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional siloxane Unit unit:) Hydrolyzed and condensed MQ silicone resin TD-2020, 1.5 parts by weight of a free radical initiator dibenzoyl peroxide, 125 parts by weight of boron nitride, 25 parts by weight of decabromodiphenyl ether, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • M unit monofunctional siloxane unit
  • TD-2020 Hydrolyzed and condensed MQ silicone resin
  • 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 parts by weight of a 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. Will be 4
  • a copper foil having a thickness of 10Z was vacuum laminated and cured in a press for 70 minutes, a curing pressure of 60 kg/cm 2 , and a curing temperature of 220 ° C to obtain a high-frequency circuit substrate.
  • the structural formula of the styrene-based modified polyphenylene ether resin is:
  • the molecular weight of the styryl-modified polyphenylene ether is 50 ⁇ x ⁇ 60, 25 ⁇ y ⁇ 45, 75 ⁇ x+y ⁇ 100, the molecular weight of the styryl-modified polyphenylene ether is
  • a methacrylate-modified polyphenylene ether resin 70 parts by weight of a methacrylate-modified polyphenylene ether resin, 30 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional group MQ silicone resin SY-1 obtained by hydrolysis and condensation of silicon oxide unit (Q unit:), 2 parts by weight of radical initiator 4,4-di(tert-butylperoxy:) n-butyl valerate, 98 weight A portion of silicon carbide, 40 parts by weight of a flame retardant tris(2,6-dimethylphenyl)phosphine, dissolved in a mixed solvent of toluene and methyl ethyl ketone, and adjusted to a suitable viscosity to obtain a resin gum.
  • M unit: monofunctional siloxane unit having a three-dimensional network structure containing an unsaturated double bond
  • the resin paste was impregnated with 119 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 sheets of 7628 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 10Z 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-frequency circuit substrate.
  • the structural formula of the methacrylate-modified polyphenylene ether is
  • the molecular weight of the methacrylate-modified polyphenylene ether is 10,000 g/mol.
  • a methacrylate-based modified polyphenylene ether resin 40 parts by weight of a monofunctional siloxane unit (M unit:) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional group MQ silicone resin SY-2 obtained by hydrolysis and condensation of silicon oxide unit (Q unit:), 1.5 parts by weight of a radical initiator dibenzoyl peroxide, 125 parts by weight of aluminum nitride, and 25 parts by weight of decabromo
  • the diphenyl ether is mixed, dissolved in a toluene solvent, and adjusted to a suitable viscosity.
  • 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 2116 prepreg was prepared by impregnating the resin glue with 575 parts by weight of a 2116 glass fiber cloth, controlling it to a single weight by means of a pinch shaft, and drying it in an oven to remove the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were provided with a copper foil of 10Z thickness, vacuum-laminated and solidified in a press for 90 minutes, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the molecular weight of the methacrylate-modified polyphenylene ether resin is 8000 g/mol

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Abstract

本发明公开了一种树脂组合物，所述树脂组合物包括：不饱和热固性改性聚苯醚树脂；和，含有不饱和双键的具有三维网状结构的由单官能度硅氧烷单元(M单元)与四官能度硅氧单元(Q单元)水解缩合而成的MQ有机硅树脂。本发明还公开了采用如上所述的树脂组合物制备的高频电路基板以及如上所述的树脂组合物在本领域的应用。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，非常适合作为高频电子设备的电路基板。

Description

一种树脂组合物及其在高频电路板中的应用 技术领域
本发明涉及一种树脂组合物， 具体地， 本发明涉及一种树脂组合物及其在 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、 介电性能等综合性能提出了更高的要求。
就介电性能而言， 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 输速率的高速化， 必须开发低介电常数的基板。 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、 介电常数 Dk、 介质损耗因子 Df的关系为： 基板介电常数 Dk越小、 介质损耗因子 Df越小， 信号损失就越小。 因此开发具有低的介质常数 Dk及低的介质损耗因子 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， 使之成为热 固性树脂。 该树脂热固化后具有优异的耐热、 介电等综合性能， 成为制备高频 电路基板的理想材料。
分子链末端或侧链带活性基团可固化的改性聚苯醚树脂在高频电路基板中 的应用方式一般为与交联剂配合组成树脂组合物。 交联剂带有可与改性聚苯醚 反应的活性基团。 根据文献调研， 对于带有 c=c双键的改性聚苯醚， 通常采用 的交联剂有聚丁二烯、 丁二烯苯乙烯共聚物等。 如 CN 101370866A , CN 102161823, CN 102304264专利采用聚丁二烯或丁二烯苯乙烯共聚物作为改性聚 苯醚的交联剂， 制备高频电路基板。 虽然板材的介电等综合性能优秀， 但聚丁 二烯或丁二烯苯乙烯共聚物降低了板材的耐热性能及层间粘合力。
采用含有不饱和双键的有机硅化合物作为改性聚苯醚的交联剂， 可解决聚 丁二烯或丁二烯苯乙烯共聚物作为聚苯醚交联剂带来的板材的耐热性能及层间 粘合力不足的问题。专利 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正切， 非常适合 作为高频电子设备的电路基板。
但是专利 CN 102993683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， 但由于分子量偏小， 存 在上胶烘片过程中挥发的问题。
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树脂组合物， 该热固性树脂组合物具有低的介质常数 Dk及低的介质损耗因子 Df， 耐热性能、 层间粘合力性能优异等， 满足了高频电路基板对介电性能、 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：
一种树脂组合物， 包括改性聚苯醚树脂和含有不饱和双键的具有三维网状 结构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而 成的 MQ有机硅树脂。
所述改性聚苯醚树脂， 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、 低吸水率和介电性能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由单官能度硅氧垸单元 (M单元:) 与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂作为改性聚苯醚的 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。 而且， 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ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优异的介电性能。 含有不饱和双键的具 有三维网状结构的由单官能度硅氧垸单元 (M单元：)与四官能度硅氧单元 单元:) 水解缩合而成的 MQ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。
改性聚苯醚树脂具有优异的低介电常数及低介质损耗正切等性能， 采用含 有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能 度硅氧单元 单元:)水解缩合而成的 MQ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介电性能、 吸水性、 耐热性、 层间粘合力、 弯曲强 度等综合性能良好。 与聚丁二烯、 丁苯共聚物作为交联剂相比， 基板有更高的 耐热性和层间粘合力。 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由单官能度硅氧垸单元 (M 单元：) 与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂不存在上胶烘片时 挥发的问题。
优选地， 所述改性聚苯醚树脂具有如下结构：
Figure imgf000005_0001
其中， 1 ^x^ 100, l ^y^ lOO, 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等。
M选自：
Figure imgf000005_0002
N选自 -0-、 -CO-, SO、 -SC -、 -S02-或 -C(CH3)2-中的任意一种。
R2、 R4、 R6、 R8、 Ru、 R13、 R15和 R17均独立地选自取代或未取代的 C1-C8 直链垸基、 取代或未取代的 C1-C8支链垸基或取代或未取代的苯基中的任意一 种。
Ri 、 R5、 R7、 Ri。、 Ri2、 R14和 R16均独立地选自氢原子、 取代或未取代 的 C1-C8直链垸基、 取代或未取代的 C1-C8支链垸基或取代或未取代的苯基中 的任意一种。
R9选自：
Figure imgf000006_0001
其中， A为亚芳香基、 羰基、 或碳原子数为 1-10的亚垸基。 Z为 0-10的整 数。 R21、 R22、 R23均独自的选自氢原子或碳原子数 1-10的垸基。
优选地， 所述改性聚苯醚树脂的数均分子量为 500-10000 g/mol , 优选 800-8000 g/mol, 进一歩优选 1000-7000 g/mol。
所述甲基丙烯酸酯基改性聚苯醚树脂的一个非限制性实例是 SA9000。
所述含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M单元:) 与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂，其不饱和双键含 量高， 固化后可形成高密度交联空间三维网络结构， 具有高玻璃化转变温， 且 不含极性基团， 具有优异的介电性能。 所述含有不饱和双键的具有三维网状结 构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而成 的 MQ有机硅树脂分子结构含有 Si-0键， 热分解温度高， 可提高树脂混合体系 固化物的耐热性。
优选地， 所述含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单 元 (M单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂如下 式：
(Z1Z2Z3Si01/2)x (Si04/2)y
其中， l x 100， l ^y^ lOO , 2^x+y^200, 且 0.01 x/y 10;
Zi、 z2、 z3三者至少一个为含不饱和双键的基团， 其余两者独立地选自取 代或未取代的 C1-C8直链垸基、 取代或未取代的 C1-C8支链垸基、 取代或未取 代的苯基。
所述 MQ有机硅树脂的一个非限制性实例是 DT-2020 (广州得尔塔有机硅 技术开发有限公司）。 DT-2020的 Zl、 Z2、 Z3分别为乙烯基、 甲基、 甲基。
另外为了提高 有机硅树脂与热固性改性聚苯醚树脂的相容性和交联密 度， 我们合成了不同于 DT-2020的 MQ有机硅树脂 SY-1和 SY-2。 SY-1的 Zl、 Z2、 Z3分别为乙烯基、 乙烯基、 乙烯基。 SY-2的 Zl、 Z2、 Z3分别为乙烯基、 苯基、 苯基
以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 网状结构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩 合而成的 MQ有机硅树脂的重量为 10-100重量份。
优选地， 本发明所述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 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， 本发明所述树脂组合物还包括阻燃剂。 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一种或者至少两种的混合物; 更优选地， 所述阻燃剂选自溴系阻燃剂、 磷系阻燃剂或氮系阻燃剂中的一种或 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、 十溴二苯乙垸、 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 十溴二苯乙垸和六溴苯的混合物， 十溴二苯醚和乙撑双四溴邻苯二甲酰亚胺的 混合物， 十溴二苯乙垸、 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、 十溴二苯乙垸、 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、 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、 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 0.2-10μηι， 例如 0.5μηι、 1μιη、 2μιη、 3μιη、 5μιη、 8μιη、 9μιη， 例如， 可选 择粒径为 0.2-10μιη的球形二氧化硅。
所述树脂组合物包括： 以甲基丙烯酸酯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由单官能度硅氧垸单元 (Μ 单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂的重量和为 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 5-40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、 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。
所述阻燃剂的重量份例如 5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、 39重量份。 阻燃剂的含量太高， 会导致耐热性和层间粘合力的降低。
以改性聚苯醚树脂、 含有不饱和双键的具有三维网状结构的由单官能度硅 氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂 和阻燃剂的重量和为 100重量份计， 所述粉末填料的重量为 10-150重量份。
所述粉末填料的重量例如 10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、 145重量份。
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脂组合物不同的特性。
例如， 本发明所述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、 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， 所述树脂组合物还可以含有各种添加剂， 例如硅垸偶联剂、 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、 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、 混合所述的甲基丙烯酸酯基改性聚苯醚树脂、 含有不饱和双键的具有三维网状 结构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而 成的 MQ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、 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， Ν,Ν- 二甲基甲酰胺、 Ν,Ν-二甲基乙酰胺、 Ν-甲基 -2-吡咯垸酮等含氮类溶剂。 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。
以改性聚苯醚树脂、 含有不饱和双键的具有三维网状结构的由单官能度硅 氧垸单元 (Μ单元：)与四官能度硅氧单元 单元:)水解缩合而成的 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、 220重量份。
所述干燥温度为 80-220°C，例如 90°C、 110°C、 150°C、 170°C、 190°C、 200°C。 所述干燥时间为 l-30min， 例如 5min、 8min、 13min、 17min、 21min、 24min、 28min。
本发明的目的之四在于提供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。
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、 115min。 所述层压的温度为 180-220°C， 例如 185 °C、 190°C、
195 °C、 200 °C、 205 °C、 210°C、 215 °C。 所述层压的压力为 40-60kg/cm2， 例如
45kg/cm2、 50kg/cm 55kg/cm 58kg/cm2。
本发明的目的之五在于提供一种如上所述的制备方法制备得到的高频电路 基板。 采用本发明所述的方法可以制备得到具有优异的介电性能、 耐热性能， 吸水率低、 层间粘结力高、 弯曲强度高的高频电路基板。
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由单官能度硅氧垸 单元 (M单元：)与四官能度硅氧单元 单元:)水解缩合而成的 有机硅树脂的重 量为 10-90重量份。以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 由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂的重量和为 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 5-40重量份； 以改性聚苯醚树脂、 含有不饱和双键的具有 三维网状结构的由单官能度硅氧垸单元 (M单元：)与四官能度硅氧单元 (Q单元:)水 解缩合而成的 MQ有机硅树脂和阻燃剂的重量和为 100重量份计， 所述粉末填 料的重量为 10-150重量份；
(2)将改性聚苯醚树脂、 含有不饱和双键的具有三维网状结构的由单官能 度硅氧垸单元 (M单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 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， 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 1ΜΗζ。
与现有技术相比， 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由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂作为改性聚 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由单官能度硅氧垸单元 (M 单 元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ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优异的介电性能；
(3 ) 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单 元:)与四官能度硅氧单元 单元:)水解缩合而成的 MQ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由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ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由单官能度硅氧垸单元 (M单元:) 与四官能度硅氧单元 单元:)水解缩合而成的 MQ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由单 官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 有 机硅树脂制备的高频电路基板玻璃化转变温度高、 耐热性好、 吸水率低、 层间 粘合力高、 弯曲强度高、 介电性能优异， 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歩说明本发明的技术方案。
图 1 : 本发明所述高频电路基板的一个实施方案的示意图。
本发明说明书附图中标记如下所示：
1和 10为铜箔， 铜箔优选高剥离反转铜箔、 低轮廓铜箔、 超低轮廓铜箔。
2、 3、 4、 5、 6、 7、 8、 9为预浸料， 该实施方案预浸料张数为 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。
具体实施方式 制备例
制备例 1 在三口烧瓶中加入六乙烯基二硅氧垸、 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正硅酸乙酯水解 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 MQ树脂 SY-1 , 分子量 Mn为 10000。
制备例 2 在三口烧瓶中加入二乙烯基四苯基二硅氧垸、 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 MQ树脂 SY-2 , 分子量 Mn为 10000。 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： 实施例 表 1所示为实施例及对比例所用原料。 表 1实施例 1-3所用原料 产品名称
制造厂商 材料描述
或牌号 甲基丙烯酸酯基改性聚苯醚树脂， 分子量 Mn为
Sabic SA9000
3000。 三菱化学公
St-PPE-1 苯乙烯基改性聚苯醚树脂， 分子量 Mn为 2000。 司 含有不饱和双键的具有三维网状结构的由单官能度 广州得尔塔
硅氧烷单元 (M单元：)与四官能度硅氧单元 单元：)水 有机硅技术
TD-2020 解缩合而成的 MQ有机硅树脂，其中 DT-2020的 Zl、 开发有限公
Z2、 Z3分别为乙烯基、 甲基、 甲基， 分子量 Mn为 司
10000。 含有不饱和双键的具有三维网状结构的由单官能度 硅氧垸单元 (M单元)与四官能度硅氧单元 (Q单元)水 自制 SY-1 解缩合而成的 MQ有机硅树脂， 其中 SY-1的 Zl、 Z2、 Z3分别为乙烯基、 乙烯基、 乙烯基， 分子量 Mn 为 10000。 含有不饱和双键的具有三维网状结构的由单官能度 硅氧烷单元 (M单元:)与四官能度硅氧单元 单元：)水 自制 SY-2 解缩合而成的 MQ有机硅树脂，其中 DT-2020的 Zl、 Z2、 Z3分别为乙烯基、 苯基、 苯基， 分子量 Mn为 10000。 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 上海高桥 DCP 过氧化二异丙苯 东莞芯威化
BPO 过氧化二苯甲酰 工 Sibelco 525 熔融二氧化硅
SJS-0020 球形二氧化硅 美国雅宝 BT-93W 溴系阻燃剂
Exolit
德国科莱恩 磷系阻燃剂
OP935 上海宏和 2116 玻璃纤维布 实施例 1 将 90重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末 SA9000, 10重量份的 含有不饱和双键的具有三维网状结构的由单官能度硅氧烷单元 (M单元)与四官 能度硅氧单元 (Q单元)水解缩合而成的 MQ有机硅树脂 TD-2020, 1.0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 10Z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°C， 制得高频电路基板。 基材综合性能如表 2所示。 实施例 2 将 80重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末 SA9000, 20重量份的 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M单元)与四官 能度硅氧单元 (Q单元)水解缩合而成的 MQ有机硅树脂 TD-2020, 3.0重量份的 自由基引发剂 DCP, 60重量份的熔融二氧化硅 525， 30重量份的阻燃剂 BT-93W 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 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 10Z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°C， 制得高频电路基板。 基材综合 性能如表 2所示。
实施例 3
将 70重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末 SA9000, 30重量份的 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官 能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 TD-2020, 3.0重量份的 自由基引发剂过氧化苯甲酰 （BPO) , 170重量份的球形二氧化硅 SJS-0020, 15 重量份的阻燃剂 Exolit OP935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等均匀分散在混合液中， 制得树脂 胶液。 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 10Z 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°C， 制得高频电路基板。 基材综合性能如表 2所示。
实施例 4
将 90重量份的苯乙烯基改性聚苯醚树脂粉末 St-PPE-1， 10重量份的含有不 饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅 氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 TD-2020, 1.0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 10Z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°C， 制得高频 电路基板。 基材综合性能如表 2所示。 实施例 5
将 80重量份的苯乙烯基改性聚苯醚树脂粉末 St-PPE-1， 20重量份的含有不 饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅 氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 TD-2020, 3.0重量份的自由基 引发剂 DCP, 60重量份的熔融二氧化硅 525， 30重量份的阻燃剂 BT-93W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 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 10Z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°C， 制得高频电路基板。 基材综合性 能如表 2所示。
实施例 6
将 80重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末 SA9000, 20重量份的 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官 能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 SY-1， 3.0重量份的自由 基引发剂 DCP, 60重量份的熔融二氧化硅 525， 30重量份的阻燃剂 BT-93W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 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 10Z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°C， 制得高频电路基板。 基材综合性 能如表 2所示。
实施例 7 将 80重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末 SA9000, 20重量份的 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官 能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 SY-2 , 3.0重量份的自由 基引发剂 DCP, 60重量份的熔融二氧化硅 525， 30重量份的阻燃剂 BT-93W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 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 10Z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°C， 制得高频电路基板。 基材综合性 能如表 2所示。
比较例 1
将实施例 2 中的含有不饱和双键的具有三维网状结构的由单官能度硅氧垸 单元 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂换为 线性含不饱和双键的有机硅化合物 RH-Vi306， 其余与实施例 2相同。 如表 2所 示为实施例 1-7和对比例组成 1-2和性能测试结果。
比较例 2
将实施例 2 中的含有不饱和双键的具有三维网状结构的由单官能度硅氧垸 单元 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂换为 环形含不饱和双键的有机硅化合物 WD-V4, 其余与实施例 2相同。 如表 2所示 为实施例 1-7和对比例组成 1-2和性能测试结果。 ¾>
表 2
。
原料和
实施例 1 实施例 2 实施例 3 实施例 4 实施例 5 实施例 6 实施例 7 对比例 1 对比例 2 性能
SA9000 90 80 70 0 0 80 80 80 80
St-PPE-1 0 0 0 90 80 0 0 0 0
TD-2020 10 20 30 10 20 0 0 0 0
RH-Vi30 0 0 0 0
0 0 0 20 0 6
WD-V4 0 0 0 0 0 0 0 0 20
SY-1 0 0 0 0 0 20 0 0 0
SY-2 0 0 0 0 0 0 20 0 0
DCP 1 3 0 1 3 3 3 3 3
BPO 0 0 3 0 0 0 0 0 0
525 0 60 0 0 60 60 60 60 60
SJS-0020 0 0 170 0 0 0 0 0 0
BT-93W 0 30 0 0 30 30 30 30 30
Exolit 0 0 0 0
0 0 15 0 0 OP935
2116 80 155 230 80 155 155 155 155 155 树脂相
容性 差 差 差 差 差 差 好 差 差 玻璃化
转
205.0 208.4 213.2 210.5 215.6 231.8 210.0 198.2 215.0 变温度
(°C)
热分解
468.0 435.3 458.5 469.1 438.7 4407.6 437.2 421.7 424.1 温度 (°c)
>300 >300 >300 >300 >300 >300 >300 >300 >300 吸水率 0.08 0.08 0.08 0.07 0.07 0.08 0.08 0.08 0.08 层间粘 1.06-2.2 1.95-2.5 1.73-1.9 1.45-1.9 1.23-1.8 2.75-3.5 2.14-2.6 1.44-1.6 1.62-2.5 合力 1 6 8 5 9 9 4 1 6 弯曲强
)又 456 486 493 451 476 492 479 359 421
(Mpa)
介电常
数 3.64 3.75 4.13 3.63 3.60 3.80 3.78 4.03 3.71 (10GHz)
介质损
耗正切 0.0078 0.0075 0.0073 0.0062 0.0060 0.0071 0.0073 0.0075 0.0072 (10GHz) 从表 2数据可以看出，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由单官能度硅氧垸单元 (M 单元：)与 四官能度硅氧单元 单元:)水解缩合而成的 树脂 TD-2020作为交联剂，得到 的高频电路基板具有更高的弯曲强度。 与环形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由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 单元:)水解缩合而成的 树脂 TD-2020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 结构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩合而 成的 MQ有机硅树脂作为交联剂所制备的高频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、 高的弯曲强度及优异的 介电性能， 因此含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M单元：)与四官能度硅氧单元 单元:)水解缩合而成的 有机硅树脂是一种综 合性能优异的交联剂， 可用于高频电路基板的制备。
另外， 由表 2可知， 相对于 MQ树脂交联剂 TD-2020, SY-1交联 SA9000, 基材具有更高的玻璃化转变温度， 表明增加 乙烯基含量可高基材的交联密 度。 相对于 MQ树脂交联剂 TD-2020, SY-2交联 SA9000, 与 SA9000具有更好 的相容性， 表明含有苯环结构的 树脂可增加与含苯环结构树脂的相容性。
实施例 8
将 70重量份的甲基丙烯酸酯基改性聚苯醚树脂， 30重量份的含有不饱和双 键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 TD-2020, 2重量份的自由基引发剂 4,4- 二 (叔丁基过氧化：)戊酸正丁酯， 98重量份的碳化硅， 40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 119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 10Z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°C， 制得高频电路基板。
所述甲基丙烯酸酯基改性聚苯醚的结构式为：
Figure imgf000023_0001
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 10000g/mol。
实施例 9
将 60重量份的甲基丙烯酸酯基改性聚苯醚树脂， 40重量份的含有不饱和双 键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 TD-2020, 1.5重量份的自由基引发剂 过氧化二苯甲酰， 125 重量份的氮化铝， 25 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， 使粉末填和阻燃剂等 均匀分散在混合液中， 制得树脂胶液。 用 575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 10Z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°C， 制得高频电路基板。
所述甲基丙烯酸酯基改性聚苯醚的结构式为：
Figure imgf000024_0001
50<x<100, 甲基丙烯酸酯基改性聚苯醚树脂的分子量为 8000g/mol;
实施例 10
将 50重量份的苯乙烯基改性聚苯醚树脂， 50重量份的含有不饱和双键的具 有三维网状结构的由单官能度硅氧垸单元 (M单元：)与四官能度硅氧单元 单元:) 水解缩合而成的 MQ有机硅树脂 TD-2020, 1重量份的自由基引发剂过氧化二苯 甲酰， 100重量份的氧化铝， 30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 10Z 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°C， 制得高频电路基板。
所述苯乙烯基改性聚苯醚树脂的结构式为：
Figure imgf000024_0002
5<y<15， 苯乙烯基改性聚苯醚树脂的分子量为 1000g/mol。
实施例 11
将 60重量份的苯乙烯基改性聚苯醚树脂， 40重量份的含有不饱和双键的具 有三维网状结构的由单官能度硅氧垸单元 (M单元：)与四官能度硅氧单元 单元:) 水解缩合而成的 MQ有机硅树脂 TD-2020, 1.5重量份的自由基引发剂过氧化二 苯甲酰， 125 重量份的氮化硼， 25 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
10Z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°C， 制得高频电路基板。
所述苯乙烯基改性聚苯醚树脂的结构式为：
Figure imgf000025_0001
50<x<60, 25<y<45 , 75<x+y<100, 苯乙烯基改性聚苯醚的分子量为
Figure imgf000025_0002
实施例 12
将 70重量份的甲基丙烯酸酯基改性聚苯醚树脂， 30重量份的含有不饱和双 键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 SY-1 , 2重量份的自由基引发剂 4,4-二 (叔丁基过氧化：)戊酸正丁酯， 98重量份的碳化硅， 40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 119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 10Z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°C， 制得高频电路基板。 所述甲基丙烯酸酯基改性聚苯醚的结构式为
Figure imgf000026_0001
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 10000g/mol。
实施例 13
将 60重量份的甲基丙烯酸酯基改性聚苯醚树脂， 40重量份的含有不饱和双 键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂 SY-2, 1.5重量份的自由基引发剂过氧 化二苯甲酰， 125 重量份的氮化铝， 25 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， 使粉末填和阻燃剂等均匀 分散在混合液中， 制得树脂胶液。 用 575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 10Z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°C， 制得高频电路基板。
所述甲基丙烯酸酯基改性聚苯醚的结构式为：
Figure imgf000026_0002
50<x<100, 甲基丙烯酸酯基改性聚苯醚树脂的分子量为 8000g/mol;
表 3所示为实施例 8-13高频电路基板性能测试结果。 实施例 实施例 实施例 实施例 性能 实施例 8 实施例 9
10 11 12 13 玻璃化转
198.4 201.3 215.2 206.9 221.7 201.5 变温度 (°c) 热分解
449.1 453.3 459.4 453.8 456.7 459.1 温度 (°c) 耐浸悍性
〉300 〉300 〉300 〉300 〉300 〉300
288。C (秒：） 吸水率 0.08 0.08 0.08 0.08 0.08 0.08 层间粘合力 1.56-2.23 1.31-2.41 1.27-2.62 1.44-1.61 2.56-2.89 1.52-2.68 弯曲强度
484 471 460 478 492 481 (Mpa) 介电常数
3.85 3.76 4.08 3.63 3.80 3.75 (10GHz) 介质损耗正切
0.0086 0.0073 0.0069 0.0070 0.0080 0.0074 (10GHz) 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

权 利 要 求 书
1、 一种树脂组合物， 其特征在于， 所述树脂组合物包括不饱和热固性改性 聚苯醚树脂； 和， 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单 元 (M单元)与四官能度硅氧单元 (Q单元)水解缩合而成的 有机硅树脂。
2、 如权利要求 1所述的树脂组合物， 其特征在于， 所述改性聚苯醚树脂具 有如下结构：
Figure imgf000028_0001
其中，
N选自 -0-、 -CO-、 SO、 -SC -、 -S02-或 -C(C¾)2-中的任意一种；
R2、 R4、 R6、 R8、 Ru、 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；
Ri、 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直链垸基、 取代或未取代的 C1-C8支链垸基或取代或未取代的苯基中 的任意一种； 并且
R9选自：
Figure imgf000029_0001
其中， A为亚芳香基、 羰基、 或碳原子数为 1-10的亚垸基。 Z为 0-10的整 数。 R21、 R22、 R23均独立地为氢原子或碳原子数 1-10的垸基；
3、 如权利要求 1或 2所述的树脂组合物， 其特征在于， 所述改性聚苯醚树 脂的数均分子量为 500-10000 g/molo
4、 如权利要求 3所述的树脂组合物， 其特征在于， 所述改性聚苯醚树脂的 数均分子量为 800-8000 g/molo
5、 如权利要求 4所述的树脂组合物， 其特征在于， 所述改性聚苯醚树脂的 数均分子量为 1000-7000 g/molo
6、 如前述权利要求任一项所述的树脂组合物， 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单官能度硅氧垸单元 (M 单元：)与四官能度硅氧 单元 单元:)水解缩合而成的 MQ有机硅树脂是由如下通式代表的化合物：
(Z1Z2Z3Si01/2)x (Si04/2)y
其中， l x 100， l^y^lOO, 2^x+y^200, 且 0.01 x/y 10;
Zi、 z2、 z3三者至少一个为含不饱和双键的基团， 其余两者独立地选自取 代或未取代的 C1-C8直链垸基、 取代或未取代的 C1-C8支链垸基、 取代或未取 代的苯基。
7、 如前述权利要求任一项所述的树脂组合物， 其特征在于， 所述树脂组合 物还包括自由基引发剂。
8、 如权利要求 7所述的树脂组合物， 其特征在于， 所述自由基引发剂选自 有机过氧化物引发剂。
9、 如权利要求 8所述的树脂组合物， 其特征在于， 所述有机过氧化物引发 剂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、 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。
10、 如前述权利要求任一项所述的树脂组合物， 其特征在于， 所述树脂组 合物还包括阻燃剂。
11、 如权利要求 10所述的树脂组合物， 其特征在于， 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一种或者至少两种的混合物。
12、 如权利要求 10所述的树脂组合物， 其特征在于， 所述阻燃剂选自溴系 阻燃剂、 磷系阻燃剂或氮系阻燃剂中的一种或者至少两种的混合物。
13、 如权利要求 12所述的树脂组合物， 其特征在于， 所述溴系阻燃剂选自 十溴二苯醚、 六溴苯、 十溴二苯乙垸、 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。
14、 如权利要求 11所述的树脂组合物， 其特征在于， 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。
15、 如权利要求 11或 12所述的树脂组合物， 其特征在于， 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。
16、 如前述权利要求任一项所述的树脂组合物， 其特征在于， 所述树脂组 合物还包括粉末填料。
17、 如权利要求 16所述的树脂组合物， 其特征在于， 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、 钛酸钡或钛酸锶的一种或至少 两种的混合物。
18、 如前述权利要求任一项所述的树脂组合物， 其特征在于， 所述树脂组 合物包括：
以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 网状结构的由单官能度硅氧垸单元 单元：)与四官能度硅氧单元 单元:)水解缩 合而成的 MQ有机硅树脂的重量为 10-100重量份。
19、 如权利要求 18所述的树脂组合物， 其特征在于， 以改性聚苯醚树脂和 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官 能度硅氧单元 (Q单元:)水解缩合而成的 MQ有机硅树脂的重量和为 100重量份 计， 自由基引发剂的重量为 1-3重量份， 阻燃剂的重量为 5-40重量份。
20、 如权利要求 19所述的树脂组合物， 其特征在于， 以改性聚苯醚树脂、 含有不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官 能度硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂和阻燃剂的重量和为 100 重量份计， 粉末填料的重量为 10-150重量份。
21、 一种树脂胶液， 其特征在于， 其是将如前述权利要求任一项所述的树 脂组合物溶解或分散在溶剂中得到。
22、 一种预浸料， 其特征在于， 其是将玻璃纤维布浸润在如权利要求 21所 述的树脂胶液后， 干燥得到。
23、 如权利要求 22所述的预浸料， 其特征在于， 以改性聚苯醚树脂、 含有 不饱和双键的具有三维网状结构的由单官能度硅氧垸单元 (M 单元：)与四官能度 硅氧单元 单元:)水解缩合而成的 MQ有机硅树脂、阻燃剂和粉末填料的总重量 为 100重量份计， 玻璃纤维布的重量为 50-230重量份。
24、 一种高频电路基板， 其特征在于， 所述高频电路基板由如权利要求 22 或 23所述的预浸料制成.
25、 如权利要求 24所述的高频电路基板， 其特征在于， 所述高频电路基板 是通过以下方法制得的： 重叠至少一张所述预浸料， 在预浸料的两侧放置铜箔， 层压成型， 得到高频电路基板。
26、 如前述权利要求任一项所述的树脂组合物在制备树脂胶液、 预浸料和 高频电路基板中的应用。
PCT/CN2014/084109 2014-05-06 2014-08-11 一种树脂组合物及其在高频电路板中的应用 Ceased WO2015169002A1 (zh)

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