WO2022000629A1 - Resin composition, prepreg, laminated board, preparation method for prepreg, preparation method for laminated board and application thereof - Google Patents

Resin composition, prepreg, laminated board, preparation method for prepreg, preparation method for laminated board and application thereof Download PDF

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Publication number
WO2022000629A1
WO2022000629A1 PCT/CN2020/103774 CN2020103774W WO2022000629A1 WO 2022000629 A1 WO2022000629 A1 WO 2022000629A1 CN 2020103774 W CN2020103774 W CN 2020103774W WO 2022000629 A1 WO2022000629 A1 WO 2022000629A1
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parts
resin
styrene
resin composition
prepreg
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PCT/CN2020/103774
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French (fr)
Chinese (zh)
Inventor
夏克强
王和志
张鹏
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瑞声声学科技(深圳)有限公司
瑞声科技（南京）有限公司
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Publication of WO2022000629A1 publication Critical patent/WO2022000629A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present application relates to the field of communication materials, in particular to a resin composition, a prepreg, a laminate, a method for preparing a prepreg, a method for preparing a laminate, and applications thereof.
  • 5G communication technology is the fifth generation of mobile communication technology, which was developed to meet the needs of mobile Internet and Internet of Everything services after 2020. Compared with 4G communication technology, 5G communication technology has the characteristics of faster information transmission rate, stronger spectrum utilization efficiency, lower delay, more reliable information transmission and higher link density.
  • FR-4 is by far the most widely used substrate.
  • FR-4 is a kind of substrate with epoxy resin as matrix resin and glass fiber cloth as reinforcement material.
  • the thermal conductivity of epoxy resin and glass fiber cloth is poor, and the general thermal conductivity of FR-4 is only 0.25W/(m.K). Therefore, its heat dissipation performance can no longer meet the heat dissipation requirements of current high-power devices.
  • high thermal conductivity FR-4 One of the existing methods to solve this problem is to prepare high thermal conductivity FR-4.
  • the most common method for preparing high thermal conductivity FR-4 is to add a large proportion of thermally conductive fillers, such as silicon carbide (SiC), aluminum oxide (Al). 2 O 3 ), aluminum nitride (AlN) and boron nitride (BN), etc.
  • thermally conductive fillers such as silicon carbide (SiC), aluminum oxide (Al). 2 O 3 ), aluminum nitride (AlN) and boron nitride (BN), etc.
  • the increase of fillers will increase its dielectric constant and reduce the electrical insulation performance.
  • the dielectric constant of the commonly used high thermal conductivity FR-4 is mostly above 4.5, and the dielectric loss is above 0.01. Therefore, how to develop a prepreg with both low dielectric loss and high thermal conductivity and its copper clad laminate is a technical problem that needs to be solved urgently at present.
  • One of the objectives of the present application is to provide a resin composition with high thermal conductivity and low dielectric loss.
  • a resin composition comprising the following components in parts by weight:
  • thermally conductive filler 20-40 parts of hydrocarbon resin containing CC unsaturated bond, 10-40 parts of thermally conductive filler, 1-3 parts of silane coupling agent and 0.1-10 parts of initiator, the thermally conductive filler is selected from One, two or more selected from silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide.
  • the second purpose of the present application is to provide a prepreg with high thermal conductivity and low dielectric loss.
  • a prepreg comprises a reinforcing material and a resin layer covering the reinforcing material, and the material of the resin layer is the above-mentioned resin composition.
  • the third purpose of this application is to provide the preparation method of the above-mentioned prepreg, and the technical scheme is as follows:
  • a preparation method of a prepreg comprising the following processes:
  • the above-mentioned resin composition is dissolved in a solvent to make glue
  • the impregnated reinforcing material is heated and semi-cured to form the prepreg.
  • the fourth purpose of this application is to provide a laminate with high thermal conductivity and low dielectric loss, and the technical solution is as follows:
  • a laminate comprising the above-mentioned prepreg and a conductive metal sheet stacked on one or both sides of the prepreg.
  • the fifth purpose of this application is to provide the preparation method of the above-mentioned laminate, and the technical scheme is as follows:
  • a preparation method of a laminate comprising the following processes:
  • One side or both sides of the above-mentioned prepreg is covered with a conductive metal sheet, and pressed into shape to form the laminate.
  • the sixth purpose of the present application is to provide the application of the above-mentioned resin composition, the above-mentioned prepreg or the above-mentioned laminate in the field of circuit board preparation.
  • the dielectric loss of the resin is reduced, and the thermal conductivity of the resin is improved by using a thermally conductive filler, and a resin composition with high thermal conductivity and low dielectric loss can be obtained by appropriate component ratio.
  • prepregs and laminates with high thermal conductivity and low dielectric loss can be obtained, so as to meet the needs of high-frequency communications.
  • the thermal conductivity is improved by adding thermal conductive fillers;
  • the overall dielectric loss of the prepreg meets the requirements of high-frequency communication equipment (5G communication equipment).
  • the present application discloses a resin composition, comprising the following components in parts by weight: 20-40 parts of a hydrocarbon resin containing CC unsaturated bonds, 10-40 parts of a thermally conductive filler, 1-3 parts of a Silane coupling agent and 0.1 to 10 parts of initiator, thermally conductive filler selected from one, two or more of silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide kind.
  • Hydrocarbon resins containing CC unsaturated bonds have lower dielectric loss, and at the same time, their polymer chains contain reactive functional groups with CC unsaturated bonds, which can interact between the polymer chains and between them and silane coupling agents.
  • Initiator also known as free radical initiator, refers to a class of compounds that are easily decomposed into free radicals (ie primary free radicals) by heat, which can be used to initiate free radical polymerization and copolymerization of olefinic and diene monomers, and can also be used for The cross-linking curing and polymer cross-linking reaction of unsaturated polyester, therefore, the introduction of the initiator can make the cross-linking reaction more thorough, improve the resin strength, enhance the uniformity of the resin material, reduce the polarity of the resin, and strengthen the resin and the resin. Compatibility of thermally conductive fillers, etc.
  • the silica is preferably modified fused silica, and the modified fused silica is a silica modified with a silane coupling agent.
  • the silane coupling agent is selected from vinyltrimethylsiloxane, Any one of 3-aminopropyltrimethylsiloxane or (2,3-glycidoxy)propyltrimethylsiloxane, etc.
  • the particle size of the modified fused silica is preferably 0.1 um-100um, more preferably 0.1um-50um.
  • the hydrocarbon resin containing CC unsaturated bonds is selected from at least one of polydiene resins, cyanate resins, benzocyclobutene resins or polyphenylene ether resins terminated with functional groups containing CC unsaturated bonds more preferably, two or more selected from the above-mentioned resins.
  • 20 to 40 parts of hydrocarbon resin containing CC unsaturated bonds include 10 to 20 parts of polydiene resin and 10 to 20 parts of CC unsaturated bond-containing hydrocarbon resin functional group terminated polyphenylene ether resin. That is, the resin composition includes the following components in parts by weight: 10 parts-20 parts of polydiene-based resin, 10 parts-20 parts of polyphenylene ether resin capped with a functional group containing CC unsaturated bonds, 10 parts- 40 parts of thermally conductive filler and 1 part to 3 parts of silane coupling agent.
  • the hydrocarbon resin containing C-C unsaturated bonds is a low molecular weight resin, preferably, its average molecular weight is 800-5000, more preferably, its average molecular weight is 1000-3000.
  • the average molecular weight of the polydiene resin is 800-5000, and more preferably, the average molecular weight is 1000-3000.
  • the average molecular weight of the polyphenylene ether resin capped with a functional group containing a C-C unsaturated bond is 800-5000, and more preferably, its average molecular weight is 1000-3000.
  • the silane coupling agent is selected from vinyl silane coupling agents, amino silane coupling agents, acrylic silane coupling agents, phenyl silane coupling agents, epoxy silane coupling agents or reactive polymer-based coupling agents One, two or more of the joint agents.
  • the vinylsilane coupling agent can be vinyltrimethylsiloxane, etc.
  • the aminosilane coupling agent can be 3-aminopropyltrimethylsiloxane, etc.
  • the phenylsilane coupling agent can be phenyltrimethylsiloxane Siloxane and the like
  • the epoxy silane coupling agent may be (2,3-glycidoxy)propyltrimethylsiloxane and the like.
  • Reactive polymer-based coupling agent for example, can be BYK-C8003, a reactive polymer-based coupling agent launched by BYK, which is specially designed to improve unsaturated polyester and vinyl ester resins cured by free radical initiators Mechanical properties of glass fiber reinforced materials.
  • Polydiene resin refers to the molecular structure containing two or more double bonds, and can participate in the construction of the cross-linking system, preferably, polydiene resin is selected from polyisoprene resin, polybutylene Diene resins (such as Caoda Chemical's B1000, B2000 and polybutadiene), polydivinylbenzene resins, polydicyclopentadiene homopolymer resins, isoprene-styrene copolymer resins, butadiene Styrene-styrene copolymer resin, styrene-divinylbenzene copolymer resin, styrene-butadiene-divinylbenzene copolymer resin, hydrogenated styrene-butadiene-divinylbenzene copolymer resin, One, two or more of styrene-butadiene-maleic anhydride copolymer resins or maleated s
  • the polyphenylene ether resin terminated with a functional group containing a C-C unsaturated bond may be an acrylic-terminated polyphenylene ether resin and/or a 4-vinylbenzene-terminated polyphenylene ether resin.
  • the acrylic-terminated polyphenylene ether resin may be a methacrylic acid polyphenylene ether resin, for example, SA-9000 product of Sabic Company.
  • the 4-vinylbenzene terminated polyphenylene ether resin may be vinylbenzyl ether polyphenylene ether resin, for example, OPE-2st product and OPE-1st product of Mitsubishi Gas Chemical Corporation.
  • the initiator is selected from the group consisting of dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl dicumyl peroxide, tert-butyl hydroperoxide, diisopropyl benzene One, two or more of propylbenzene hydroperoxide, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide or p-amyl hydroperoxide. More preferably, the initiator may be di-tert-butyl dicumyl peroxide (BIPB) and/or dicumyl peroxide (DCP).
  • BIPB di-tert-butyl dicumyl peroxide
  • DCP dicumyl peroxide
  • the resin composition of the present application further comprises 0.5 to 10 parts of thermoplastic elastomer material.
  • the introduction of thermoplastic elastomer material can increase the toughness of the sheet and improve the compatibility.
  • thermoplastic elastomer material Preferably, a high molecular weight thermoplastic elastomer material is used.
  • a high molecular weight thermoplastic elastomer material is used in combination with a low molecular weight hydrocarbon resin containing CC unsaturated bonds. High resin with good dispersibility and good compatibility.
  • the average molecular weight of the thermoplastic elastomer material is 10,000-100,000.
  • the thermoplastic elastomeric material may be selected from styrene-butadiene block copolymers, styrene-butadiene-styrene triblock copolymers, styrene-isoprene block copolymers, styrene-isoprene One, two or more of diene-styrene copolymer or polyphenylene ether polymer, or the thermoplastic elastomer material is selected from styrene-butadiene block copolymer, styrene-butadiene -One or two kinds of hydrogenated resin corresponding to styrene triblock copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene copolymer or polyphenylene ether polymer or more.
  • the resin composition of the present application further includes 1 part to 15 parts of a flame retardant.
  • the flame retardant may be a phosphorus-containing flame retardant and/or a bromine-containing flame retardant.
  • the phosphorus-containing flame retardant is selected from phosphazene compounds (for example, hexaphenoxy cyclophosphazene (HPCTP) or SPB-100 of Otsuka Chemical), phosphoric acid ester compounds (PX-200 of Daihachi Chemical), nitrogen Phosphorus flame retardants (for example, melamine polyphosphate (Melapur 200FF) from BASF), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), or diethylaluminum phosphate One, two or more of flame retardants (OP-935, OP-945), etc.
  • phosphazene compounds for example, hexaphenoxy cyclophosphazene (HPCTP) or SPB-100 of Otsuka Chemical
  • PX-200 of Daihachi Chemical
  • nitrogen Phosphorus flame retardants for example, melamine polyphosphate (Melapur 200FF) from BASF
  • DOPO
  • the bromine-containing flame retardant may be selected from one, two or more of decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, decabromcyclododecane, and the like.
  • the resin composition includes the following components by weight:
  • the polydiene resin can be 10 parts, 12 parts, 15 parts or 20 parts
  • the polyphenylene ether resin capped with the functional group containing CC unsaturated bond can be 10 parts, 12 parts, 15 parts or 20 parts
  • the thermoplastic elastomer material can be 0.5 parts, 1 part, 2 parts or 3 parts
  • the thermally conductive filler can be 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts
  • the silane coupling agent can be 1 part, 1.5 parts or 2 parts
  • the initiator can be 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts
  • the flame retardant can be 1 part, 3.5 parts or 6 parts.
  • the present application also discloses a prepreg, which includes a reinforcing material and a resin layer covering the reinforcing material, and the material of the resin layer is the above-mentioned resin composition.
  • the weight part of the reinforcing material is 20-40 parts, and the weight part of the resin layer is 60-80 parts.
  • the reinforcing material is glass fiber cloth. More preferably, the reinforcing material is electronic-grade glass fiber cloth, and the weight portion of the electronic-grade glass fiber cloth can be 20 parts, 30 parts or 40 parts.
  • the preparation method of above-mentioned prepreg comprises the following process:
  • the above-mentioned resin composition is dissolved in a solvent to form a glue solution, the reinforcing material is then immersed in the glue solution, and the impregnated reinforcing material is heated and semi-cured to form a prepreg.
  • the present application also discloses a laminate, comprising the above-mentioned prepreg and a conductive metal sheet stacked on one or both sides of the prepreg.
  • the prepreg may be one sheet, or two or more prepregs stacked in sequence.
  • the conductive metal sheet is copper foil.
  • the preparation method of the above-mentioned laminate comprises the following processes:
  • the prepreg can be one prepreg, or two or more laminates stacked in sequence.
  • the above-mentioned resin composition, prepreg or laminate can be applied to a circuit board, preferably, a circuit board in a 5G communication device.
  • the resin composition includes the following components in parts by weight:
  • the heating rate of lamination was controlled at 3°C/min; the pressure of lamination was kept at 3MPa throughout the whole process; the temperature of the prepreg was controlled at 220°C and kept for 100min.
  • the properties of the prepared copper clad laminates are shown in Table 1.
  • Example 2 The difference between Example 2 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
  • the resin composition includes the following components in parts by weight:
  • Example 3 The difference between Example 3 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
  • the resin composition includes the following components in parts by weight:
  • methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 13 parts of aluminum oxide, 8 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyl trimethylsiloxane, di-tert-butyl 1 part of base dicumyl peroxide (BIPB) initiator.
  • SA9000 methacrylic polyphenylene ether resin
  • BIPB base dicumyl peroxide
  • Example 4 The difference between Example 4 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
  • the resin composition includes the following components in parts by weight:
  • Example 5 The difference between Example 5 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
  • the resin composition includes the following components in parts by weight:
  • methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 21 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyl trimethyl siloxane, di-tert-butyl diisopropyl peroxide 1 part of benzene (BIPB) initiator.
  • SA9000 methacrylic polyphenylene ether resin
  • BIPB benzene
  • the difference between the comparative example and the above-mentioned examples is that the resin composition of the comparative example is not filled with a thermally conductive filler.
  • the resin composition includes the following components in parts by weight:
  • the copper clad laminates of Examples 1-5 can achieve lower dielectric loss and excellent high thermal conductivity at the same time, the flame retardancy reaches UL 94V-0 level, and has a high glass transition temperature , Excellent heat and humidity resistance and heat resistance.
  • 5G communication equipment requires the dielectric loss to be lower than 0.01 and the dielectric constant to be lower than 4.5.
  • the thermal conductivity of the comparative example is about 10 times lower than that of Examples 1-5.
  • other parameters of the comparative example can meet the requirements of 5G communication equipment.
  • other components except the thermal conductive filler The formed resin composition has lower dielectric loss.
  • Examples 1-4 and Example 5 the difference is that Examples 1-4 use two types of thermally conductive fillers, while Example 5 uses one type of thermally conductive filler. Observing the thermal conductivity parameters in Table 1, it can be seen that To: Better thermal conductivity can be obtained by using two thermally conductive fillers.
  • Example 1-2 uses BN and modified fused silica as thermally conductive fillers, and Example 1-2 has a smaller dielectric constant, Below 3.8, the dielectric constant of Example 3 is as high as 4.62, and the dielectric loss of Example 4 is as high as 0.0098. Therefore, preferably, the thermally conductive fillers are BN and modified fused silica.
  • the more preferred embodiment is the embodiment 1-2, and each performance parameter is better.

Abstract

The present application provides a resin composition, a prepreg, a laminated board, a preparation method for the prepreg, a preparation method for the laminated board and an application thereof. The resin composition is prepared from the following components in parts by weight: 20-40 parts of a hydrocarbon resin containing C-C unsaturated bonds, 10-40 parts of a thermal conductive filler, 1-3 parts of a silane coupling agent, and 0.1-10 parts of an initiator; the thermal conductive filler is selected from one, two, or more of silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide. The prepreg and the laminated board are prepared from the resin composition; the prepreg and the laminated board in the present application have high thermal conductivity and low dielectric loss, can be applied to a circuit board, and are particularly suitable for being applied to a circuit board of a high-frequency 5G communication device.

Description

树脂组合物、半固化片、层压片、半固化片的制备方法、层压片的制备方法及其应用Resin composition, prepreg, laminate, preparation method of prepreg, preparation method of laminate and application thereof 【技术领域】【Technical field】
本申请涉及通信材料领域，具体涉及一种树脂组合物、半固化片、层压片、半固化片的制备方法、层压片的制备方法及其应用。The present application relates to the field of communication materials, in particular to a resin composition, a prepreg, a laminate, a method for preparing a prepreg, a method for preparing a laminate, and applications thereof.
【背景技术】【Background technique】
5G通讯技术是移动通讯技术的第5代技术，是为满足2020年后移动互联网和万物互联网业务的需求发展而来。相比于4G通讯技术，5G通讯技术具有更快的信息传输速率、更强的频谱利用效率、更低的延时、更可靠的信息传输和更高的链接密度等特点。5G communication technology is the fifth generation of mobile communication technology, which was developed to meet the needs of mobile Internet and Internet of Everything services after 2020. Compared with 4G communication technology, 5G communication technology has the characteristics of faster information transmission rate, stronger spectrum utilization efficiency, lower delay, more reliable information transmission and higher link density.
在5G天线应用领域，更高的频率以及互联密度就要求所使用的线路板基板具有更稳定的介质常数、更低的介质损耗以及高效的散热性能。对于普遍使用的天线线路板基板，FR-4是目前为止使用最广泛的基板。FR-4是以环氧树脂作基体树脂、以玻璃纤维布为增强材料的一类基板。但是，环氧树脂和玻纤布的导热性均较差，一般通用的FR-4热导率仅为0.25W/(m.K)。因此，其散热性能已不能满足目前大功率器件的散热需求。In the field of 5G antenna applications, higher frequency and interconnection density require the circuit board substrate used to have a more stable dielectric constant, lower dielectric loss and efficient heat dissipation. For the commonly used antenna circuit board substrate, FR-4 is by far the most widely used substrate. FR-4 is a kind of substrate with epoxy resin as matrix resin and glass fiber cloth as reinforcement material. However, the thermal conductivity of epoxy resin and glass fiber cloth is poor, and the general thermal conductivity of FR-4 is only 0.25W/(m.K). Therefore, its heat dissipation performance can no longer meet the heat dissipation requirements of current high-power devices.
解决该问题的其中一种现有方法是制备高导热FR-4，目前制备高导热型FR-4最常用的方法是添加较大比例的导热填料，比如碳化硅(SiC)、氧化铝(Al 2O 3)、氮化铝(AlN)和氮化硼(BN)等，然而填料的增加，又会增加其介质常数，降低电绝缘性能。目前常用的高导热FR-4的介质常数大多为4.5以上，介质损耗在0.01以上。因此如何研发出一种兼具低介质损耗和高导热性能的半固化片及其覆铜板是目前急需解决的技术难题。 One of the existing methods to solve this problem is to prepare high thermal conductivity FR-4. At present, the most common method for preparing high thermal conductivity FR-4 is to add a large proportion of thermally conductive fillers, such as silicon carbide (SiC), aluminum oxide (Al). 2 O 3 ), aluminum nitride (AlN) and boron nitride (BN), etc. However, the increase of fillers will increase its dielectric constant and reduce the electrical insulation performance. At present, the dielectric constant of the commonly used high thermal conductivity FR-4 is mostly above 4.5, and the dielectric loss is above 0.01. Therefore, how to develop a prepreg with both low dielectric loss and high thermal conductivity and its copper clad laminate is a technical problem that needs to be solved urgently at present.
【申请内容】【Contents of application】
本申请的目的之一在于提供一种高导热、低介质损耗的树脂组合物。One of the objectives of the present application is to provide a resin composition with high thermal conductivity and low dielectric loss.
本申请的技术方案如下：The technical solution of this application is as follows:
一种树脂组合物，包括以下重量份数的组份：A resin composition, comprising the following components in parts by weight:
20份-40份的含有C-C不饱和键的碳氢树脂、10份-40份的导热填料、1份-3份的硅烷偶联剂和0.1份-10份的引发剂，所述导热填料选自二氧化硅、碳化硅、三氧化二铝、氮化铝、氧化镁铝、氮化硼或二氧化钛中的一种、两种或多种。20-40 parts of hydrocarbon resin containing CC unsaturated bond, 10-40 parts of thermally conductive filler, 1-3 parts of silane coupling agent and 0.1-10 parts of initiator, the thermally conductive filler is selected from One, two or more selected from silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide.
本申请的目的之二在于提供一种高导热、低介质损耗的半固化片。The second purpose of the present application is to provide a prepreg with high thermal conductivity and low dielectric loss.
本申请的技术方案如下：The technical solution of this application is as follows:
一种半固化片，包括增强材料以及包覆所述增强材料的树脂层，所述树脂层的材料为上述的树脂组合物。A prepreg comprises a reinforcing material and a resin layer covering the reinforcing material, and the material of the resin layer is the above-mentioned resin composition.
本申请的目的之三在于提供上述半固化片的制备方法，技术方案如下：The third purpose of this application is to provide the preparation method of the above-mentioned prepreg, and the technical scheme is as follows:
一种半固化片的制备方法，包括以下过程：A preparation method of a prepreg, comprising the following processes:
将上述的树脂组合物用溶剂溶解制成胶液；The above-mentioned resin composition is dissolved in a solvent to make glue;
将增强材料浸渍在所述胶液中；Impregnating the reinforcing material in the glue;
加热浸渍后的所述增强材料使其半固化，形成所述半固化片。The impregnated reinforcing material is heated and semi-cured to form the prepreg.
本申请的目的之四在于提供一种高导热、低介质损耗的层压板，技术方案如下：The fourth purpose of this application is to provide a laminate with high thermal conductivity and low dielectric loss, and the technical solution is as follows:
一种层压板，包括上述的半固化片和叠加在所述半固化片的单面或双面的导电金属片。A laminate comprising the above-mentioned prepreg and a conductive metal sheet stacked on one or both sides of the prepreg.
本申请的目的之五在于提供上述层压板的制备方法，技术方案如下：The fifth purpose of this application is to provide the preparation method of the above-mentioned laminate, and the technical scheme is as follows:
一种层压板的制备方法，包括以下过程：A preparation method of a laminate, comprising the following processes:
将上述的半固化片的单面或双面覆上导电金属片，压合成型，形成所述层压板。One side or both sides of the above-mentioned prepreg is covered with a conductive metal sheet, and pressed into shape to form the laminate.
本申请的目的之六在于提供上述的树脂组合物、上述的半固化片或上述的层压板在线路板制备领域的应用。The sixth purpose of the present application is to provide the application of the above-mentioned resin composition, the above-mentioned prepreg or the above-mentioned laminate in the field of circuit board preparation.
本申请的有益效果在于：The beneficial effects of this application are:
通过使用含有C-C不饱和键的碳氢树脂，降低树脂的介质损耗，通过使用导热填料，提高树脂的导热性，通过适当的组份配比，得到高导热性同时低介质损耗的树脂组合物。By using the hydrocarbon resin containing C-C unsaturated bonds, the dielectric loss of the resin is reduced, and the thermal conductivity of the resin is improved by using a thermally conductive filler, and a resin composition with high thermal conductivity and low dielectric loss can be obtained by appropriate component ratio.
通过采用高导热、低介质损耗的树脂组合物制备形成半固化片和层压板，能够得到高导热、低介质损耗的半固化片和层压板，从而能够满足高频通信的需求。By using resin compositions with high thermal conductivity and low dielectric loss to prepare and form prepregs and laminates, prepregs and laminates with high thermal conductivity and low dielectric loss can be obtained, so as to meet the needs of high-frequency communications.
【具体实施方式】【detailed description】
下面结合具体实施方式对本申请作进一步说明。The present application will be further described below in conjunction with specific embodiments.
为了得到高导热、低介质损耗的半固化片和覆铜板，本申请从两方面入手，一方面，通过增加导热填料来提高导热性，另一方面，调整树脂的材料，降低树脂的介质损耗，从而降低半固化片整体的介质损耗，满足高频通信设备(5G通信设备)的要求。In order to obtain prepregs and CCLs with high thermal conductivity and low dielectric loss, this application starts from two aspects. On the one hand, the thermal conductivity is improved by adding thermal conductive fillers; The overall dielectric loss of the prepreg meets the requirements of high-frequency communication equipment (5G communication equipment).
降低树脂的介质损耗，除了需要选用介质损耗低的树脂作为反应物外，还需要使各树脂之间能够充分反应，交联固化能力强，材质均匀性高，以及与导热填料的兼容性强等，尽可能的降低半固化片树脂的极性。To reduce the dielectric loss of the resin, in addition to selecting a resin with low dielectric loss as the reactant, it is also necessary to make the resins fully react, strong cross-linking and curing ability, high material uniformity, and strong compatibility with thermally conductive fillers, etc. , to reduce the polarity of the prepreg resin as much as possible.
本申请公开了一种树脂组合物，包括以下重量份数的组份：20份-40份的含有C-C不饱和键的碳氢树脂、10份-40份的导热填料、1份-3份的硅烷偶联剂和0.1份-10份的引发剂，导热填料选自二氧化硅、碳化硅、氧化铝、氮化铝、氧化镁铝、氮化硼或二氧化钛中的一种、两种或多种。含有C-C不饱和键的碳氢树脂具有较低的介质损耗，同时，其高分子链中含有C-C不饱和键的可反应型官能团，其高分子链之间以及其与硅烷偶联剂之间能充分反应，交联成网状结构，得到介质损耗低的半固化片，以及能够和导热填料具有较高的兼容性等。引发剂又称自由基引发剂，指一类容易受热分解成自由基(即初级自由基)的化合物，可用于引发烯类、双烯类单体的自由基聚合和共聚合反应，也可用于不饱和聚酯的交联固化和高分子交联反应，因此，引发剂的引入可以使交联反应更彻底，提高树脂强度，增强树脂材料的均匀性，降低树脂的极性，以及增强树脂与导热填料的兼容性等。The present application discloses a resin composition, comprising the following components in parts by weight: 20-40 parts of a hydrocarbon resin containing CC unsaturated bonds, 10-40 parts of a thermally conductive filler, 1-3 parts of a Silane coupling agent and 0.1 to 10 parts of initiator, thermally conductive filler selected from one, two or more of silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide kind. Hydrocarbon resins containing CC unsaturated bonds have lower dielectric loss, and at the same time, their polymer chains contain reactive functional groups with CC unsaturated bonds, which can interact between the polymer chains and between them and silane coupling agents. Fully reacted and cross-linked into a network structure to obtain a prepreg with low dielectric loss and high compatibility with thermally conductive fillers. Initiator, also known as free radical initiator, refers to a class of compounds that are easily decomposed into free radicals (ie primary free radicals) by heat, which can be used to initiate free radical polymerization and copolymerization of olefinic and diene monomers, and can also be used for The cross-linking curing and polymer cross-linking reaction of unsaturated polyester, therefore, the introduction of the initiator can make the cross-linking reaction more thorough, improve the resin strength, enhance the uniformity of the resin material, reduce the polarity of the resin, and strengthen the resin and the resin. Compatibility of thermally conductive fillers, etc.
二氧化硅优选改性熔融型二氧化硅，改性熔融型二氧化硅为采用硅烷偶联剂改性的二氧化硅，优选的，硅烷偶联剂选自乙烯基三甲基硅氧烷、3-氨丙基三甲基硅氧烷或(2，3-环氧丙氧)丙基三甲基硅氧烷等中的任意 一种，改性熔融型二氧化硅的粒径优选为0.1um-100um，更优选为0.1um-50um。The silica is preferably modified fused silica, and the modified fused silica is a silica modified with a silane coupling agent. Preferably, the silane coupling agent is selected from vinyltrimethylsiloxane, Any one of 3-aminopropyltrimethylsiloxane or (2,3-glycidoxy)propyltrimethylsiloxane, etc., the particle size of the modified fused silica is preferably 0.1 um-100um, more preferably 0.1um-50um.
优选的，含有C-C不饱和键的碳氢树脂选自聚二烯烃类树脂、氰酸脂树脂、苯并环丁烯树脂或用含有C-C不饱和键的官能团封端的聚苯醚树脂中的至少一种，更优选的，选自上述树脂中的两种或多种。Preferably, the hydrocarbon resin containing CC unsaturated bonds is selected from at least one of polydiene resins, cyanate resins, benzocyclobutene resins or polyphenylene ether resins terminated with functional groups containing CC unsaturated bonds more preferably, two or more selected from the above-mentioned resins.
在本具体实施例中，较优的，20份-40份的含有C-C不饱和键的碳氢树脂包括10份-20份的聚二烯烃类树脂和10份-20份的含有C-C不饱和键的官能团封端的聚苯醚树脂。即，树脂组合物包括以下重量份数的组份：10份-20份的聚二烯烃类树脂、10份-20份的用含有C-C不饱和键的官能团封端的聚苯醚树脂、10份-40份的导热填料和1份-3份的硅烷偶联剂。In this specific embodiment, preferably, 20 to 40 parts of hydrocarbon resin containing CC unsaturated bonds include 10 to 20 parts of polydiene resin and 10 to 20 parts of CC unsaturated bond-containing hydrocarbon resin functional group terminated polyphenylene ether resin. That is, the resin composition includes the following components in parts by weight: 10 parts-20 parts of polydiene-based resin, 10 parts-20 parts of polyphenylene ether resin capped with a functional group containing CC unsaturated bonds, 10 parts- 40 parts of thermally conductive filler and 1 part to 3 parts of silane coupling agent.
优选的，含有C-C不饱和键的碳氢树脂采用低分子量的树脂，优选的，其平均分子量为800-5000，更优选的，其平均分子量为1000-3000。Preferably, the hydrocarbon resin containing C-C unsaturated bonds is a low molecular weight resin, preferably, its average molecular weight is 800-5000, more preferably, its average molecular weight is 1000-3000.
优选的，聚二烯烃类树脂的平均分子量为800-5000，更优选的，其平均分子量为1000-3000。用含有C-C不饱和键的官能团封端的聚苯醚树脂的平均分子量为800-5000，更优选的，其平均分子量为1000-3000。Preferably, the average molecular weight of the polydiene resin is 800-5000, and more preferably, the average molecular weight is 1000-3000. The average molecular weight of the polyphenylene ether resin capped with a functional group containing a C-C unsaturated bond is 800-5000, and more preferably, its average molecular weight is 1000-3000.
优选的，硅烷偶联剂选自乙烯基硅烷偶联剂、氨基硅烷偶联剂、丙烯酸基硅烷偶联剂、苯基硅烷偶联剂、环氧基硅烷偶联剂或反应型聚合物类偶联剂中的一种、两种或多种。乙烯基硅烷偶联剂可以为乙烯基三甲基硅氧烷等，氨基硅烷偶联剂可以为3-氨丙基三甲基硅氧烷等，苯基硅烷偶联剂可以为苯基三甲基硅氧烷等，环氧基硅烷偶联剂可以为(2，3-环氧丙氧)丙基三甲基硅氧烷等。Preferably, the silane coupling agent is selected from vinyl silane coupling agents, amino silane coupling agents, acrylic silane coupling agents, phenyl silane coupling agents, epoxy silane coupling agents or reactive polymer-based coupling agents One, two or more of the joint agents. The vinylsilane coupling agent can be vinyltrimethylsiloxane, etc., the aminosilane coupling agent can be 3-aminopropyltrimethylsiloxane, etc., and the phenylsilane coupling agent can be phenyltrimethylsiloxane Siloxane and the like, and the epoxy silane coupling agent may be (2,3-glycidoxy)propyltrimethylsiloxane and the like.
反应型聚合物类偶联剂，例如，可以为毕克化学推出的反应型聚合物类偶联剂BYK-C8003，专用于提高由自由基引发剂引发固化的不饱和聚酯和乙烯基酯树脂玻璃纤维增强材料的机械性能。Reactive polymer-based coupling agent, for example, can be BYK-C8003, a reactive polymer-based coupling agent launched by BYK, which is specially designed to improve unsaturated polyester and vinyl ester resins cured by free radical initiators Mechanical properties of glass fiber reinforced materials.
聚二烯烃类树脂是指分子结构中含有两个或两个以上的双键，并能参与到交联体系的构建，优选的，聚二烯烃类树脂选自聚异戊二烯树脂、聚丁二烯树脂(如曹达化学的B1000、B2000和聚丁二烯)、聚二乙烯基苯树脂、聚双环戊二烯类均聚物树脂、异戊二烯-苯乙烯共聚物树脂、丁二烯- 苯乙烯共聚物树脂、苯乙烯-二乙烯基苯共聚物树脂、苯乙烯-丁二烯-二乙烯基苯共聚物树脂、氢化苯乙烯-丁二烯-二乙烯基苯共聚物树脂、苯乙烯-丁二烯-马来酸酐共聚物树脂或马来酸酐化苯乙烯-丁二烯共聚物树脂中的一种、两种或多种。Polydiene resin refers to the molecular structure containing two or more double bonds, and can participate in the construction of the cross-linking system, preferably, polydiene resin is selected from polyisoprene resin, polybutylene Diene resins (such as Caoda Chemical's B1000, B2000 and polybutadiene), polydivinylbenzene resins, polydicyclopentadiene homopolymer resins, isoprene-styrene copolymer resins, butadiene Styrene-styrene copolymer resin, styrene-divinylbenzene copolymer resin, styrene-butadiene-divinylbenzene copolymer resin, hydrogenated styrene-butadiene-divinylbenzene copolymer resin, One, two or more of styrene-butadiene-maleic anhydride copolymer resins or maleated styrene-butadiene copolymer resins.
优选的，用含有C-C不饱和键的官能团封端的聚苯醚树脂可以为丙烯酸封端的聚苯醚树脂和/或4-乙烯基苯封端的聚苯醚树脂。具体的，丙烯酸封端的聚苯醚树脂可以为甲基丙烯酸聚苯醚树脂，例如，Sabic公司的SA-9000产品。4-乙烯基苯封端的聚苯醚树脂可以为乙烯苄基醚聚苯醚树脂，例如，三菱瓦斯化学公司的OPE-2st产品和OPE-1st产品。Preferably, the polyphenylene ether resin terminated with a functional group containing a C-C unsaturated bond may be an acrylic-terminated polyphenylene ether resin and/or a 4-vinylbenzene-terminated polyphenylene ether resin. Specifically, the acrylic-terminated polyphenylene ether resin may be a methacrylic acid polyphenylene ether resin, for example, SA-9000 product of Sabic Company. The 4-vinylbenzene terminated polyphenylene ether resin may be vinylbenzyl ether polyphenylene ether resin, for example, OPE-2st product and OPE-1st product of Mitsubishi Gas Chemical Corporation.
优选的，引发剂选自过氧化二苯甲酰、过氧化苯甲酸叔丁酯、过氧化二异丙苯、二叔丁基过氧化二异丙基苯、过氧化氢叔丁醇、二异丙苯过氧化氢、过氧化甲乙酮、1，1，3，3-四甲基丁基过氧化氢或特戊基过氧化氢中的一种、两种或者多种。进一步更优选的，引发剂可以为二叔丁基过氧化二异丙基苯(BIPB)和/或过氧化二异丙苯(DCP)。Preferably, the initiator is selected from the group consisting of dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl dicumyl peroxide, tert-butyl hydroperoxide, diisopropyl benzene One, two or more of propylbenzene hydroperoxide, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide or p-amyl hydroperoxide. More preferably, the initiator may be di-tert-butyl dicumyl peroxide (BIPB) and/or dicumyl peroxide (DCP).
优选的，本申请的树脂组合物还包括0.5份-10份的热塑性弹性体材料。热塑性弹性体材料的引入可以增加板材的韧性，提高相容性。Preferably, the resin composition of the present application further comprises 0.5 to 10 parts of thermoplastic elastomer material. The introduction of thermoplastic elastomer material can increase the toughness of the sheet and improve the compatibility.
优选的，采用高分子量的热塑性弹性体材料，优选的，采用高分子量的热塑性弹性体材料和低分子量的含有C-C不饱和键的碳氢树脂配合，能够得到均匀性好、交联度高、强度高、分散性好、兼容性佳的树脂。优选的，热塑性弹性体材料的平均分子量为10000-100000。Preferably, a high molecular weight thermoplastic elastomer material is used. Preferably, a high molecular weight thermoplastic elastomer material is used in combination with a low molecular weight hydrocarbon resin containing CC unsaturated bonds. High resin with good dispersibility and good compatibility. Preferably, the average molecular weight of the thermoplastic elastomer material is 10,000-100,000.
热塑性弹性体材料可以选自苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯共聚物或聚苯醚聚合物中的一种、两种或多种，或者所述热塑性弹性体材料选自苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯共聚物或聚苯醚聚合物对应的氢化树脂中的一种、两种或多种。The thermoplastic elastomeric material may be selected from styrene-butadiene block copolymers, styrene-butadiene-styrene triblock copolymers, styrene-isoprene block copolymers, styrene-isoprene One, two or more of diene-styrene copolymer or polyphenylene ether polymer, or the thermoplastic elastomer material is selected from styrene-butadiene block copolymer, styrene-butadiene -One or two kinds of hydrogenated resin corresponding to styrene triblock copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene copolymer or polyphenylene ether polymer or more.
优选的，本申请的树脂组合物还包括1份-15份的阻燃剂。Preferably, the resin composition of the present application further includes 1 part to 15 parts of a flame retardant.
阻燃剂可以为含磷阻燃剂和/或含溴阻燃剂。The flame retardant may be a phosphorus-containing flame retardant and/or a bromine-containing flame retardant.
具体的，含磷阻燃剂选自磷腈化合物(例如，六苯氧基环磷腈(HPCTP)或大冢化学的SPB-100)、磷酸酯化合物(大八化学的PX-200)、氮磷阻燃剂(例如，巴斯夫公司的聚磷酸三聚氰胺(Melapur 200FF))、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)或二乙基磷酸铝阻燃剂(OP-935，OP-945)等中的一种、两种或多种。Specifically, the phosphorus-containing flame retardant is selected from phosphazene compounds (for example, hexaphenoxy cyclophosphazene (HPCTP) or SPB-100 of Otsuka Chemical), phosphoric acid ester compounds (PX-200 of Daihachi Chemical), nitrogen Phosphorus flame retardants (for example, melamine polyphosphate (Melapur 200FF) from BASF), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), or diethylaluminum phosphate One, two or more of flame retardants (OP-935, OP-945), etc.
具体的，含溴阻燃剂可以选自十溴二苯醚、十溴二苯乙烷、四溴双酚A或十溴环十二烷等中的一种、两种或多种。Specifically, the bromine-containing flame retardant may be selected from one, two or more of decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, decabromcyclododecane, and the like.
在本具体实施例中，优选的，树脂组合物包括以下重量份数的组份：In this specific embodiment, preferably, the resin composition includes the following components by weight:
聚二烯烃类树脂10份-20份、用含有C-C不饱和键的官能团封端的聚苯醚树脂10份-20份、热塑性弹性体材料0.5份-3份、导热填料10份-30份、硅烷偶联剂1份-2份、引发剂0.5份-3份和阻燃剂1份-6份。具体的，聚二烯烃类树脂可以为10份、12份、15份或20份，用含有C-C不饱和键的官能团封端的聚苯醚树脂可以为10份、12份、15份或20份，热塑性弹性体材料可以为0.5份、1份、2份或3份，导热填料可以为10份、15份、20份、25份、或30份，硅烷偶联剂可以为1份、1.5份或2份，引发剂可以为0.5份、1份、1.5份、2份、2.5份或3份，阻燃剂可以为1份、3.5份或6份。10-20 parts of polydiene resin, 10-20 parts of polyphenylene ether resin capped with functional group containing CC unsaturated bond, 0.5-3 parts of thermoplastic elastomer material, 10-30 parts of thermally conductive filler, silane 1-2 parts of coupling agent, 0.5-3 parts of initiator and 1-6 parts of flame retardant. Specifically, the polydiene resin can be 10 parts, 12 parts, 15 parts or 20 parts, and the polyphenylene ether resin capped with the functional group containing CC unsaturated bond can be 10 parts, 12 parts, 15 parts or 20 parts, The thermoplastic elastomer material can be 0.5 parts, 1 part, 2 parts or 3 parts, the thermally conductive filler can be 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts, and the silane coupling agent can be 1 part, 1.5 parts or 2 parts, the initiator can be 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, and the flame retardant can be 1 part, 3.5 parts or 6 parts.
本申请还公开了一种半固化片，其包括增强材料以及包覆增强材料的树脂层，树脂层的材料为上述的树脂组合物。The present application also discloses a prepreg, which includes a reinforcing material and a resin layer covering the reinforcing material, and the material of the resin layer is the above-mentioned resin composition.
优选的，增强材料的重量份数为20份-40份，树脂层的重量份数为60份-80份。Preferably, the weight part of the reinforcing material is 20-40 parts, and the weight part of the resin layer is 60-80 parts.
优选的，增强材料为玻璃纤维布。更优选的，增强材料为电子级玻璃纤维布，电子级玻璃纤维布的重量份数可以为20份、30份或40份。Preferably, the reinforcing material is glass fiber cloth. More preferably, the reinforcing material is electronic-grade glass fiber cloth, and the weight portion of the electronic-grade glass fiber cloth can be 20 parts, 30 parts or 40 parts.
上述半固化片的制备方法，包括以下过程：The preparation method of above-mentioned prepreg comprises the following process:
将上述树脂组合物用溶剂溶解制成胶液，然后将增强材料浸渍在胶液中，将浸渍后的增强材料加热使其半固化，形成半固化片。The above-mentioned resin composition is dissolved in a solvent to form a glue solution, the reinforcing material is then immersed in the glue solution, and the impregnated reinforcing material is heated and semi-cured to form a prepreg.
本申请还公开了一种层压板，包括上述的半固化片和叠加在半固化片的单面或双面的导电金属片。半固化片可以是一张，也可以是两张或两张 以上的依次叠加的半固化片。The present application also discloses a laminate, comprising the above-mentioned prepreg and a conductive metal sheet stacked on one or both sides of the prepreg. The prepreg may be one sheet, or two or more prepregs stacked in sequence.
优选的，导电金属片为铜箔。Preferably, the conductive metal sheet is copper foil.
上述层压板的制备方法，包括以下过程：The preparation method of the above-mentioned laminate comprises the following processes:
将上述的半固化片的单面或双面覆上导电金属片，然后层压成型，形成层压板。半固化片可以是一张半固化片，也可以是两张或两张以上的层压板依次叠加。One or both sides of the above-mentioned prepreg are covered with a conductive metal sheet, and then laminated to form a laminate. The prepreg can be one prepreg, or two or more laminates stacked in sequence.
上述的树脂组合物、半固化片或层压板可以被应用在线路板上，优选的，被应用在5G通信设备中的线路板上。The above-mentioned resin composition, prepreg or laminate can be applied to a circuit board, preferably, a circuit board in a 5G communication device.
具体实施例。specific examples.
实施例1Example 1
树脂组合物包括以下重量份数的组份：The resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)12份、丁二烯-苯乙烯共聚物树脂10份、聚丁二烯树脂2份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、氮化硼(BN)13份、改性熔融型二氧化硅8份、十溴二苯醚阻燃剂3.5份、乙烯基三甲基硅氧烷1.5份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1份。12 parts of methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 13 parts of boron nitride (BN), 8 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyltrimethylsiloxane, 2 parts of 1 part of tert-butyl dicumyl peroxide (BIPB) initiator.
制备半固化片：To prepare the prepreg:
1)按照上述重量份数称取各组份。1) Weigh each component according to the above parts by weight.
2)将甲基丙烯酸聚苯醚树脂树脂放入混胶瓶中，再向混胶瓶中加入溶剂甲苯32份和丁酮17份，搅拌直至甲基丙烯酸聚苯醚树脂树脂完全溶解。2) Put the methacrylic acid polyphenylene ether resin resin into the mixing bottle, and then add 32 parts of solvent toluene and 17 parts of methyl ethyl ketone to the mixing bottle, and stir until the methacrylic acid polyphenylene ether resin resin is completely dissolved.
3)再向混胶瓶中加入丁二烯-苯乙烯共聚物树脂、聚丁二烯树脂和溶解后的SBS树脂(10％-15％固含量)，搅拌至混合均匀。3) Add butadiene-styrene copolymer resin, polybutadiene resin and dissolved SBS resin (10%-15% solid content) into the mixing bottle, and stir until the mixture is uniform.
4)再向混胶瓶中加入BN、二氧化硅、BIPB引发剂、乙烯基三甲基硅氧烷，搅拌至混合均匀。4) Add BN, silicon dioxide, BIPB initiator and vinyl trimethyl siloxane to the mixing bottle, and stir until the mixture is uniform.
5)将混合后的混合物乳化分散(转速为2000r/min-4000r/min)制得胶液，调整胶液的固含量为55％。5) Emulsify and disperse the mixed mixture (rotation speed is 2000r/min-4000r/min) to obtain a glue solution, and adjust the solid content of the glue solution to 55%.
6)将30重量份的电子级玻璃纤维布在上述胶液中浸渍后，经过特定 间隙的滚轴后，在140℃-170℃的高温烘箱中烘烤2min-8min，即可制得半固化片。6) After immersing 30 parts by weight of electronic-grade glass fiber cloth in the above glue solution, after passing through a roller with a specific gap, bake it in a high-temperature oven at 140°C-170°C for 2min-8min to obtain a prepreg.
制备覆铜层压板：To prepare the copper clad laminate:
采用4张上述半固化片叠放整齐，双面覆上18um的铜箔，置于真空热油压机中，进行压合成型，压合程序如下：Four sheets of the above-mentioned prepregs are stacked neatly, covered with 18um copper foil on both sides, and placed in a vacuum hot oil press for pressing and forming. The pressing procedure is as follows:
层压的升温速率控制在3℃/min；层压的压力全程保持3MPa；控制半固化片的温度在220℃，并保温100min。制得的覆铜层压板的性能如表1所示。The heating rate of lamination was controlled at 3°C/min; the pressure of lamination was kept at 3MPa throughout the whole process; the temperature of the prepreg was controlled at 220°C and kept for 100min. The properties of the prepared copper clad laminates are shown in Table 1.
实施例2Example 2
实施例2与实施例1的不同之处，仅在于树脂组合物不同，半固化片和覆铜层压板的制备方法和参数均与实施例1相同。The difference between Example 2 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
在本实施例中，树脂组合物包括以下重量份数的组份：In this embodiment, the resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)12份、丁二烯-苯乙烯共聚物树脂10份、聚丁二烯树脂2份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、氮化硼(BN)8份、改性熔融型二氧化硅13份、十溴二苯醚阻燃剂3.5份、乙烯基三甲基硅氧烷1.5份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1份。12 parts of methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 8 parts of boron nitride (BN), 13 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyltrimethylsiloxane, 2 parts 1 part of tert-butyl dicumyl peroxide (BIPB) initiator.
实施例3Example 3
实施例3与实施例1的不同之处，仅在于树脂组合物不同，半固化片和覆铜层压板的制备方法和参数均与实施例1相同。The difference between Example 3 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
在本实施例中，树脂组合物包括以下重量份数的组份：In this embodiment, the resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)12份、丁二烯-苯乙烯共聚物树脂10份、聚丁二烯树脂2份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、三氧化二铝13份、改性熔融型二氧化硅8份、十溴二苯醚阻燃剂3.5份、乙烯基三甲基硅氧烷1.5份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1份。12 parts of methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 13 parts of aluminum oxide, 8 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyl trimethylsiloxane, di-tert-butyl 1 part of base dicumyl peroxide (BIPB) initiator.
实施例4Example 4
实施例4与实施例1的不同之处，仅在于树脂组合物不同，半固化片和覆铜层压板的制备方法和参数均与实施例1相同。The difference between Example 4 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
在本实施例中，树脂组合物包括以下重量份数的组份：In this embodiment, the resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)12份、丁二烯-苯乙烯共聚物树脂10份、聚丁二烯树脂2份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、氧化镁铝13份、改性熔融型二氧化硅8份、十溴二苯醚阻燃剂3.5份、乙烯基三甲基硅氧烷1.5份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1份。12 parts of methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part (SBS resin), 13 parts of magnesium aluminum oxide, 8 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyl trimethyl siloxane, di-tert-butyl 1 part of dicumyl peroxide (BIPB) initiator.
实施例5Example 5
实施例5与实施例1的不同之处，仅在于树脂组合物不同，半固化片和覆铜层压板的制备方法和参数均与实施例1相同。The difference between Example 5 and Example 1 is that the resin composition is different, and the preparation methods and parameters of the prepreg and the copper-clad laminate are the same as those of Example 1.
在本实施例中，树脂组合物包括以下重量份数的组份：In this embodiment, the resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)12份、丁二烯-苯乙烯共聚物树脂10份、聚丁二烯树脂2份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、改性熔融型二氧化硅21份、十溴二苯醚阻燃剂3.5份、乙烯基三甲基硅氧烷1.5份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1份。12 parts of methacrylic polyphenylene ether resin (trade name SA9000), 10 parts of butadiene-styrene copolymer resin, 2 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of SBS resin, 21 parts of modified fused silica, 3.5 parts of decabromodiphenyl ether flame retardant, 1.5 parts of vinyl trimethyl siloxane, di-tert-butyl diisopropyl peroxide 1 part of benzene (BIPB) initiator.
对比例Comparative ratio
对比例与上述实施例的不同之处在于，对比例的树脂组合物中未填加导热填料。The difference between the comparative example and the above-mentioned examples is that the resin composition of the comparative example is not filled with a thermally conductive filler.
在对比例中，树脂组合物包括以下重量份数的组份：In the comparative example, the resin composition includes the following components in parts by weight:
甲基丙烯酸聚苯醚树脂树脂(商品牌号为SA9000)15份、丁二烯-苯乙烯共聚物树脂13份、聚丁二烯树脂2.5份、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS树脂)1份、十溴二苯醚阻燃剂4份、乙烯基三甲基硅氧烷 2份、二叔丁基过氧化二异丙基苯(BIPB)引发剂1.5份。采用甲苯38份和丁酮23份溶解上述树脂组合物，制成固含量为55％的胶液。15 parts of methacrylic acid polyphenylene ether resin (trade name SA9000), 13 parts of butadiene-styrene copolymer resin, 2.5 parts of polybutadiene resin, styrene-butadiene-styrene triblock copolymer 1 part of compound (SBS resin), 4 parts of decabromodiphenyl ether flame retardant, 2 parts of vinyl trimethicone, and 1.5 parts of di-tert-butyl dicumyl peroxide (BIPB) initiator. 38 parts of toluene and 23 parts of methyl ethyl ketone were used to dissolve the above resin composition to prepare a glue solution with a solid content of 55%.
对上述实施例1-5和对比例制得的覆铜层压板进行剥离强度、玻璃化转化温度、导热系数、介质常数、介质损耗、阻燃性、耐热性和吸水率的性能测试，具体测试方法和性能参数见表1。The performance tests of peel strength, glass transition temperature, thermal conductivity, dielectric constant, dielectric loss, flame retardancy, heat resistance and water absorption were performed on the copper clad laminates prepared in the above-mentioned Examples 1-5 and Comparative Examples. The test methods and performance parameters are shown in Table 1.
表1：各实施例和对比例的覆铜箔层压板性能Table 1: Copper Clad Laminate Properties of Examples and Comparative Examples
Figure PCTCN2020103774-appb-000001
Figure PCTCN2020103774-appb-000001
Figure PCTCN2020103774-appb-000002
Figure PCTCN2020103774-appb-000002
从上述表1可以看到：实施例1-5的覆铜层压板可以同时达到较低介质损耗和优异的高导热性，阻燃性达到UL 94V-0等级，具有较高的玻璃化转变温度，优良的耐湿热性和耐热性。通常5G通信设备要求介质损耗低于0.01，介质常数低于4.5。It can be seen from the above Table 1 that the copper clad laminates of Examples 1-5 can achieve lower dielectric loss and excellent high thermal conductivity at the same time, the flame retardancy reaches UL 94V-0 level, and has a high glass transition temperature , Excellent heat and humidity resistance and heat resistance. Generally, 5G communication equipment requires the dielectric loss to be lower than 0.01 and the dielectric constant to be lower than 4.5.
通过对比例可以看到：对比例的导热系数相比实施例1-5，低约10倍，但是，对比例的其它参数能够满足5G通信设备要求，可见，由除导热填料外的其它组份构成的树脂组合物具有较低的介质损耗。It can be seen from the comparative example that the thermal conductivity of the comparative example is about 10 times lower than that of Examples 1-5. However, other parameters of the comparative example can meet the requirements of 5G communication equipment. It can be seen that other components except the thermal conductive filler The formed resin composition has lower dielectric loss.
将实施例1-4和实施例5相比，区别在于，实施例1-4采用了两种导热填料，而实施例5采用了一种导热填料，观察表1中的导热系数参数，可以看到：采用两种导热填料可以得到更好的导热性能。Comparing Examples 1-4 and Example 5, the difference is that Examples 1-4 use two types of thermally conductive fillers, while Example 5 uses one type of thermally conductive filler. Observing the thermal conductivity parameters in Table 1, it can be seen that To: Better thermal conductivity can be obtained by using two thermally conductive fillers.
将实施例1-2和实施例3-4相比，区别在于，实施例1-2采用了BN和改性熔融型二氧化硅为导热填料，实施例1-2具有更小的介质常数，低于3.8，而实施例3的介质常数高达4.62，实施例4的介质损耗高达0.0098，因此，优选的，导热填料为BN和改性熔融型二氧化硅。Comparing Example 1-2 and Example 3-4, the difference is that Example 1-2 uses BN and modified fused silica as thermally conductive fillers, and Example 1-2 has a smaller dielectric constant, Below 3.8, the dielectric constant of Example 3 is as high as 4.62, and the dielectric loss of Example 4 is as high as 0.0098. Therefore, preferably, the thermally conductive fillers are BN and modified fused silica.
在实施例1-5中，较优选的实施例为实施例1-2，各项性能参数均较优。In the embodiment 1-5, the more preferred embodiment is the embodiment 1-2, and each performance parameter is better.
以上所述的仅是本申请的实施方式，在此应当指出，对于本领域的普通技术人员来说，在不脱离本申请创造构思的前提下，还可以做出改进，但这些均属于本申请的保护范围。The above are only the embodiments of the present application. It should be pointed out that for those of ordinary skill in the art, improvements can be made without departing from the creative concept of the present application, but these belong to the present application. scope of protection.

Claims (20)

  1. 一种树脂组合物，其特征在于，包括以下重量份数的组份：A resin composition, characterized in that, comprises the following components by weight:
    20份-40份的含有C-C不饱和键的碳氢树脂、10份-40份的导热填料、1份-3份的硅烷偶联剂和0.1份-10份的引发剂；20-40 parts of hydrocarbon resin containing C-C unsaturated bond, 10-40 parts of thermally conductive filler, 1-3 parts of silane coupling agent and 0.1-10 parts of initiator;
    所述导热填料选自二氧化硅、碳化硅、三氧化二铝、氮化铝、氧化镁铝、氮化硼或二氧化钛中的一种、两种或多种。The thermally conductive filler is selected from one, two or more of silicon dioxide, silicon carbide, aluminum oxide, aluminum nitride, magnesium aluminum oxide, boron nitride or titanium dioxide.
  2. 根据权利要求1所述的树脂组合物，其特征在于，所述含有C-C不饱和键的碳氢树脂选自聚二烯烃类树脂、氰酸脂树脂、苯并环丁烯树脂或用含有C-C不饱和键的官能团封端的聚苯醚树脂中的一种、两种或多种。The resin composition according to claim 1, wherein the hydrocarbon resin containing CC unsaturated bonds is selected from the group consisting of polydiene resins, cyanate resins, benzocyclobutene resins or resins containing CC One, two or more of polyphenylene ether resins terminated with functional groups of saturated bonds.
  3. 根据权利要求2所述的树脂组合物，其特征在于，所述20份-40份的含有C-C不饱和键的碳氢树脂为10份-20份的所述聚二烯烃类树脂和10份-20份的所述用含有C-C不饱和键的官能团封端的聚苯醚树脂。The resin composition according to claim 2, wherein the 20 parts-40 parts of the hydrocarbon resin containing CC unsaturated bonds are 10 parts-20 parts of the polydiene resin and 10 parts- 20 parts of the polyphenylene ether resin terminated with a functional group containing a CC unsaturated bond.
  4. 根据权利要求3所述的树脂组合物，其特征在于，所述聚二烯烃类树脂的平均分子量为800-5000，所述用含有C-C不饱和键的官能团封端的聚苯醚树脂的平均分子量为800-5000。The resin composition according to claim 3, wherein the average molecular weight of the polydiene resin is 800-5000, and the average molecular weight of the polyphenylene ether resin terminated with a functional group containing a CC unsaturated bond is 800-5000.
  5. 根据权利要求2或3或4所述的树脂组合物，其特征在于，所述硅烷偶联剂选自乙烯基硅烷偶联剂、氨基硅烷偶联剂、丙烯酸基硅烷偶联剂、苯基硅烷偶联剂、环氧基硅烷偶联剂或反应型聚合物类偶联剂中的一种、两种或多种；The resin composition according to claim 2, 3 or 4, wherein the silane coupling agent is selected from the group consisting of vinyl silane coupling agent, amino silane coupling agent, acryl silane coupling agent, phenyl silane One, two or more of coupling agents, epoxy silane coupling agents or reactive polymer coupling agents;
    所述聚二烯烃类树脂选自聚异戊二烯树脂、聚丁二烯树脂、聚二乙烯基苯树脂、聚双环戊二烯类均聚物树脂、异戊二烯-苯乙烯共聚物树脂、丁二烯-苯乙烯共聚物树脂、苯乙烯-二乙烯基苯共聚物树脂、苯乙烯-丁二烯-二乙烯基苯共聚物树脂、氢化苯乙烯-丁二烯-二乙烯基苯共聚物树脂、苯乙烯-丁二烯-马来酸酐共聚物树脂或马来酸酐化苯乙烯-丁二烯共聚物树脂中的一种、两种或多种；The polydiene resin is selected from polyisoprene resin, polybutadiene resin, polydivinylbenzene resin, polydicyclopentadiene homopolymer resin, isoprene-styrene copolymer resin , butadiene-styrene copolymer resin, styrene-divinylbenzene copolymer resin, styrene-butadiene-divinylbenzene copolymer resin, hydrogenated styrene-butadiene-divinylbenzene copolymer one, two or more of styrene-butadiene-maleic anhydride copolymer resin or maleic anhydride-based styrene-butadiene copolymer resin;
    所述用含有C-C不饱和键的官能团封端的聚苯醚树脂为丙烯酸封端的聚苯醚树脂和/或4-乙烯基苯封端的聚苯醚树脂；The polyphenylene ether resin terminated with a functional group containing a C-C unsaturated bond is an acrylic-terminated polyphenylene ether resin and/or a 4-vinylbenzene-terminated polyphenylene ether resin;
    所述引发剂选自过氧化二苯甲酰、过氧化苯甲酸叔丁酯、过氧化二异丙苯、二叔丁基过氧化二异丙基苯、过氧化氢叔丁醇、二异丙苯过氧化氢、过氧化甲乙酮、1，1，3，3-四甲基丁基过氧化氢或特戊基过氧化氢中的一种、两种或者多种。The initiator is selected from dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl dicumyl peroxide, tert-butyl hydroperoxide, diisopropyl One, two or more of benzene hydroperoxide, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide or p-amyl hydroperoxide.
  6. 根据权利要求1-4任意一项所述的树脂组合物，其特征在于，还包括0.5份-10份的热塑性弹性体材料。The resin composition according to any one of claims 1-4, characterized in that, further comprising 0.5 to 10 parts of thermoplastic elastomer material.
  7. 根据权利要求6所述的树脂组合物，其特征在于，所述热塑性弹性体材料的平均分子量为10000-100000。The resin composition according to claim 6, wherein the average molecular weight of the thermoplastic elastomer material is 10,000-100,000.
  8. 根据权利要求7所述的树脂组合物，其特征在于，所述热塑性弹性体材料选自苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯共聚物或聚苯醚聚合物中的一种、两种或多种，或者所述热塑性弹性体材料选自苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯共聚物或聚苯醚聚合物对应的氢化树脂中的一种、两种或多种。The resin composition according to claim 7, wherein the thermoplastic elastomer material is selected from the group consisting of styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, benzene One, two or more of ethylene-isoprene block copolymer, styrene-isoprene-styrene copolymer or polyphenylene ether polymer, or the thermoplastic elastomer material is selected from benzene Ethylene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene copolymer or One, two or more of the hydrogenated resins corresponding to the polyphenylene ether polymer.
  9. 根据权利要求6所述的树脂组合物，其特征在于，还包括阻燃剂1份-15份。The resin composition according to claim 6, further comprising 1 to 15 parts of a flame retardant.
  10. 根据权利要求9所述的树脂组合物，其特征在于，所述阻燃剂为含磷阻燃剂和/或含溴阻燃剂。The resin composition according to claim 9, wherein the flame retardant is a phosphorus-containing flame retardant and/or a bromine-containing flame retardant.
  11. 根据权利要求10所述的树脂组合物，其特征在于，The resin composition according to claim 10, wherein
    所述含磷阻燃剂选自磷腈化合物、磷酸酯化合物、氮磷阻燃剂、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或二乙基磷酸铝阻燃剂中的一种、两种或多种；The phosphorus-containing flame retardant is selected from phosphazene compounds, phosphoric acid ester compounds, nitrogen phosphorus flame retardants, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or diethylphosphoric acid One, two or more of aluminum flame retardants;
    所述含溴阻燃剂选自十溴二苯醚、十溴二苯乙烷、四溴双酚A或十溴环十二烷中的一种、两种或多种。The bromine-containing flame retardant is selected from one, two or more of decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A or decabromcyclododecane.
  12. 根据权利要求9所述的树脂组合物，其特征在于，The resin composition according to claim 9, wherein,
    所述聚二烯烃类树脂的重量份数为10份-20份；The parts by weight of the polydiene resin are 10 parts to 20 parts;
    所述用含有C-C不饱和键的官能团封端的聚苯醚树脂的重量份数为10 份-20份；The parts by weight of the polyphenylene ether resin end-capped with a functional group containing a C-C unsaturated bond are 10 parts to 20 parts;
    所述热塑性弹性体材料的重量份数为0.5份-3份；The parts by weight of the thermoplastic elastomer material are 0.5 to 3 parts;
    所述导热填料的重量份数为10份-30份；The parts by weight of the thermally conductive filler are 10 to 30 parts;
    所述硅烷偶联剂的重量份数为1份-2份；The parts by weight of the silane coupling agent are 1 part to 2 parts;
    所述引发剂的重量份数为0.5份-3份；The weight part of the initiator is 0.5 part-3 part;
    所述阻燃剂的重量份数为1份-6份。The weight part of the flame retardant is 1 part to 6 parts.
  13. 一种半固化片，其特征在于，包括增强材料以及包覆所述增强材料的树脂层，所述树脂层的材料为权利要求1-12任意一项所述的树脂组合物。A prepreg, characterized in that it comprises a reinforcing material and a resin layer covering the reinforcing material, and the material of the resin layer is the resin composition according to any one of claims 1-12.
  14. 根据权利要求13所述的半固化片，其特征在于，所述增强材料的重量份数为20份-40份，所述树脂层的重量份数为60份-80份。The prepreg according to claim 13, characterized in that, the weight part of the reinforcing material is 20-40 parts, and the weight part of the resin layer is 60-80 parts.
  15. 根据权利要求13或14所述的半固化片，其特征在于，所述增强材料为玻璃纤维布。The prepreg according to claim 13 or 14, wherein the reinforcing material is glass fiber cloth.
  16. 一种半固化片的制备方法，其特征在于，包括以下过程：A method for preparing a prepreg, comprising the following steps:
    将权利要求1-12任意一项所述的树脂组合物用溶剂溶解制成胶液；Dissolving the resin composition according to any one of claims 1-12 in a solvent makes glue;
    将增强材料浸渍在所述胶液中；Impregnating the reinforcing material in the glue;
    加热浸渍后的所述增强材料使其半固化，形成所述半固化片。The impregnated reinforcing material is heated and semi-cured to form the prepreg.
  17. 一种层压板，其特征在于，包括如权利要求13-15任意一项所述的半固化片和叠加在所述半固化片的单面或双面的导电金属片。A laminate, characterized in that it comprises the prepreg according to any one of claims 13-15 and a conductive metal sheet stacked on one or both sides of the prepreg.
  18. 根据权利要求17所述的层压板，其特征在于，所述导电金属片为铜箔。The laminate according to claim 17, wherein the conductive metal sheet is copper foil.
  19. 一种层压板的制备方法，其特征在于，包括以下过程：A method for preparing a laminate, comprising the following steps:
    将如权利要求13-15任意一项所述的半固化片的单面或双面覆上导电金属片，压合成型，形成所述层压板。One or both sides of the prepreg according to any one of claims 13 to 15 are covered with a conductive metal sheet, and pressed into shape to form the laminate.
  20. 权利要求1-12任意一项所述的树脂组合物、权利要求13-15任意一项所述的半固化片或权利要求17-18任意一项所述的层压板在线路板制备领域的应用。Application of the resin composition according to any one of claims 1-12, the prepreg according to any one of claims 13-15 or the laminate according to any one of claims 17-18 in the field of circuit board preparation.
PCT/CN2020/103774 2020-06-30 2020-07-23 Resin composition, prepreg, laminated board, preparation method for prepreg, preparation method for laminated board and application thereof WO2022000629A1 (en)

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