WO2021007814A1 - 粘接片、其制备方法及使用该粘接片的覆铜层压板 - Google Patents

粘接片、其制备方法及使用该粘接片的覆铜层压板 Download PDF

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Publication number
WO2021007814A1
WO2021007814A1 PCT/CN2019/096387 CN2019096387W WO2021007814A1 WO 2021007814 A1 WO2021007814 A1 WO 2021007814A1 CN 2019096387 W CN2019096387 W CN 2019096387W WO 2021007814 A1 WO2021007814 A1 WO 2021007814A1
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Prior art keywords
parts
adhesive sheet
sheet according
adhesive piece
polyphenylene ether
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PCT/CN2019/096387
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English (en)
French (fr)
Inventor
王宏远
王和志
张翼蓝
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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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Application filed by 瑞声声学科技(深圳)有限公司, 瑞声科技（南京）有限公司 filed Critical 瑞声声学科技(深圳)有限公司
Priority to PCT/CN2019/096387 priority Critical patent/WO2021007814A1/zh
Priority to CN201910648158.2A priority patent/CN110408332A/zh
Publication of WO2021007814A1 publication Critical patent/WO2021007814A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • This application relates to the technical field of adhesive sheets, in particular to an adhesive sheet, a preparation method thereof, and a copper clad laminate using the adhesive sheet.
  • the adhesive sheet has electrical, thermal and mechanical properties (including low dielectric constant and low dissipation factor) comparable to the materials of each layer.
  • the existing adhesive sheet is mainly prepared by blending modified polyphenylene ether and polyolefin. Because the structure of polyphenylene ether is quite different from that of commonly used polyolefins, it is easy to separate after curing, resulting in less polyolefin addition. Therefore, the manufacturing cost is relatively high, and the prepared adhesive sheet also has the disadvantages of poor heat resistance and poor fluidity.
  • This application mainly solves the technical problems of poor heat resistance, poor fluidity, and high manufacturing cost of the existing adhesive sheet.
  • This application provides an adhesive sheet, a preparation method thereof and a copper clad laminate using the adhesive sheet.
  • This application provides an adhesive sheet, which includes the following components in parts by mass: 25 to 65 parts of matrix resin, 20 to 60 parts of fiber reinforcement, 10 to 40 parts of filler, and 0 to 15 parts of flame retardant, ,
  • the base resin comprises the following components in parts by mass: 20 to 70 parts of modified polyphenylene ether, 30 to 70 parts of polydiene polymer and 0 to 5 parts of initiator.
  • the modified polyphenylene ether is a low-molecular-weight polyphenylene ether capped with a reactive functional group, and its molecular weight is 800-6000, preferably 900-4000.
  • the low molecular weight polyphenylene ether includes a plurality of structural units of the following structures:
  • R 1 , R 2 , R 3 and R 4 independently represent any one of hydrogen, an alkyl group or an ester group.
  • the reactive functional group of the low molecular weight polyphenylene ether includes any one of an unsaturated ester and an unsaturated olefin, and the structural formula of the reactive functional group is:
  • X is any one of -C 6 H 4 -, -CH 2 -, -O-, -COO-, and R is any one of -CH 3 , -C 6 H 5 or H.
  • the polydiene polymer includes dicyclopentadiene polymer, polydivinylbenzene, poly1,2butadiene, styrene/divinylbenzene copolymer, styrene/butadiene Either a copolymer or a styrene/isoprene copolymer.
  • the molecular weight of the polydiene polymer is 3,000 to 180,000.
  • the initiator is a free radical initiator, which includes any one of peroxide initiators, azo initiators and dicumin.
  • the fiber reinforcement is one or more of glass fiber, quartz fiber and organic fiber.
  • the filler is an inorganic filler whose surface has been modified by a coupling agent, and the inorganic filler includes one or more of silica, titanium dioxide, and organic polymer microspheres.
  • the flame retardant includes one or more of phosphorus-containing flame retardants, nitrogen-containing flame retardants and bromine-containing flame retardants.
  • the thickness of the adhesive sheet is 20-200 ⁇ m.
  • This application also provides a method for preparing a sound-absorbing material.
  • the following components are weighed according to the mass parts: 25 to 65 parts of matrix resin, 20 to 60 parts of fiber reinforcement, 10 to 40 parts of filler, and 0 to 0 parts of flame retardant. 15 copies;
  • the impregnated fiber reinforcement is dried and cut to obtain an adhesive sheet.
  • the present application also provides a copper-clad laminate, which is laminated with the above-mentioned adhesive sheet.
  • the adhesive sheet of the present application Compared with related technologies, the adhesive sheet of the present application, its preparation method and the copper clad laminate using the adhesive sheet have the following beneficial effects:
  • the use of adhesive sheets in copper clad laminates solves the problems of defects and bursts in the processing of multilayer copper clad laminates caused by insufficient heat resistance of the adhesive sheets, and can ensure that the multilayer laminate
  • the full flow and filling of the resin during the preparation of the copper laminate ensures the quality and batch stability of the product, and the adhesive sheet has a lower dielectric loss after curing, which can meet the needs of the future high-frequency field.
  • the application provides an adhesive sheet, which comprises the following components in parts by mass: 25 to 65 parts of matrix resin, 20 to 60 parts of fiber reinforcement, 10 to 40 parts of filler, and 0 to 15 parts of flame retardant.
  • the base resin includes 20 to 70 parts of modified polyphenylene ether, 30 to 70 parts of polydiene polymer, and 0 to 5 parts of initiator. Because polyphenylene ether has the disadvantages of high melting point, poor fluidity, and high material cost, this application adds polydiene polymer to polyphenylene ether and modifies polyphenylene ether under the action of initiators, which can prepare and process A matrix resin with good performance, low cost, excellent dielectric properties and heat resistance of the cured product, low CTE and low water absorption rate.
  • polydiene polymers to modify polyphenylene ether, without losing the low dielectric properties and heat resistance of PPO, while improving the toughness of the polymer, it can also effectively reduce the cost of polyphenylene ether resin, and polydiene
  • the chemical structure of these polymers is similar to that of polyphenylene ether. Compared with other olefins, the blending of polydiene polymers and PPO is not prone to phase separation.
  • the modified polyphenylene ether is a low-molecular-weight polyphenylene ether capped with a reactive functional group, and its molecular weight is 800-6000, preferably 900-4000.
  • the low molecular weight polyphenylene ether includes a plurality of structural units of the following structures:
  • each of R 1 , R 2 , R 3 and R 4 independently represents any one of hydrogen, an alkyl group, or an ester group.
  • the reactive functional groups of the low-molecular-weight polyphenylene ether include, but are not limited to, unsaturated esters and unsaturated olefins.
  • the structural formula of the reactive functional groups is:
  • X is any one of -C 6 H 4 -, -CH 2 -, -O-, -COO-, and R is any one of -CH 3 , -C 6 H 5 or H.
  • the polydiene polymers used for polyphenylene ether modification include but are not limited to dicyclopentadiene polymers, polydivinylbenzene, poly1,2butadiene, styrene/divinylbenzene copolymers Any one of styrene/butadiene copolymer and styrene/isoprene copolymer.
  • the molecular weight of the polydiene polymer is 3,000 to 180,000.
  • the initiator is a free radical initiator, which includes, but is not limited to, any one of peroxide initiators, azo initiators, and dicumin.
  • the fiber reinforcement is one or more of glass fiber, quartz fiber and organic fiber, and the use of the fiber reinforcement can make the adhesive sheet have relatively high mechanical strength.
  • the filler is an inorganic filler whose surface is modified and modified by a coupling agent, and the inorganic filler includes but is not limited to silica, titanium dioxide and organic polymer microspheres.
  • the filler particle size is 0.1-10 ⁇ m, preferably 0.1-4 ⁇ m.
  • the particle size of the filler should be appropriate. Too large a particle size can easily lead to uneven glue formation. When the fiber reinforcement is immersed in the glue to make an adhesive sheet, the filler is in the fiber reinforcement. The surface distribution is not uniform, and the defects of dry flowers and excessive glue flow will appear in different positions, resulting in scrapping of the board; too small particle size, easy to produce agglomeration, resulting in similar results with too large particle size.
  • the flame retardants include, but are not limited to, phosphorus-containing flame retardants, nitrogen-containing flame retardants, and bromine-containing flame retardants.
  • the thickness of the adhesive sheet is 20-200 ⁇ m.
  • the application also provides a method for preparing the adhesive sheet, which specifically includes the following steps:
  • Step S1 Weigh the following components according to the mass parts: 25 to 65 parts of matrix resin, 20 to 60 parts of fiber reinforcement, 10 to 40 parts of filler, and 0 to 15 parts of flame retardant;
  • the types of the matrix resin, fiber reinforcement, filler, and flame retardant are the same as those used in the above-mentioned adhesive sheet, and will not be repeated here.
  • Step S2 adding the base resin, filler, and flame retardant to a suitable solvent, and mixing uniformly to form a glue
  • the solvent used is determined according to the types of the base resin, filler, and flame retardant. Mixing can be carried out at a certain temperature, and at the same time with stirring, it is conducive to uniform mixing.
  • Step S3 immersing the fiber reinforcement in the glue
  • the fiber reinforcement is completely immersed in the glue solution, and fully immersed so that the glue solution completely fills the internal space and surface of the fiber reinforcement body.
  • Step S4 drying the impregnated fiber reinforcement, and cutting to obtain an adhesive sheet.
  • the drying condition is 150°C for 3-6 minutes.
  • the following examples show the performance of the adhesive sheet of the present application.
  • the polyphenylene ether is SABIC acrylate-terminated polyphenylene ether, the brand is SA9000, the molecular weight is about 2300, and the polydivinylbenzene has a molecular weight of 100,000-18.
  • the filler is spherical nano-silica with a particle size of 0.1-2 ⁇ m, and the solvent is toluene.
  • this application selects polydivinylbenzene and polyphenylene ether with higher reactivity and multifunctional groups to prepare matrix resin, and the adhesive sheet is made by reinforcing glass fiber cloth and silica filler.
  • the overall performance is excellent.
  • the fluidity of the adhesive sheet is maintained at 5%-15%, and the resin flows well; the heat resistance can reach more than 200°C, and the heat resistance is good; after curing, the Df (1GHz) is maintained at 0.001 ⁇ 0.002.
  • the electric loss is low, which can meet the needs of the high-frequency field in the future; the higher the amount of polydivinylbenzene, the lower the amount of other components, and the lower cost.
  • the present application also provides a copper clad laminate, which includes a substrate, an adhesive sheet and a copper foil stacked in sequence, wherein the adhesive sheet is the adhesive sheet described above, and the copper foil passes through the The adhesive sheet is adhered to the substrate.
  • the preparation process of the copper clad laminate is as follows: stacking at least one adhesive sheet on each of the upper and lower surfaces of the substrate, and then covering the surface of the adhesive sheet with copper foil and then hot pressing and curing in a hot press.
  • the adhesive sheets shown in Examples 1-3 were used in copper clad laminates to prepare various copper clad laminates including the compositions shown in Table 2 below.
  • the heat resistance of the copper clad laminate can reach 215°C or more, and the thermal decomposition temperature can reach 410°C or more.
  • the CTE is close to copper foil, and the copper peel strength of the copper clad laminate is above 0.65N/mm, which solves the problems of defects in the processing of the multilayer printed circuit board caused by the insufficient heat resistance of the adhesive sheet, and the failure of the board;
  • the water absorption rate of the copper clad laminate is less than 0.1%, and the stability of the electrical properties of the substrate is greatly improved; the dielectric loss of the copper clad laminate can reach 0.001 at 1 GHz, which can meet the needs of future high-frequency applications .

Abstract

本申请提供了一种粘接片。所述粘接片包括按质量份数计的如下组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份，其中所述基体树脂包括按质量份数计的如下组份：改性聚苯醚20～70份、聚二烯烃类聚合物30～70份和引发剂0～5份。本申请同时提供一种粘接片的制备方法和使用该粘接片的覆铜层压板。本申请提供的粘接片和覆铜层压板耐热性能够达到200℃以上，解决了因粘接片耐热性不足而导致多层覆铜层压板在加工过程中出现缺陷、爆板等问题，而且粘接片流动度保持在5％-15％时间，可以保证多层覆铜层压板制备过程中树脂的充分流动和填充，保证制品的质量和批次稳定性；粘接片固化后具有更低的介电损，能够满足未来高频领域的需求。

Description

粘接片、其制备方法及使用该粘接片的覆铜层压板 【技术领域】
本申请涉及粘接片技术领域，尤其涉及一种粘接片、其制备方法以及使用该粘接片的覆铜层压板。
【背景技术】
覆铜层压板制作过程中，经常需要使用粘接片在热和/或压力下将两种或更多种材料层粘合到一起。使用时，粘接片或其部分可以流动并完全填充空间且提供电路之间、电路与电层之间、两个导电层之间或电路与介电层之间的粘合。粘接片具有与各层材料相当的电性质、热性质和机械性质(包括低介电常数和低耗散因数)。现有粘接片主要由改性聚苯醚与聚烯烃共混制备而成，由于聚苯醚与常用的聚烯烃结构差异较大，固化后易产生分离，导致聚烯烃的添加量较少，因此制造成本较高，而且制得的粘接片还存在耐热性差、流动性差的缺点。
因此，实有必要提供一种改进的粘接片及其制备方法以解决上述问题。
【发明内容】
本申请主要是解决现有粘接片耐热性差、流动性差、制造成本高的技术问题，本申请提供一种粘接片、其制备方法及使用该粘接片的覆铜层压板。
本申请提供一种粘接片，其包括按质量份数计的如下组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份，，其中所述基体树脂包括按质量份数计的如下组份：改性聚苯醚20～70份、聚二烯烃类聚合物30～70份和引发剂0～5份。
优选的，所述改性聚苯醚为可反应性官能团封端的低分子量聚苯醚，其分子量为800-6000，优选为900-4000。
优选的，所述低分子量聚苯醚包括复数个以下结构的结构单元：
Figure PCTCN2019096387-appb-000001
其中R 1、R 2、R 3和R 4独立地表示氢、烷基或酯基中的任意一种。
优选的，所述低分子量聚苯醚的可反应性官能团包括不饱和酯和不饱和烯烃中的任意一种，所述可反应性官能团的结构式为：
Figure PCTCN2019096387-appb-000002
其中X为-C 6H 4-、-CH 2-、-O-、-COO-中的任意一种，R为-CH 3、-C 6H 5或H中的任意一种。
优选的，所述聚二烯烃类聚合物包括双环戊二烯类聚合物、聚二乙烯基苯、聚1,2丁二烯、苯乙烯/二乙烯基苯共聚物、苯乙烯/丁二烯共聚物和苯乙烯/异戊二烯共聚物中的任意一种。
优选的，所述聚二烯烃类聚合物的分子量为3000-180000。
优选的，所述引发剂为自由基引发剂，其包括过氧化物类引发剂、偶氮类引发剂和联枯中的任意一种。
优选的，所述纤维增强体为玻璃纤维、石英纤维和有机纤维中的一种或多种。
优选的，所述填料为表面经过偶联剂修饰改性的无机填料，所述无机填料包括二氧化硅、二氧化钛和有机聚合物微球中的一种或多种。
优选的，所述阻燃剂包括含磷阻燃剂、含氮阻燃剂和含溴阻燃剂中的一种或多种。
优选的，所述粘接片的厚度为20～200μm。
本申请同时提供一种吸音材料的制备方法，按照质量份数分别称取以下各组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15 份；
将所述基体树脂、填料和阻燃剂加入到适当的溶剂中，混合均匀形成胶液；
将所述纤维增强体浸渍于所述胶液中；
将浸渍后的所述纤维增强体烘干，经裁切后得到粘接片。
本申请同时提供一种覆铜层压板，所述覆铜层压板叠设有上文所述的粘接片。
与相关技术相比，本申请的粘接片、其制备方法及使用该粘接片的覆铜层压板具有以下有益效果：
1、选用与改性聚苯醚结构相似的聚二烯烃类聚合物作为改性组分与之共混制备粘接片，制得的粘接片耐热性能够达到200℃以上，流动度保持在5％-15％，改善了基体树脂聚苯醚粘度大、流动性差的问题；
2、不损失聚苯醚低介电性能和耐热性的同时，提高聚合物韧性；
3、聚二烯烃聚合物添加量较多，有效地降低聚苯醚树脂的成本；
4、由于聚二烯烃类聚合物与改性聚苯醚结构化学结构接近，改善了其他烯烃类与聚苯醚共混易发生相分离的问题；
5、将粘接片使用到覆铜层压板中，解决了因粘接片耐热性不足而导致多层覆铜层压板在加工过程中出现缺陷、爆板等问题，而且可以保证多层覆铜层压板制备过程中树脂的充分流动和填充，保证制品的质量和批次稳定性，粘接片固化后具有更低的介电损，能够满足未来高频领域的需求。
【具体实施方式】
下面对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。
本申请提供一种粘接片，其包括按质量份数计的如下组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份。
按质量份数计，所述基体树脂包括改性聚苯醚20～70份、聚二烯烃类聚合物30～70份和引发剂0～5份。由于聚苯醚存在熔点高、流动性差、材料成 本高的缺点，本申请在聚苯醚中加入聚二烯烃类聚合物并在引发剂的作用下对聚苯醚进行改性，可制备出加工性能良好、成本低、固化物介电性能和及耐热性优异、CTE和吸水吸湿率低的基体树脂。采用聚二烯烃类聚合物对聚苯醚进行改性，不损失PPO低介电性能和耐热性的同时，提高聚合物韧性，还可以有效地降低聚苯醚树脂的成本，而且聚二烯烃类聚合物与聚苯醚化学结构接近，相较于他烯烃类，聚二烯烃类聚合物与PPO共混不易发生相分离的问题。
优选地，所述改性聚苯醚为可反应性官能团封端的低分子量聚苯醚，其分子量为800-6000，优选为900-4000。
所述低分子量聚苯醚包括复数个以下结构的结构单元：
Figure PCTCN2019096387-appb-000003
其中对于每个结构单元，每个R 1、R 2、R 3和R 4独立地表示氢、烷基或酯基中的任意一种。
所述低分子量聚苯醚的可反应性官能团包括但不限于不饱和酯和不饱和烯烃等，所述可反应性官能团的结构式为：
Figure PCTCN2019096387-appb-000004
其中X为-C 6H 4-、-CH 2-、-O-、-COO-中的任意一种，R为-CH 3、-C 6H 5或H中的任意一种。
聚苯醚改性用的所述聚二烯烃类聚合物包括但不限于双环戊二烯类聚合物、聚二乙烯基苯、聚1,2丁二烯、苯乙烯/二乙烯基苯共聚物、苯乙烯/丁二烯共聚物和苯乙烯/异戊二烯共聚物中的任意一种。优选地，所述聚二烯烃类聚合物的分子量为3000-180000。
所述引发剂为自由基引发剂，其包括但不限于过氧化物类引发剂、偶氮类引发剂和联枯中的任意一种。
所述纤维增强体为玻璃纤维、石英纤维和有机纤维中的一种或多种，使用纤维增强体可以使粘接片具有相对高的机械强度。
所述填料为表面经过偶联剂修饰改性的无机填料，所述无机填料包括但不限于二氧化硅、二氧化钛和有机聚合物微球。
所述填料粒径为0.1～10μm，优选为0.1～4μm。所述填料的粒径应当适宜，粒径过大易导致形成的胶液不均匀，当将所述纤维增强体浸渍于所述胶液制作粘接片时，所述填料在所述纤维增强体表面分布就不均匀，不同位置会出现干花和流胶过大的缺陷，导致板材报废；粒径过小，易产生团聚，导致结果与粒径过大相似。
所述阻燃剂包括但不限于含磷阻燃剂、含氮阻燃剂和含溴阻燃剂。
优选地，所述粘接片的厚度为20～200μm。
本申请还提供一种粘接片的制备方法，具体包括以下步骤：
步骤S1，按照质量份数分别称取以下各组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份；
在该步骤中，所述基体树脂份、纤维增强体、填料和阻燃剂的种类上文所述粘接片所用的种类相同，在此不再赘述。
步骤S2，将所述基体树脂、填料和阻燃剂加入到适当的溶剂中，混合均匀形成胶液；
在该步骤中，所使用的溶剂根据所述基体树脂、填料和阻燃剂的种类来确定。混合可以在一定的温度下进行，同时伴随搅拌，有利于混合均匀。
步骤S3，将所述纤维增强体浸渍于所述胶液中；
在该步骤中，将所述纤维增强体完全浸没在所述胶液中，充分浸渍，使所述胶液完全填充所述纤维增强体的内部空间及表面。
步骤S4，将浸渍后的所述纤维增强体烘干，经裁切后得到粘接片。
在该步骤中，干燥条件为150℃下干燥3-6min。
下面将结合具体实施例解释本申请的实施方式。
以下实施例表明本申请的粘接片的性能。制备具有下表1中所示组成的多种粘接片，其中聚苯醚为SABIC丙烯酸酯封端的聚苯醚，牌号为SA9000，分子量为2300左右，聚二乙烯基苯，分子量10万～18万，填料为球形纳米二氧化硅，粒径0.1～2μm，溶剂为甲苯。
表1
Figure PCTCN2019096387-appb-000005
从表1可看出，本申请选用反应活性较高、多官能团的聚二乙烯基苯与聚苯醚共混制备基体树脂，并通过玻纤布和二氧化硅填料增强制得的粘接片综合性能优异，其中粘接片流动度保持在5％-15％，树脂流动好；耐热性能够达到200℃以上，耐热性好；固化后Df(1GHz)在维持在0.001～0.002，介电损耗低，能够满足未来高频领域的需求；聚二乙烯基苯的用量较高，可以相对降低其他组份的用量，成本较低。
本申请还提供一种覆铜层压板，其包括依次叠设的基板、粘接片和铜箔，其中所述粘接片为由上文所述的粘接片，所述铜箔通过所述粘接片粘合于所述基板。所述覆铜板层压板的制备过程为：在基板上下表面各叠设至少一块粘接片，然后在粘接片表面覆上铜箔后在热压机中热压固化成型。
将实施例1-3所示的粘接片使用到覆铜层压板中，制备包括下表2中所示组成的多种覆铜层压板。其中所使用的铜箔为电解铜，铜箔的粗糙度为Rz＝1.2μm，热压固化成型的条件为：压力3MPa，温度220℃，时间2h。
表2
Figure PCTCN2019096387-appb-000006
从表2中可看出，由于本申请的覆铜层压板使用了本申请的粘接片，所述覆铜层压板耐热性能够达到215℃以上，热分解温度达到410℃以上，基板的CTE接近铜箔，覆铜层压板的铜剥离强度达到0.65N/mm以上，解决了因粘接片耐热性不足所导致多层印刷电路板在加工过程中出现缺陷，爆板等问题；所述覆铜层压板吸水吸湿率低于0.1％，基板电性能的稳定性大幅度得到改善；所述覆铜层压板板介电损耗在1GHz下可达到0.001，能够满足未来高频领域应用的需求。
以上所述的仅是本申请的实施例，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。

Claims (14)

  1. 一种粘接片，其特征在于，所述粘接片包括按质量份数计的如下组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份，其中所述基体树脂包括按质量份数计的如下组份：改性聚苯醚20～70份、聚二烯烃类聚合物30～70份和引发剂0～5份。
  2. 根据权利要求1所述的粘接片，其特征在于，所述改性聚苯醚为可反应性官能团封端的低分子量聚苯醚，其分子量为800-6000，优选为900-4000。
  3. 根据权利要求2所述的粘接片，其特征在于，所述低分子量聚苯醚包括复数个以下结构的结构单元：
    Figure PCTCN2019096387-appb-100001
    其中R 1、R 2、R 3和R 4独立地表示氢、烷基或酯基中的任意一种。
  4. 根据权利要求2所述的粘接片，其特征在于，所述低分子量聚苯醚的可反应性官能团包括不饱和酯和不饱和烯烃中的任意一种，所述可反应性官能团的结构式为：
    Figure PCTCN2019096387-appb-100002
    其中X为-C 6H 4-、-CH 2-、-O-、-COO-中的任意一种，R为-CH 3、-C 6H 5或H中的任意一种。
  5. 根据权利要求1所述的粘接片，其特征在于，所述聚二烯烃类聚合物包括双环戊二烯类聚合物、聚二乙烯基苯、聚1,2丁二烯、苯乙烯/二乙烯基苯共聚物、苯乙烯/丁二烯共聚物和苯乙烯/异戊二烯共聚物中的任意一种。
  6. 根据权利要求5所述的粘接片，其特征在于，所述聚二烯烃类聚合物的分子量为3000-180000。
  7. 根据权利要求1所述的粘接片，其特征在于，所述引发剂为自由基引发剂，其包括过氧化物类引发剂、偶氮类引发剂和联枯中的任意一种。
  8. 根据权利要求1所述的粘接片，其特征在于，所述纤维增强体为玻璃纤维、石英纤维和有机纤维中的一种或多种。
  9. 根据权利要求1所述的粘接片，其特征在于，所述填料为表面经过偶联剂修饰改性的无机填料，所述无机填料包括二氧化硅、二氧化钛和有机聚合物微球中的一种或多种。
  10. 根据权利要求1所述的粘接片，其特征在于，所述填料的粒径为0.1～10μm，优选为0.1～4μm。
  11. 根据权利要求1所述的粘接片，其特征在于，所述阻燃剂包括含磷阻燃剂、含氮阻燃剂和含溴阻燃剂中的一种或多种。
  12. 根据权利要求1所述的粘接片，其特征在于，所述粘接片的厚度为20～200μm。
  13. 一种粘接片的制备方法，其特征在于，包括以下步骤：
    按照质量份数分别称取以下各组份：基体树脂25～65份、纤维增强体20～60份、填料10～40份和阻燃剂0～15份，其中所述基体树脂包括按质量份数计的如下组份：改性聚苯醚20～70份、聚二烯烃类聚合物30～70份和引发剂0～5份；
    将所述基体树脂、填料和阻燃剂加入到适当的溶剂中，混合均匀形成胶液；
    将所述纤维增强体浸渍于所述胶液中；
    将浸渍后的所述纤维增强体烘干，经裁切后得到粘接片。
  14. 一种覆铜层压板，其特征在于，所述覆铜层压板叠设有权利要求1所述的粘接片或采用权利要求13所述的粘接片的制备方法制备得到的粘接片。
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