CN111559138A - 一种烯烃基覆铜板 - Google Patents

一种烯烃基覆铜板 Download PDF

Info

Publication number
CN111559138A
CN111559138A CN202010470259.8A CN202010470259A CN111559138A CN 111559138 A CN111559138 A CN 111559138A CN 202010470259 A CN202010470259 A CN 202010470259A CN 111559138 A CN111559138 A CN 111559138A
Authority
CN
China
Prior art keywords
olefin
clad plate
copper foil
based copper
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010470259.8A
Other languages
English (en)
Inventor
周学琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhuhai Guoneng Composite Material Technology Co ltd
Original Assignee
Zhuhai Guoneng Composite Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhuhai Guoneng Composite Material Technology Co ltd filed Critical Zhuhai Guoneng Composite Material Technology Co ltd
Priority to CN202010470259.8A priority Critical patent/CN111559138A/zh
Publication of CN111559138A publication Critical patent/CN111559138A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明涉及一种烯烃基覆铜板，由表面处理铜箔、玻璃布树脂绝缘材料组成；所述烯烃基覆铜板的制备方法包括以下步骤：将表面处理铜箔与半固化片叠合后热压，得到烯烃基覆铜板；所述表面处理铜箔由含双键碳氢物处理铜箔粗糙面得到，具有一种低介电常数和低损耗因子的基体，用于制作高频高速应用领域的层压板。

Description

一种烯烃基覆铜板
技术领域
本发明涉及一种热固性烯烃基覆铜板，可用于高频高速通讯领域材料的制备。
背景技术
覆铜板（copper clad laminate，CCL）是制作印刷线路板（print circuit board，PCB）的基础材料，是PCB的上游基本材料，占PCB成本的35%左右。CCL将补强材料浸以树脂，一面或两面覆以铜箔，经热压而成的一种板状材料。通过在CCL上打孔、电镀等工序后，便形成了PCB。作为PCB的基础，CCL很大程度上决定了PCB板（电路板）的性能。5G时期的频段比4G时期更高，导致传输过程中会有更高的损耗。为了解决这个问题，需要使用更低损耗（更低的介电常数和介电损耗）的材料。而对于电路板来说，其介电常数和介电损耗主要由覆铜板中的绝缘层材料决定。因此以介电性能良好的树脂材料作为覆铜板绝缘层的原材料将成为大趋势。烯烃类基板已经成为研究高频基板的重点方向，纵观现有技术，都是在树脂基体上做研究，从未有关于铜箔处理的技术更新，而铜箔与介质层的界面效应对覆铜板的应用非常关键，尤其关系剥离强度。比如现有技术以改性聚苯醚树脂、烯烃类化合物、交联助、阻燃剂制备树脂组合物，通过含磷酸酐化合物和环氧改性碳氢树脂反应，将含磷原子很好地引入碳氢树脂的固化交联体系中，获得同时满足无卤阻燃和低介电常数、低介质损耗值的基板材料；通过使用硅芳炔树脂、含不饱和键的聚苯醚树脂、丁二烯聚合物树脂组合物，制得的覆金属层压板可以至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个；还公开了热固性树脂组合物包括溶剂可溶性的多官能乙烯基芳香族共聚物、聚丁二烯树脂，制作的半固化片及覆铜箔层压板具有良好的韧性，且保持了高的玻璃化转变温度、低的吸水率、介电特性和耐湿热性，适合高频高速印制线路板领域使用，并适合于多层印制线路板加工。
发明内容
本发明所要解决的技术问题是提供一种烯烃基覆铜板，该复合材料基板损耗因子低，在低铜箔粗糙度Rz下，剥离强度高、吸水率低，尤其是在烯烃树脂基础上，以低粗糙度获得符合要求的剥离强度，适合天线及基站等要求高频的应用。
本发明采取如下技术方案：
一种烯烃基覆铜板，由表面处理铜箔、玻璃布树脂绝缘材料组成；所述烯烃基覆铜板的制备方法包括以下步骤：将表面处理铜箔与半固化片叠合后热压，得到烯烃基覆铜板；所述表面处理铜箔由含双键碳氢物处理铜箔粗糙面得到。
本发明公开的烯烃基覆铜板，其制备方法包括以下步骤；
（1）将烯烃聚合物溶入溶剂中，搅拌下加入填料、固化剂，搅拌得到胶液；所述烯烃聚合物包括丁二烯、苯乙烯、聚丁二烯、聚苯乙烯或者丁二烯与苯乙烯的共聚物；
（2）将玻璃布浸渍胶液，得到预浸料；加热预浸料，得到半固化片；
（4）将5～10张半固化片叠合，上下各压覆一张表面处理铜箔，热压得到烯烃基覆铜板；所述表面处理铜箔由含双键碳氢物处理铜箔粗糙面得到。
本发明中，所述含双键碳氢物为含有双键的、仅由碳氢组成的物质，比如丁二烯、苯乙烯、聚丁二烯、聚苯乙烯或者丁二烯与苯乙烯的共聚物；所述铜箔的毛面粗糙度Rz为1～10微米；所述铜箔的厚度为5～70微米，比如所述铜箔为1盎司铜箔或者半盎司铜箔，优选铜箔的毛面粗糙度Rz为1～5微米，进一步优选铜箔的毛面粗糙度Rz为1～3微米；铜箔为RTF铜箔或者HVLP铜箔。
现有技术公开了一种电子复合材料基板，该热固性电子复合材料包括丁二烯、苯乙烯、丁二烯苯乙烯共聚物或苯乙烯丁二烯苯乙烯共聚物，可制得低损耗因子基板，并且耐热、耐水、剥离等性能优异，但是为了提高剥离强度采用的铜箔为STD铜箔，需要高的粗糙度，限定1盎司铜箔的铜瘤高度为8～12微米，半盎司铜箔的铜瘤高度为6～10微米，铜箔粗糙面经过乙烯基偶联剂处理，这样导致制备的基板PIM性能较差；本发明采用新的技术方案，在低粗糙度情况下，得到与现有技术近似的剥离强度，尤其是极大改善了PIM性能，降低了信号失真。
本发明中，所述半固化片由玻璃布浸渍胶液制备得到；所述胶液包括烯烃聚合物、溶剂、填料、固化剂；烯烃聚合物、填料、固化剂的质量比为100∶（50～300）∶（2～4）；玻璃布为2116玻璃布、1080玻璃布或106玻璃布。
本发明中，所述填料的粒径为30～50微米；所述固化剂包括过氧化二异丙苯、过氧化苯甲酸叔丁酯、2,5-二（2-乙基己酰过氧）-2,5-二甲基己烷中的一种或几种；所述胶液的固含量为80～85%。
本发明中，所述填料包括二氧化硅、二氧化钛、钛酸钡、氮化硼、氧化铝中的一种或一种以上的混合物。
本发明中，所述半固化片位于两张表面处理铜箔之间；所述半固化片为5～10张。
本发明中，热压的温度为150～300℃，时间为20～75分钟，压力为35kg/cm2～80kg/cm2。
本发明公开了所述烯烃基覆铜板在制备高频材料中的应用；所述高频材料包括电路板。
本发明的热固性电子复合材料用于制作高频高速应用领域的层压板、半固化片和纯胶片，烯烃聚合物包括丁二烯、苯乙烯、聚丁二烯、聚苯乙烯、丁二烯/苯乙烯共聚物中的一种或几种；其中丁二烯/苯乙烯共聚物包括丁二烯-苯乙烯共聚物或苯乙烯-丁二烯-苯乙烯共聚物等；二氧化硅包括结晶型二氧化硅、无定型二氧化硅、球形二氧化硅、气相二氧化硅等一种或者多种。
本发明具有如下优点：
本发明烯烃聚合物可以是丁二烯、苯乙烯的聚合产物，比如丁二烯苯乙烯共聚物、苯乙烯丁二烯苯乙烯共聚物，因树脂分子结构中含有刚性较好的苯环及高乙烯基含量提供固化交联时所需要的大量不饱和乙烯基，可提高固化时的交联密度，从而提高材料的优良的耐高温性能和刚性，烯烃聚合物如D1101(Kraton公司)和FG1901(Kraton公司)。
本发明的纤维玻璃布起到提高基板的尺寸稳定性，减少固化过程中材料收缩的作用；固化剂起到加速反应的作用，当本发明的组合物被加热时，固化剂分解产生自由基，引发聚合物的分子链发生交联，固化剂为过氧化二异丙苯DCP、过氧化苯甲酸叔丁酯、2，5-二（2-乙基己酰过氧）-2，5-二甲基己烷。
本发明的热固性电子复合材料中所采用的树脂不是环氧类树脂，而是采用低介电的双键类聚合物材料，同时搭配填料技术，可制得低损耗因子基板，尤其是，本发明克服了现有技术需要采用高铜箔铜瘤以提高树脂体系剥离强度的缺陷，可以在较低的毛面（粗糙面）粗糙度Rz的情况下，取得接近1N/mm的剥离强度，得到的基板传送损耗极低。
附图说明
图1为本发明表面处理铜箔实物照片；
图2为PIM测试仪照片。
具体实施方式
本发明将含双键碳氢物溶液涂在铜箔粗糙面上，去除溶剂，得到表面处理铜箔。
本发明以烯烃聚合物溶入溶剂中，搅拌下加入填料、固化剂，搅拌得到胶液；再利用玻璃布浸渍、加热得到半固化片，最后与表面处理铜箔叠合热压，得到烯烃基覆铜板；三个步骤操作简单。
本发明的颗粒填料为结晶型二氧化硅、无定型二氧化硅、球形二氧化硅、气相二氧化硅、二氧化钛、钛酸钡、氮化硼、氧化铝、玻璃纤维等一种或者多种，颗粒填料起着提高胶液固体含量、改善材料尺寸稳定性、降低CTE等目的；优先颗粒填料为二氧化硅，其中粒径30～50微米，可采用的二氧化硅填料如FB-35(Denka公司)、525（Sibelco公司）。
本发明所用原料都为覆铜板领域常规原料，涉及的测试方法为覆铜板常规的标准测试方法；铜箔一般为压延铜箔或者电解铜箔（压延铜箔或者电解铜箔的选择不影响本发明技术效果的实现，一般为电解铜箔，按粗糙度为RTF铜箔或者HVLP铜箔），其一面制备铜瘤形成粗糙面，再用含双键碳氢物处理，得到本发明的铜箔；现有技术采用高铜瘤高度来提高剥离强度，而本发明首次采用含双键碳氢物处理低粗糙度铜箔，解决了残铜率高以及提高剥离强度。
实施例1
将苯乙烯与丁二烯的嵌段共聚物（D1101 SBS）的二甲苯溶液涂覆在铜箔粗糙面上，自然晾干，挥发去除溶剂，得到表面处理铜箔，在铜箔粗糙面形成共聚物膜层，厚度为15微米，实物照片参见图1。
将100重量份的苯乙烯与丁二烯的嵌段共聚物（D1101）溶于甲苯，搅拌下加入100重量份的二氧化硅（525）、2.5重量份的固化剂DCP，搅拌得到胶液（固含量为80%），使用1080纤维玻璃布（上海宏和，布厚0.056mm）浸渍以上胶液得到预浸料，然后烘干去除溶剂后制得半固化片，胶含量为（（半固化片的重量-对应玻璃布的重量）/半固化片的重量）为65%；将8张半固化片叠合，在其两侧压覆表面处理铜箔，在压机中经过高温热压固化后制成烯烃基覆铜板。
上述烘干的温度为90℃，时间为3.5分钟，热压的温度为230℃，时间为50分钟，压力为70kg/cm2；其物性数据如表1所示。
本实施例中，填料的粒径为30～40微米；铜箔为1盎司铜箔，铜箔的毛面粗糙度Rz为2.9微米。
实施例2
将苯乙烯与丁二烯的嵌段共聚物（D1101 SBS）的二甲苯溶液涂覆在铜箔粗糙面上，自然晾干，挥发去除溶剂，得到表面处理铜箔，在铜箔粗糙面形成共聚物膜层，厚度为20微米。
将100重量份的苯乙烯与丁二烯的嵌段共聚物（D1101）溶于甲苯，搅拌下加入250重量份的二氧化硅（525）、3.5重量份的固化剂DCP，搅拌得到胶液（固含量为80%），使用1080纤维玻璃布浸渍以上树脂液然后烘干去除溶剂后制得半固化片，胶含量为（（半固化片的重量-对应玻璃布的重量）/半固化片的重量）为68%；再将8张半固化片叠合，在其两侧压覆表面处理铜箔，在压机中经过高温热压固化后制成烯烃基覆铜板；烘干的温度为100℃，时间为3分钟，热压的温度为240℃，时间为45分钟，压力为80kg/cm2；其物性数据如表1所示。
本实施例中，填料的粒径为40～50微米；铜箔为0.5盎司铜箔，铜箔的毛面粗糙度Rz为2.2微米。
对比例1
制作工艺与实施例1相同，采用现有1盎司铜箔（毛面粗糙度Rz为2.9微米），即未经过烯烃表面处理，其余一样，其物性数据如表1所示。
对比例2
制作工艺与实施例1相同，其中铜箔粗糙面经过乙烯基偶联剂乙烯基三甲基硅烷处理，而不是含双键碳氢物处理，其余一样；其物性数据如表1所示。
实施例3
制作工艺与实施例1相同，其中填料为氮化铝，而不是二氧化硅，其余一样；其物性数据如表1所示。
以上所有原料都是市购产品，得到的产品性能测试方法为常规方法，在实施例一的基础上，将二氧化硅替换为钛酸钡、氧化铝等填料，性能接近。
表1 实施例以及对比例产品性能
Figure 647000DEST_PATH_IMAGE001
介电性能根据IPC TM-650 2.5.5方法测试；根据IPC TM-650 2.6.2.1方法测试吸湿率，实施例都小于0.1%；剥离强度根据IPC TM-650 2.4.8方法测试。
对比例4
制作工艺与实施例1相同，采用现有毛面粗糙度Rz为10微米的1盎司铜箔，经过同样的苯乙烯与丁二烯的嵌段共聚物（D1101 SBS）表面处理，其余一样。
对比例5
制作工艺与实施例1相同，采用现有毛面粗糙度Rz为10微米的1盎司铜箔，经过乙烯基偶联剂乙烯基三甲基硅烷表面处理，其余一样。
采用PIM测试仪测试PIM（2600MHz），参见图2（试验样条参见图左下角），实施例1、实施例2的产品PIM分别为-162 dBc、-161 dBc；对比例4、对比例5分别为-148 dBc、-150dBc，信号失真较大。
如上物性分析所述，与一般的复合材料相比，本发明的烯烃覆铜板拥有更加优异的介电常数和损耗因子，高频高速性能很好，完全满足未来5G市场的需求。
以上实施例，并非对本发明的组合物的电子复合材料作任何限制，凡是依据本发明的技术实施或组合物或含量对以上实施例所做的任何细微修改，等同变化与修饰，均仍属于本发明的技术方案的范围内。

Claims (10)

1.一种烯烃基覆铜板，其特征在于，所述烯烃基覆铜板由表面处理铜箔、玻璃布树脂绝缘材料组成；所述烯烃基覆铜板的制备方法包括以下步骤：将表面处理铜箔与半固化片叠合后热压，得到烯烃基覆铜板；所述表面处理铜箔由含双键碳氢物处理铜箔粗糙面得到。
2.根据权利要求1所述烯烃基覆铜板，其特征在于：所述含双键碳氢物为丁二烯、苯乙烯、聚丁二烯、聚苯乙烯或者丁二烯与苯乙烯的共聚物；所述铜箔的毛面粗糙度Rz为1～10微米；所述铜箔的厚度为5～70微米。
3.根据权利要求1所述烯烃基覆铜板的制备方法，其特征在于：所述半固化片由玻璃布浸渍胶液制备得到；所述胶液包括烯烃聚合物、溶剂、填料、固化剂。
4.根据权利要求3所述烯烃基覆铜板，其特征在于：烯烃聚合物、填料、固化剂的质量比为100∶（50～300）∶（2～4）；玻璃布为2116玻璃布、1080玻璃布或106玻璃布。
5.根据权利要求3所述烯烃基覆铜板，其特征在于：所述填料的粒径为30～50微米；所述固化剂包括过氧化二异丙苯、过氧化苯甲酸叔丁酯、2,5-二（2-乙基己酰过氧）-2,5-二甲基己烷中的一种或几种；所述胶液的固含量为80～85%。
6.根据权利要求5所述烯烃基覆铜板，其特征在于：所述填料包括二氧化硅、二氧化钛、钛酸钡、氮化硼、氧化铝中的一种或一种以上的混合物。
7.根据权利要求1所述烯烃基覆铜板，其特征在于：所述半固化片位于两张表面处理铜箔之间；所述半固化片为5～10张。
8.根据权利要求1所述烯烃基覆铜板，其特征在于：热压的温度为150～300℃，时间为20～75分钟，压力为35kg/cm2～80kg/cm2。
9.权利要求1所述烯烃基覆铜板在制备高频材料中的应用。
10.根据权利要求9所述的应用，其特征在于，所述高频材料包括电路板。
CN202010470259.8A 2020-05-28 2020-05-28 一种烯烃基覆铜板 Pending CN111559138A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010470259.8A CN111559138A (zh) 2020-05-28 2020-05-28 一种烯烃基覆铜板

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010470259.8A CN111559138A (zh) 2020-05-28 2020-05-28 一种烯烃基覆铜板

Publications (1)

Publication Number Publication Date
CN111559138A true CN111559138A (zh) 2020-08-21

Family

ID=72068456

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010470259.8A Pending CN111559138A (zh) 2020-05-28 2020-05-28 一种烯烃基覆铜板

Country Status (1)

Country Link
CN (1) CN111559138A (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266602A (zh) * 2020-11-23 2021-01-26 江苏诺德新材料股份有限公司 一种碳氢复合材料及其制造的高频覆铜板
CN113444471A (zh) * 2021-07-20 2021-09-28 郴州功田电子陶瓷技术有限公司 一种应用于多层高频覆铜板粘结片的组合物及其应用
CN113500831A (zh) * 2020-12-31 2021-10-15 苏州益可泰电子材料有限公司 服务器用高速覆铜板

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5474884A (en) * 1977-11-29 1979-06-15 Fujitsu Ltd Preparation of copper-clad laminate
JPH07166145A (ja) * 1993-12-15 1995-06-27 Sumitomo Bakelite Co Ltd 銅張積層板用接着剤
CN204894661U (zh) * 2015-06-08 2015-12-23 广东生益科技股份有限公司 一种电路基板用预浸夹心结构体及由其制备的电路基板、印刷电路板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5474884A (en) * 1977-11-29 1979-06-15 Fujitsu Ltd Preparation of copper-clad laminate
JPH07166145A (ja) * 1993-12-15 1995-06-27 Sumitomo Bakelite Co Ltd 銅張積層板用接着剤
CN204894661U (zh) * 2015-06-08 2015-12-23 广东生益科技股份有限公司 一种电路基板用预浸夹心结构体及由其制备的电路基板、印刷电路板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266602A (zh) * 2020-11-23 2021-01-26 江苏诺德新材料股份有限公司 一种碳氢复合材料及其制造的高频覆铜板
CN113500831A (zh) * 2020-12-31 2021-10-15 苏州益可泰电子材料有限公司 服务器用高速覆铜板
CN113444471A (zh) * 2021-07-20 2021-09-28 郴州功田电子陶瓷技术有限公司 一种应用于多层高频覆铜板粘结片的组合物及其应用

Similar Documents

Publication Publication Date Title
CN107964203B (zh) 一种低介电预浸料组合物、覆铜板及其制作方法
CN101328277B (zh) 一种复合材料、用其制作的高频电路基板及制作方法
CN111559138A (zh) 一种烯烃基覆铜板
CN102161823B (zh) 复合材料、用其制作的高频电路基板及其制作方法
EP2595460B1 (en) Composite material and high frequency circuit substrate manufactured with the composite material and the manufacturing method thereof
CN111154197A (zh) 一种碳氢树脂组合物及其制备方法与应用
TWI410187B (zh) 用於高速及高頻印刷電路板之層壓板
EP3037475A1 (en) Phenoxy cyclotriphosphazene active ester, halogen-free resin composition and use thereof
CN114410046A (zh) 一种用于高频覆铜板的碳氢树脂基板材料的制备方法
WO2000026269A1 (en) Vinyl terminated polybutadienes containing urethane or ester residues
CN112679936B (zh) 一种热固性树脂组合物及包含其的树脂胶液、预浸料、层压板、覆铜板和印刷电路板
CN112111176B (zh) 一种氮化硼包覆聚四氟乙烯复合填料及其制备的半固化片和高导热型碳氢覆铜板
TW202204512A (zh) 高頻基板用樹脂組成物及金屬積層板
CN114085525A (zh) 一种低热膨胀系数树脂组合物及其应用
CN111605267B (zh) 一种阻燃烯烃基板及其制备方法
WO2023183131A1 (en) Materials for printed circuit boards
CN111683464A (zh) 一种覆铜板的制备方法
CN114479212B (zh) 聚丁二烯和环氧化聚丁二烯组合物、胶粘剂、涂胶金属箔、半固化片、层压板及制备方法
CN114559712B (zh) 一种耐高温低损耗的覆铜板及其制备工艺
JPH1017685A (ja) プリプレグ及び積層板
CN115232461A (zh) 一种热固性聚苯醚树脂基复合材料、制备方法和应用
CN113896916A (zh) 一种基于高Tg超高分子量聚乙烯纤维布的半固化片及覆铜板的制备方法
CN109082019B (zh) 一种聚合物树脂及其在高频电路板中的应用
CN114133748B (zh) 一种低介电树脂组合物及其应用
CN109053944B (zh) 一种聚合物树脂及其在高频电路板中的应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200821