WO2022007004A1 - Preparation method for composite dielectric copper-clad substrate, and printed circuit board - Google Patents

Preparation method for composite dielectric copper-clad substrate, and printed circuit board Download PDF

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Publication number
WO2022007004A1
WO2022007004A1 PCT/CN2020/103897 CN2020103897W WO2022007004A1 WO 2022007004 A1 WO2022007004 A1 WO 2022007004A1 CN 2020103897 W CN2020103897 W CN 2020103897W WO 2022007004 A1 WO2022007004 A1 WO 2022007004A1
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Prior art keywords
fluorine
preset
weight
preparation
composite
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PCT/CN2020/103897
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French (fr)
Chinese (zh)
Inventor
黄国创
王和志
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瑞声声学科技(深圳)有限公司
瑞声科技(新加坡)有限公司
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Publication of WO2022007004A1 publication Critical patent/WO2022007004A1/en

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    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers

Definitions

  • the invention relates to the technical field of the preparation of composite dielectric copper clad laminates, in particular to a preparation method of composite dielectric copper clad laminates and a printed circuit board.
  • Polytetrafluoroethylene has excellent microwave performance, its dielectric constant ( ⁇ r) is 2.0 ⁇ 2.2, dielectric loss (tan ⁇ ) is 0.0002 ⁇ 0.0003, and it has good chemical stability and thermal stability. Suitable for high frequency microwave circuits.
  • the composite medium prepared by compounding fine electronic ceramics with PTFE resin as the matrix has a series of advantages such as excellent high-frequency dielectric properties, low-cost metallization, convenient circuit processing and installation, and is not easy to be broken when used in vibration occasions.
  • ⁇ r dielectric constant
  • tan ⁇ dielectric loss
  • the composite dielectric substrate obtained by impregnating glass fiber cloth with PTFE emulsion is the most common and widely used product. It has good dimensional stability and low manufacturing cost, but because the dielectric constant of glass fiber cloth itself is relatively low , so the dielectric constant of the obtained glass fiber reinforced PTFE substrate is not high, about 2.3-2.8. In order to obtain a composite material with a higher dielectric constant, it is necessary to dope ceramic powder with a high dielectric constant. At the same time, because the glass fiber cloth contains more metal oxides and metal salt impurities, the dielectric loss of the composite substrate is also high.
  • the invention mainly provides a preparation method and a printed circuit board of a composite medium copper clad plate, which can solve the problem that the thermal expansion coefficient of the composite medium copper clad substrate obtained by impregnating the PTFE emulsion with glass fiber cloth in the prior art is higher than that of the copper foil. It is not conducive to subsequent process processing and the use of devices at higher temperatures.
  • a technical solution adopted by the present invention is to provide a preparation method of a composite dielectric copper clad laminate, the preparation method comprising: forming a green substrate by using an emulsion of a fluorine-containing material and at least two ceramic filling materials, The sum of the weight of the fluorine-containing material and the at least two ceramic filling materials is 100 parts by weight, wherein the fluorine-containing material is 20-60 weight parts, and the at least two ceramic filling materials include the first ceramic filling material Materials and a second ceramic filling material, the first ceramic filling material is 1-5 parts by weight, and the second ceramic filling material is 40-70 parts by weight; the substrate green body is pre-fired to form a composite substrate ; vacuum sintering the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate; wherein the preset sintering temperature is greater than the melting point of the fluorine-containing material
  • the dielectric constant of the first ceramic filling material is greater than 30, and the dielectric constant of the second ceramic filling material is less than 30.
  • the forming of the green substrate by using the emulsion of the fluorine-containing material and the at least two ceramic filling materials includes: adding a preset amount of the emulsion of the fluorine-containing material into the container for stirring; respectively adding a preset amount of the first ceramic
  • the filling material and the second ceramic filling material are added to the emulsion of the fluorine-containing material to form a mixed emulsion; the mixed emulsion is subjected to demulsification treatment; the mixed emulsion after the demulsification is baked to form a dough forming the dough-like material to form the green substrate.
  • performing vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate includes: covering the opposite upper and lower surfaces of the composite substrate with a preset Thick copper foil; put the composite substrate covered with copper foil into a mold or a hot press; vacuum sinter the composite substrate covered with copper foil at a preset sintering temperature and a preset hot pressing pressure to form The composite dielectric copper clad laminate.
  • the preset sintering temperature ranges from 360°C to 400°C.
  • the fluorine-containing material is one of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether.
  • the ceramic filling material is at least two or a combination of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
  • the temperature range for pre-sintering the green substrate is 240° C. to 320° C.
  • the time range for the pre-sintering is 2h-12h.
  • another technical solution adopted by the present invention is to provide a printed circuit board, the printed circuit board comprising the composite dielectric copper clad laminate prepared by any of the above preparation methods.
  • the present invention provides a preparation method and a printed circuit board of a composite dielectric copper clad laminate, by adjusting the content of the ceramic filling material in the composite material and the sintering process of the composite dielectric copper clad laminate , which can effectively reduce the thermal expansion coefficient of the composite dielectric copper clad laminate, making it equivalent to the thermal expansion coefficient of copper foil.
  • FIG. 1 is a schematic flowchart of an embodiment of a method for preparing a composite dielectric copper clad laminate of the present invention.
  • FIG. 2 is a schematic flowchart of an embodiment of step S100 in FIG. 1 of the present invention.
  • FIG. 3 is a schematic flowchart of an embodiment of step S300 in FIG. 1 of the present invention.
  • FIG. 4 is a schematic diagram of a thermal expansion coefficient curve in the first embodiment of the present invention.
  • FIG. 5 is a schematic diagram of a thermal expansion coefficient curve in the second embodiment of the present invention.
  • FIG. 1 is a schematic flowchart of an embodiment of a method for preparing a composite dielectric copper clad laminate according to the present invention. As shown in FIG. 1 , the method for preparing a composite dielectric copper clad laminate provided by the present invention specifically includes the following steps.
  • a green substrate by using an emulsion of a fluorine-containing material and at least two ceramic filling materials, the sum of the weight of the fluorine-containing material and the at least two ceramic filling materials is 100 parts by weight, wherein the fluorine-containing material is 20-60 parts by weight , the at least two ceramic filling materials include a first ceramic filling material and a second ceramic filling material, the first ceramic filling material is 1-5 parts by weight, and the second ceramic filling material is 40-70 weight parts.
  • the fluorine-containing material provided in the present invention may specifically be one of polytetrafluoroethylene (PTFE), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PAVE).
  • PTFE polytetrafluoroethylene
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkyl vinyl ether
  • the ceramic filling material in the embodiment of the present invention is at least two or a combination of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
  • two ceramic filling materials are included, namely, a first ceramic filling material and a second ceramic filling material.
  • the dielectric constant of the first ceramic filling material needs to be greater than 30, and the dielectric constant of the second ceramic filling material needs to be less than 30. Therefore, in the embodiment of the present invention, the first ceramic filling material is titanium dioxide, and the second ceramic filling material is silicon dioxide, especially fused amorphous silicon dioxide.
  • the sum of the weights of the fluorine-containing material and the at least two ceramic filling materials in the embodiment of the present invention satisfies a preset weight value, that is, the polytetrafluoroethylene emulsion, the first ceramic filling material (titanium dioxide), the second ceramic filling material
  • the filler material silicon dioxide
  • the fluorine-containing material is 20-60 parts by weight, specifically 20 parts by weight, 40 parts by weight, 60 parts by weight, etc., which are not specifically limited here.
  • the fluorine-containing material may be 30-50 parts by weight, specifically 30 parts by weight, 40 parts by weight, 50 parts by weight, and the like.
  • the first ceramic filling material is 1-5 parts by weight, specifically 1 part by weight, 3 parts by weight, 5 parts by weight, etc., and in a preferred embodiment of the present invention, the first ceramic filling material can be 2-4 parts by weight, Specifically, it may be 2 parts by weight, 3 parts by weight, 4 parts by weight, or the like.
  • the second ceramic filling material is 40-70 parts by weight, specifically 40 parts by weight, 55 parts by weight, 70 parts by weight, etc., and in a preferred embodiment of the present invention, the second ceramic filling material can be 45-65 parts by weight, Specifically, it can be 45 parts by weight, 55 parts by weight, 65 parts by weight, etc., which is not specifically limited here.
  • step S100 is a schematic flowchart of an embodiment of step S100 of the present invention. As shown in FIG. 2 , step S100 further includes the following sub-steps.
  • a preset amount of the emulsion of the fluorine-containing material (the fluorine-containing material in the embodiment of the present invention is all tetrafluoroethylene) is added to a container equipped with a mechanical stirrer and fully stirred, wherein the stirring time is in the range of 20-60min, Specifically, it can be 20min, 40min, 60min, etc., which is not specifically limited here.
  • the amount of the fluorine-containing material in the present invention can be selectively added according to the above weight range, which is not specifically limited here.
  • the first ceramic filler material is slowly added to the emulsion of the fluorine-containing material, and the mixture is fully stirred until uniform.
  • the first ceramic filling material may be hydrophobic titanium dioxide, and the predetermined amount thereof may be sufficient.
  • the optional addition is carried out in the above-mentioned weight range.
  • a preset amount of the second ceramic filling material is slowly added into the emulsion after stirring evenly, and the mixture is fully stirred for 2-5 hours to make the emulsion and the ceramic filling material evenly mixed to form a mixed emulsion.
  • the preset amount of the second ceramic filling material can be selectively added according to the above-mentioned weight range.
  • demulsification refers to the complete destruction of the emulsion to become two phases that are immiscible, which is essentially to eliminate the stabilization conditions of the emulsion, to aggregate the dispersed droplets, layering process.
  • demulsification methods There are many types of demulsification methods.
  • the demulsification treatment of the mixed emulsion can be realized, and the preset amount of ethanol can be 10-20 weight parts, specifically 10 parts by weight, 15 parts by weight, 20 parts by weight, etc., which are not specifically limited here.
  • the demulsification mixed emulsion is placed in an oven, and baked within a preset temperature range, so that the mixed emulsion forms a dough-like material.
  • the preset temperature range of the oven is 100-120°C, specifically 100°C, 110°C, 120°C, etc., which is not specifically limited here.
  • the above-mentioned lump material is put into a two-roll mill or a calender, and the substrate is formed according to a certain temperature and roll speed, and at the same time, the distance between the rolls is adjusted to make the thickness of the green substrate made uniform.
  • pre-firing treatment is performed on the green substrate to sufficiently exclude stabilizers, surfactants, etc. contained in the tetrafluoroethylene emulsion itself, thereby forming a composite substrate.
  • the temperature range of the calcination is 240-320°C, specifically 240°C, 280°C, 320°C, etc., and in a preferred embodiment of the present invention, the range of the calcination temperature can be selected to be 260-290°C, 260°C, 275°C, 290°C, etc., which are not specifically limited here.
  • the time range of pre-burning is 2-12h, specifically 2h, 7h, 12h, etc. In a preferred embodiment of the present invention, the time range of this pre-burning can be selected to be 3-8h, specifically 3h, 5.5h, 8h and the like are not specifically limited here.
  • FIG. 3 is a schematic flowchart of an embodiment of step S300 of the present invention. As shown in FIG. 3 , step S300 further includes the following sub-steps.
  • the opposite upper and lower surfaces of the composite substrate are covered with a predetermined thickness of copper foil.
  • the preset thickness of the copper foil may be 10 ⁇ m-40 ⁇ m, and specifically may be 12 ⁇ m, 18 ⁇ m, 35 ⁇ m, and the like.
  • the preset thickness of the copper foil is preferably 18 ⁇ m-35 ⁇ m, and may be 18 ⁇ m, 35 ⁇ m, or 18 ⁇ m, which is not specifically limited here.
  • the copper foil-covered composite substrate is placed into a specific mold or heat press.
  • the composite substrate covered with copper foil is vacuum sintered at a preset sintering temperature and a preset hot pressing pressure at a certain time and temperature to obtain a composite dielectric copper clad laminate.
  • the preset sintering temperature in the present invention is greater than the melting point of the fluorine-containing material and less than the decomposition temperature of the fluorine-containing material.
  • the preset sintering temperature range may be 360°C-400°C, specifically 360°C, 380°C, 400°C, etc., and in a preferred embodiment of the present invention, the preset sintering temperature range may be 370°C-400°C 390°C, specifically 370°C, 380°C, 390°C, etc., which are not specifically limited here.
  • the melting point of tetrafluoroethylene is between 320°C and 345°C, so the sintering temperature of tetrafluoroethylene is higher than 345°C, and its decomposition temperature is about 400°C. The sintering temperature should not exceed 400°C.
  • the preset hot-pressing pressure range is 5Mpa-20Mpa, specifically 5Mpa, 12.5Mpa, 20Mpa, etc.
  • the preset hot-pressing pressure range can be selected 8Mpa-15Mpa, specifically 8Mpa , 11.5Mpa, 15Mpa, etc., which are not specifically limited here.
  • the sintering time range is 1-8h, specifically 1h, 4.5h, 8h, etc., and in the preferred embodiment of the present invention, the sintering time can be 2-6h, specifically 2h, 4h, 6h, etc., There is no specific limitation here.
  • the thermal expansion coefficient of the composite dielectric copper clad laminate can be effectively reduced to be equivalent to that of the copper foil.
  • PTFE tetrafluoroethylene
  • the copper foil is put into a hot press, the sintering temperature is adjusted to 380° C., the sintering hot pressing pressure is 15Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 1 .
  • PTFE tetrafluoroethylene
  • the copper foil is put into a hot press, the sintering temperature is adjusted to 380° C., the sintering hot pressing pressure is 10Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 2 .
  • PTFE tetrafluoroethylene
  • the copper foil is put into a hot press, and the sintering temperature is adjusted to 360° C., the sintering hot pressing pressure is 10Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 3 .
  • Table 1 is a comparison diagram of the Coefficient of Thermal Expansion (CTE) of the composite dielectric copper clad laminates obtained by the preparation methods of Examples 1 to 3 of the present invention, where TD represents the transverse direction and MD represents the longitudinal direction.
  • CTE Coefficient of Thermal Expansion
  • FIG. 4 is a schematic diagram of the thermal expansion coefficient curve in the first embodiment of the present invention
  • FIG. 5 is a schematic diagram of the thermal expansion coefficient curve in the second embodiment of the present invention.
  • the thermal expansion coefficient of the composite dielectric copper clad laminate can be effectively reduced to be equivalent to that of the copper foil.
  • the present invention also provides a printed circuit board, the printed circuit board includes the composite dielectric copper clad laminate prepared by the preparation method in the embodiment of the present invention, and the detailed preparation process and strength peeling test of the composite dielectric copper clad laminate are detailed above. The specific description of the implementation manner will not be repeated here.
  • the present invention provides a method for preparing a composite dielectric copper clad laminate and a printed circuit board.
  • the composite dielectric copper clad laminate can be effectively reduced.
  • the thermal expansion coefficient is equivalent to that of copper foil.

Abstract

A preparation method for a composite dielectric copper-clad substrate, and a printed circuit board. The preparation method comprises: forming a substrate green body by means of an emulsion of a fluorine-containing material and at least two types of ceramic filler materials, the total amount of the fluorine-containing material and the at least two types of ceramic filler materials being 100 parts by weight, the amount of the fluorine-containing material being 20-60 parts by weight, the at least two types of ceramic filler materials comprising a first ceramic filler material and a second ceramic filler material, the amount of the first ceramic filler material being 1-5 parts by weight, and the amount of the second ceramic filler material being 40-70 parts by weight; performing pre-sintering treatment on the substrate green body to form a composite substrate; and performing vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form a composite dielectric copper-clad substrate, the preset sintering temperature being higher than the melting point of the fluorine-containing material and lower than the decomposition temperature of the fluorine-containing material, and the preset hot pressing pressure ranging from 5 MPa to 20 MPa. By means of the implementation method, the coefficient of thermal expansion of the composite dielectric copper-clad substrate can be effectively reduced to be equivalent to that of a copper foil.

Description

复合介质覆铜板的制备方法及印刷线路板Preparation method of composite dielectric copper clad laminate and printed circuit board 技术领域technical field
本发明涉及复合介质覆铜板制备的技术领域，特别是涉及一种复合介质覆铜板的制备方法及印刷线路板。The invention relates to the technical field of the preparation of composite dielectric copper clad laminates, in particular to a preparation method of composite dielectric copper clad laminates and a printed circuit board.
背景技术Background technique
随着5G时代的来临，电子产品的发展趋向多功能化，零部件不断向轻、薄、短、小等方向发展，尤其是高密度集成电路技术的广泛应用，对民用电子产品提出高性能化、高可靠性和高安全性的要求；对工业用电子产品提出技术性能良好、低成本、高能耗的要求。With the advent of the 5G era, the development of electronic products tends to be multi-functional, and parts and components continue to develop in the direction of light, thin, short, and small, especially the wide application of high-density integrated circuit technology. , high reliability and high safety requirements; put forward the requirements of good technical performance, low cost and high energy consumption for industrial electronic products.
聚四氟乙烯(Polytetrafluoroethylene，简称PTFE)具有优异的微波性能，其介电常数(εr)为2.0～2.2，介电损耗(tanδ)0.0002~0.0003，且具有良好的化学稳定性和热稳定性，适用于高频微波电路。以PTFE树脂为基体复合精细电子陶瓷制备的复合介质，由于具有优异的高频介电性能，低成本金属化，电路加工与安装方便及在振动场合使用不易破碎等一系列优点，深受微波电路设计专家们的青睐。Polytetrafluoroethylene (PTFE) has excellent microwave performance, its dielectric constant (εr) is 2.0~2.2, dielectric loss (tanδ) is 0.0002~0.0003, and it has good chemical stability and thermal stability. Suitable for high frequency microwave circuits. The composite medium prepared by compounding fine electronic ceramics with PTFE resin as the matrix has a series of advantages such as excellent high-frequency dielectric properties, low-cost metallization, convenient circuit processing and installation, and is not easy to be broken when used in vibration occasions. Favored by design experts.
目前，玻璃纤维布浸渍PTFE乳液得到的复合介质基板是最普通、用量最广的产品，它具有较好的尺寸稳定性和较低的制造成本，但是因为玻纤布自身的介电常数较低，所以得到的玻纤增强PTFE基板其介电常数并不高，约在2.3-2.8之间，要想得到较高介电常数的复合材料需要掺杂高介电常数的陶瓷粉末。同时，由于玻纤布含有较多的金属氧化物，金属盐类杂质，所以其复合基板的介电损耗亦较高。由于金属衬底具有较低的热膨胀系数，其中又以铜金属衬底最为常见，而Cu的CTE（热膨胀系数）为16 ppm/℃，同时PTFE具有高达109 ppm/℃的线膨胀系数。为了保证微波器件的安装以及使用的可靠性，复合材料基板与金属衬底的结合性能的好坏成为关键因素，二者之间在热冲击下的应力大小决定了它们结合性能的重要因素之一。为了减小复合材料基板与金属衬底之间的应力，提高覆铜板的耐热冲击性，提高其爆板温度，避免覆铜板翘起、起泡、脱落等破坏性行为，就必须保证基板与金属箔之间具有相当的热膨胀系数。At present, the composite dielectric substrate obtained by impregnating glass fiber cloth with PTFE emulsion is the most common and widely used product. It has good dimensional stability and low manufacturing cost, but because the dielectric constant of glass fiber cloth itself is relatively low , so the dielectric constant of the obtained glass fiber reinforced PTFE substrate is not high, about 2.3-2.8. In order to obtain a composite material with a higher dielectric constant, it is necessary to dope ceramic powder with a high dielectric constant. At the same time, because the glass fiber cloth contains more metal oxides and metal salt impurities, the dielectric loss of the composite substrate is also high. Due to the low thermal expansion coefficient of metal substrates, copper metal substrates are the most common, while the CTE (coefficient of thermal expansion) of Cu is 16 ppm/°C, while PTFE has a linear expansion coefficient of up to 109 ppm/°C. In order to ensure the reliability of the installation and use of microwave devices, the bonding performance between the composite substrate and the metal substrate becomes a key factor, and the stress between the two under thermal shock determines one of the important factors for their bonding performance. . In order to reduce the stress between the composite substrate and the metal substrate, improve the thermal shock resistance of the copper clad laminate, increase the temperature of its explosion, and avoid destructive behaviors such as warping, blistering, and falling off of the copper clad laminate, it is necessary to ensure that the substrate and the Metal foils have comparable thermal expansion coefficients.
技术问题technical problem
本发明主要是提供一种复合介质覆铜板的制备方法及印刷线路板，能够解决现有技术中通过玻璃纤维布浸渍PTFE乳液得到的复合介质铜覆基板的热膨胀系数高于铜箔的热膨胀系数，不利于后道工艺加工以及器件在较高的温度下使用的问题。The invention mainly provides a preparation method and a printed circuit board of a composite medium copper clad plate, which can solve the problem that the thermal expansion coefficient of the composite medium copper clad substrate obtained by impregnating the PTFE emulsion with glass fiber cloth in the prior art is higher than that of the copper foil. It is not conducive to subsequent process processing and the use of devices at higher temperatures.
技术解决方案technical solutions
为解决上述技术问题，本发明采用的一个技术方案是：提供一种复合介质覆铜板的制备方法，所述制备方法包括：通过含氟材料的乳液及至少两种陶瓷填充材料形成基板生坯，所述含氟材料和所述至少两种陶瓷填充材料的份量之和为100重量份，其中，所述含氟材料为20-60重量份，所述至少两种陶瓷填充材料包括第一陶瓷填充材料及第二陶瓷填充材料，所述第一陶瓷填充材料为1-5重量份，所述第二陶瓷填充材料为40-70重量份；对所述基板生坯进行预烧处理以形成复合基板；以预设烧结温度及预设热压压力对所述复合基板进行真空烧结，以形成所述复合介质覆铜板；其中，所述预设烧结温度大于所述含氟材料的熔点且小于所述含氟材料的分解温度，所述预设热压压力范围为5Mpa-20Mpa。In order to solve the above-mentioned technical problems, a technical solution adopted by the present invention is to provide a preparation method of a composite dielectric copper clad laminate, the preparation method comprising: forming a green substrate by using an emulsion of a fluorine-containing material and at least two ceramic filling materials, The sum of the weight of the fluorine-containing material and the at least two ceramic filling materials is 100 parts by weight, wherein the fluorine-containing material is 20-60 weight parts, and the at least two ceramic filling materials include the first ceramic filling material Materials and a second ceramic filling material, the first ceramic filling material is 1-5 parts by weight, and the second ceramic filling material is 40-70 parts by weight; the substrate green body is pre-fired to form a composite substrate ; vacuum sintering the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate; wherein the preset sintering temperature is greater than the melting point of the fluorine-containing material and less than the The decomposition temperature of the fluorine-containing material, the preset hot pressing pressure range is 5Mpa-20Mpa.
其中，所述第一陶瓷填充材料的介电常数大于30，所述第二陶瓷填充材料的介电常数小于30。Wherein, the dielectric constant of the first ceramic filling material is greater than 30, and the dielectric constant of the second ceramic filling material is less than 30.
其中，所述通过含氟材料的乳液与至少两种陶瓷填充材料形成基板生坯包括：将预设份量的含氟材料的乳液加入容器中进行搅拌；分别将预设份量的所述第一陶瓷填充材料及所述第二陶瓷填充材料加入所述含氟材料的乳液中，以形成混合乳液；对所述混合乳液进行破乳处理；对破乳后的所述混合乳液进行烘烤以形成面团状物料；对所述面团状物料进行成型处理，以形成所述基板生坯。The forming of the green substrate by using the emulsion of the fluorine-containing material and the at least two ceramic filling materials includes: adding a preset amount of the emulsion of the fluorine-containing material into the container for stirring; respectively adding a preset amount of the first ceramic The filling material and the second ceramic filling material are added to the emulsion of the fluorine-containing material to form a mixed emulsion; the mixed emulsion is subjected to demulsification treatment; the mixed emulsion after the demulsification is baked to form a dough forming the dough-like material to form the green substrate.
其中，所述以预设烧结温度及预设热压压力对所述复合基板进行真空烧结，以形成所述复合介质覆铜板包括：在所述复合基板的相对上表面和下表面上覆盖预设厚度的铜箔；将覆盖铜箔的所述复合基板放入的模具或热压机中；以预设烧结温度及预设热压压力对所述覆盖铜箔的复合基板进行真空烧结，以形成所述复合介质覆铜板。其中，所述预设烧结温度的范围为360℃～400℃。Wherein, performing vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate includes: covering the opposite upper and lower surfaces of the composite substrate with a preset Thick copper foil; put the composite substrate covered with copper foil into a mold or a hot press; vacuum sinter the composite substrate covered with copper foil at a preset sintering temperature and a preset hot pressing pressure to form The composite dielectric copper clad laminate. Wherein, the preset sintering temperature ranges from 360°C to 400°C.
其中，所述含氟材料为聚四氟乙烯、六氟丙烯、四氟乙烯及全氟烷基乙烯基醚中的一种。Wherein, the fluorine-containing material is one of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether.
其中，所述陶瓷填充材料至少为二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的两种或组合。Wherein, the ceramic filling material is at least two or a combination of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
其中，所述对所述基板生坯进行预烧的温度范围为240℃～320℃，所述预烧的时间范围为2h-12h。Wherein, the temperature range for pre-sintering the green substrate is 240° C. to 320° C., and the time range for the pre-sintering is 2h-12h.
为解决上述技术问题，本发明采用的另一个技术方案是：提供一种印刷线路板，所述印刷线路板包括上述任一制备方法制备的复合介质覆铜板。In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a printed circuit board, the printed circuit board comprising the composite dielectric copper clad laminate prepared by any of the above preparation methods.
有益效果beneficial effect
本发明的有益效果是：区别于现有技术的情况，本发明提供一种复合介质覆铜板的制备方法及印刷线路板，通过调整复合材料中陶瓷填充材料的含量以及复合介质覆铜板的烧结工艺，能够有效的降低复合介质覆铜板的热膨胀系数，使其和铜箔的热膨胀系数相当。The beneficial effects of the present invention are: different from the situation in the prior art, the present invention provides a preparation method and a printed circuit board of a composite dielectric copper clad laminate, by adjusting the content of the ceramic filling material in the composite material and the sintering process of the composite dielectric copper clad laminate , which can effectively reduce the thermal expansion coefficient of the composite dielectric copper clad laminate, making it equivalent to the thermal expansion coefficient of copper foil.
附图说明Description of drawings
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图，其中。In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort, among which.
图1是本发明复合介质覆铜板制备方法一实施方式的流程示意图。FIG. 1 is a schematic flowchart of an embodiment of a method for preparing a composite dielectric copper clad laminate of the present invention.
图2是本发明图1中步骤S100一实施方式的流程示意图。FIG. 2 is a schematic flowchart of an embodiment of step S100 in FIG. 1 of the present invention.
图3是本发明图1中步骤S300一实施方式的流程示意图。FIG. 3 is a schematic flowchart of an embodiment of step S300 in FIG. 1 of the present invention.
图4为本发明第一实施例中热膨胀系数曲线的示意图。FIG. 4 is a schematic diagram of a thermal expansion coefficient curve in the first embodiment of the present invention.
图5为本发明第二实施例中热膨胀系数曲线的示意图。FIG. 5 is a schematic diagram of a thermal expansion coefficient curve in the second embodiment of the present invention.
本发明的实施方式Embodiments of the present invention
下面将结合本发明实施例中的附图，对本发明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发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，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他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
请一并参阅图1，图1是本发明复合介质覆铜板制备方法一实施方式的流程示意图，如图1本发明提供的复合介质覆铜板制备方法具体包括如下步骤。Please refer to FIG. 1 together. FIG. 1 is a schematic flowchart of an embodiment of a method for preparing a composite dielectric copper clad laminate according to the present invention. As shown in FIG. 1 , the method for preparing a composite dielectric copper clad laminate provided by the present invention specifically includes the following steps.
S100，通过含氟材料的乳液及至少两种陶瓷填充材料形成基板生坯，含氟材料和至少两种陶瓷填充材料的份量之和为100重量份，其中，含氟材料为20-60重量份，至少两种陶瓷填充材料包括第一陶瓷填充材料及第二陶瓷填充材料，第一陶瓷填充材料为重量份1-5，第二陶瓷填充材料为40-70重量份。S100, forming a green substrate by using an emulsion of a fluorine-containing material and at least two ceramic filling materials, the sum of the weight of the fluorine-containing material and the at least two ceramic filling materials is 100 parts by weight, wherein the fluorine-containing material is 20-60 parts by weight , the at least two ceramic filling materials include a first ceramic filling material and a second ceramic filling material, the first ceramic filling material is 1-5 parts by weight, and the second ceramic filling material is 40-70 weight parts.
其中，本发明中提供的含氟材料具体可以为聚四氟乙烯（PTFE）、六氟丙烯（HFP）、四氟乙烯（TFE）和全氟烷基乙烯基醚（PAVE）中的一种。在本发明具体实施方式中，以该含氟材料为聚四氟乙烯（PTFE）为例详细介绍本发明复合介质覆铜板的制备方法，且以剩余含氟材料的为原料制造复合介质覆铜板的方法和本实施例的制备方法类似，此处不再赘述。The fluorine-containing material provided in the present invention may specifically be one of polytetrafluoroethylene (PTFE), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PAVE). In the specific embodiment of the present invention, the preparation method of the composite dielectric copper clad laminate of the present invention is described in detail by taking the fluorine-containing material as polytetrafluoroethylene (PTFE) as an example, and the method of manufacturing the composite dielectric copper clad laminate using the remaining fluorine-containing material as raw material The method is similar to the preparation method of this embodiment, and will not be repeated here.
可选地，本发明实施例中的陶瓷填充材料至少为二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的两种或组合。在本发明具体实施方式中，包括两种陶瓷填充材料，即第一陶瓷填充材料和第二陶瓷填充材料。其中，所述第一陶瓷填充材料的介电常数需满足大于30，所述第二陶瓷填充材料的介电常数需小于30。故，本发明实施方式中，第一陶瓷填充材料为二氧化钛，第二陶瓷填充材料为二氧化硅，尤其是熔融无定形的二氧化硅。Optionally, the ceramic filling material in the embodiment of the present invention is at least two or a combination of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide. In a specific embodiment of the present invention, two ceramic filling materials are included, namely, a first ceramic filling material and a second ceramic filling material. Wherein, the dielectric constant of the first ceramic filling material needs to be greater than 30, and the dielectric constant of the second ceramic filling material needs to be less than 30. Therefore, in the embodiment of the present invention, the first ceramic filling material is titanium dioxide, and the second ceramic filling material is silicon dioxide, especially fused amorphous silicon dioxide.
可选地，本发明实施例中含氟材料和所述至少两种陶瓷填充材料的份量之和满足预设份量值，即聚四氟乙烯乳液、第一陶瓷填充材料（二氧化钛）、第二陶瓷填充材料（二氧化硅）三者加起来为100重量份。其中，含氟材料为20-60重量份，具体可以是20重量份、40重量份、60重量份等，此处不做具体限定。且在本发明优选实施方式中，含氟材料可以为30-50重量份，具体可以为30重量份、40重量份、50重量份等。第一陶瓷填充材料为1-5重量份，具体可以是1重量份、3重量份、5重量份等，且在本发明优选实施方式中，第一陶瓷填充材料可以为2-4重量份，具体可以是2重量份、3重量份、4重量份等。第二陶瓷填充材料为40-70重量份，具体可以是40重量份、55重量份、70重量份等，且在本发明优选实施方式中，第二陶瓷填充材料可以为45-65重量份，具体可以是45重量份、55重量份、65重量份等，此处不做具体限定。Optionally, the sum of the weights of the fluorine-containing material and the at least two ceramic filling materials in the embodiment of the present invention satisfies a preset weight value, that is, the polytetrafluoroethylene emulsion, the first ceramic filling material (titanium dioxide), the second ceramic filling material The filler material (silicon dioxide) adds up to 100 parts by weight. Wherein, the fluorine-containing material is 20-60 parts by weight, specifically 20 parts by weight, 40 parts by weight, 60 parts by weight, etc., which are not specifically limited here. And in a preferred embodiment of the present invention, the fluorine-containing material may be 30-50 parts by weight, specifically 30 parts by weight, 40 parts by weight, 50 parts by weight, and the like. The first ceramic filling material is 1-5 parts by weight, specifically 1 part by weight, 3 parts by weight, 5 parts by weight, etc., and in a preferred embodiment of the present invention, the first ceramic filling material can be 2-4 parts by weight, Specifically, it may be 2 parts by weight, 3 parts by weight, 4 parts by weight, or the like. The second ceramic filling material is 40-70 parts by weight, specifically 40 parts by weight, 55 parts by weight, 70 parts by weight, etc., and in a preferred embodiment of the present invention, the second ceramic filling material can be 45-65 parts by weight, Specifically, it can be 45 parts by weight, 55 parts by weight, 65 parts by weight, etc., which is not specifically limited here.
请进一步结合图2，图2为本发明步骤S100一实施方式的流程示意图，如图2，步骤S100进一步包括如下子步骤。Please further refer to FIG. 2 , which is a schematic flowchart of an embodiment of step S100 of the present invention. As shown in FIG. 2 , step S100 further includes the following sub-steps.
S110，将预设份量的含氟材料的乳液加入容器中进行搅拌。S110, adding a preset amount of the emulsion of the fluorine-containing material into the container and stirring.
将预设份量的含氟材料的乳液（本发明实施例中的含氟材料均为四氟乙烯）加入安装有机械搅拌器的容器中进行充分搅拌，其中，该搅拌时间范围为20-60min，具体可以是20min、40min、60min等，此处不做具体限定。可选地，本发明中含氟材料份量可以按照上述的重量范围进行选择性添加，此处不做具体限定。A preset amount of the emulsion of the fluorine-containing material (the fluorine-containing material in the embodiment of the present invention is all tetrafluoroethylene) is added to a container equipped with a mechanical stirrer and fully stirred, wherein the stirring time is in the range of 20-60min, Specifically, it can be 20min, 40min, 60min, etc., which is not specifically limited here. Optionally, the amount of the fluorine-containing material in the present invention can be selectively added according to the above weight range, which is not specifically limited here.
S120，分别将预设份量的第一陶瓷填充材料及第二陶瓷填充材料加入含氟材料的乳液中，以形成混合乳液。S120, respectively adding a preset amount of the first ceramic filling material and the second ceramic filling material to the emulsion of the fluorine-containing material to form a mixed emulsion.
可选地，将第一陶瓷填充材料缓慢加入含氟材料的乳液中，充分搅拌至均匀。其中，该第一陶瓷填充材料可以为疏水性的二氧化钛，且其预设份量可以。Optionally, the first ceramic filler material is slowly added to the emulsion of the fluorine-containing material, and the mixture is fully stirred until uniform. Wherein, the first ceramic filling material may be hydrophobic titanium dioxide, and the predetermined amount thereof may be sufficient.
按照上述的重量范围进行选择性添加。The optional addition is carried out in the above-mentioned weight range.
进一步，再将预设份量的第二陶瓷填充材料缓慢加入搅拌均匀后等乳液中，充分搅拌2-5h，使得乳液和陶瓷填充材料混合均匀，以形成混合乳液。可选地，该第二陶瓷填充材料其预设份量可以按照上述的重量范围进行选择性添加。Further, a preset amount of the second ceramic filling material is slowly added into the emulsion after stirring evenly, and the mixture is fully stirred for 2-5 hours to make the emulsion and the ceramic filling material evenly mixed to form a mixed emulsion. Optionally, the preset amount of the second ceramic filling material can be selectively added according to the above-mentioned weight range.
S130，对混合乳液进行破乳处理。S130, performing demulsification treatment on the mixed emulsion.
进一步，对上述的混合乳液进行破乳处理，其中，破乳是指乳状液完全破坏，成为不相混溶的两相，其实质上就是消除乳状液稳定化条件、使分散的液滴聚集、分层的过程。破乳方法种类较多，本发明实施例中，通过在边搅拌混合乳液边缓慢加入预设份量的乙醇，能够实现对混合乳液进行破乳处理，且乙醇的预设份量可以为10-20重量份，具体可以是10重量份、15重量份、20重量份等，此处不做具体限定。Further, the above-mentioned mixed emulsion is subjected to demulsification treatment, wherein, demulsification refers to the complete destruction of the emulsion to become two phases that are immiscible, which is essentially to eliminate the stabilization conditions of the emulsion, to aggregate the dispersed droplets, layering process. There are many types of demulsification methods. In the embodiment of the present invention, by slowly adding a preset amount of ethanol while stirring the mixed emulsion, the demulsification treatment of the mixed emulsion can be realized, and the preset amount of ethanol can be 10-20 weight parts, specifically 10 parts by weight, 15 parts by weight, 20 parts by weight, etc., which are not specifically limited here.
S140，对破乳后的混合乳液进行烘烤以形成团状物料。S140, baking the demulsification mixed emulsion to form a mass material.
将破乳后的混合乳液放入烤箱中，在预设温度范围内进行烘烤，以使得混合乳液形成面团状的物料。其中，烤箱的预设温度范围为100-120℃，具体可以是100℃、110℃、120℃等，此处不做具体限定。The demulsification mixed emulsion is placed in an oven, and baked within a preset temperature range, so that the mixed emulsion forms a dough-like material. The preset temperature range of the oven is 100-120°C, specifically 100°C, 110°C, 120°C, etc., which is not specifically limited here.
S150，对团状物料进行成型处理，以形成基板生坯。S150 , performing a molding process on the agglomerated material to form a green substrate.
进一步，将上述的团状物料放入双辊开炼机或压延机上，按照一定的温度和辊速进行基板的成型，同时调整辊间距使得制成的基板生坯的厚度均匀一致。Further, the above-mentioned lump material is put into a two-roll mill or a calender, and the substrate is formed according to a certain temperature and roll speed, and at the same time, the distance between the rolls is adjusted to make the thickness of the green substrate made uniform.
S200，对基板生坯进行预烧处理以形成复合基板。S200 , pre-sintering the green substrate to form a composite substrate.
进一步，对基板生坯进行预烧处理，以充分排除四氟乙烯乳液自身含有的稳定剂、表面活性剂等，从而形成复合基板。其中，该预烧的温度范围为240-320℃，具体可以是240℃、280℃、320℃等，且在本发明优选实施方式中，该预烧温度的范围可以选择为260-290℃，260℃、275℃、290℃等，此处不做具体限定。其中预烧的时间范围为2-12h，具体可以是2h、7h、12h等，在本发明优选实施方式中，该预烧的时间范围可以选择为3-8h，具体可以是3h、5.5h、8h等此处不做具体限定。Further, pre-firing treatment is performed on the green substrate to sufficiently exclude stabilizers, surfactants, etc. contained in the tetrafluoroethylene emulsion itself, thereby forming a composite substrate. Wherein, the temperature range of the calcination is 240-320°C, specifically 240°C, 280°C, 320°C, etc., and in a preferred embodiment of the present invention, the range of the calcination temperature can be selected to be 260-290°C, 260°C, 275°C, 290°C, etc., which are not specifically limited here. The time range of pre-burning is 2-12h, specifically 2h, 7h, 12h, etc. In a preferred embodiment of the present invention, the time range of this pre-burning can be selected to be 3-8h, specifically 3h, 5.5h, 8h and the like are not specifically limited here.
S300，以预设烧结温度及预设热压压力对复合基板进行真空烧结，以形成复合介质覆铜板。S300, vacuum sintering the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form a composite dielectric copper clad laminate.
进一步结合图3，图3为本发明步骤S300一实施方式的流程示意图，如图3，步骤S300进一步包括如下子步骤。Further referring to FIG. 3 , FIG. 3 is a schematic flowchart of an embodiment of step S300 of the present invention. As shown in FIG. 3 , step S300 further includes the following sub-steps.
S310，在复合基板的相对上表面和下表面上覆盖预设厚度的铜箔。S310 , covering the opposite upper and lower surfaces of the composite substrate with copper foils of a preset thickness.
可选地，在复合基板的相对上表面和下表面上覆盖预设厚度的铜箔。本发明实施例中，铜箔的预设厚度可以为10μm-40μm，具体可以是12μm、18μm、35μm等。在本发明一具体实施方式中，铜箔的预设厚度优选为18μm-35μm，具体可以为18μm、35μm、，此处不做具体限定。Optionally, the opposite upper and lower surfaces of the composite substrate are covered with a predetermined thickness of copper foil. In the embodiment of the present invention, the preset thickness of the copper foil may be 10 μm-40 μm, and specifically may be 12 μm, 18 μm, 35 μm, and the like. In a specific embodiment of the present invention, the preset thickness of the copper foil is preferably 18 μm-35 μm, and may be 18 μm, 35 μm, or 18 μm, which is not specifically limited here.
S310，将覆盖铜箔的复合基板放入的模具或热压机中。S310, put the composite substrate covered with copper foil into a mold or a hot press.
将覆盖铜箔的复合基板放入特定的模具或热压机中。The copper foil-covered composite substrate is placed into a specific mold or heat press.
S310，以预设烧结温度及预设热压压力对覆盖铜箔的复合基板进行真空烧结，以形成复合介质覆铜板。S310 , vacuum sintering the composite substrate covered with the copper foil at a preset sintering temperature and a preset hot pressing pressure to form a composite dielectric copper clad laminate.
可选地，覆盖铜箔的复合基板以预设烧结温度及预设热压压力在一定的时间和温度下做真空烧结，得到复合介质覆铜板。本发明中的预设烧结温度大于含氟材料的熔点且小于含氟材料的分解温度。具体地，该预设烧结温度范围可以为360℃-400℃，具体可以是360℃、380℃、400℃等，且在本发明优选实施方式中，该预设烧结温度范围可以为370℃-390℃，具体可以是370℃、380℃、390℃等，此处不做具体限定。具体到本发明具体实施方式中，四氟乙烯的熔点在320℃-345℃之间，因此四氟乙烯的烧结温度要大于345℃，而其分解温度约在400℃，因此四氟乙烯的预设烧结温度不能超过400℃。Optionally, the composite substrate covered with copper foil is vacuum sintered at a preset sintering temperature and a preset hot pressing pressure at a certain time and temperature to obtain a composite dielectric copper clad laminate. The preset sintering temperature in the present invention is greater than the melting point of the fluorine-containing material and less than the decomposition temperature of the fluorine-containing material. Specifically, the preset sintering temperature range may be 360°C-400°C, specifically 360°C, 380°C, 400°C, etc., and in a preferred embodiment of the present invention, the preset sintering temperature range may be 370°C-400°C 390°C, specifically 370°C, 380°C, 390°C, etc., which are not specifically limited here. Specifically in the specific embodiment of the present invention, the melting point of tetrafluoroethylene is between 320°C and 345°C, so the sintering temperature of tetrafluoroethylene is higher than 345°C, and its decomposition temperature is about 400°C. The sintering temperature should not exceed 400°C.
进一步，预设热压压力范围为5Mpa-20Mpa，具体可以是5Mpa、12.5Mpa、20Mpa等，在本发明优选实施方式中，该预设热压压力范围可以选择为8Mpa-15Mpa，具体可以是8Mpa、11.5Mpa、15Mpa等，此处不做具体限定。且本发明中烧结时间范围为1-8h，具体可以是1h、4.5h、8h等，且在本发明优选实施方式中该烧结时间可以为2-6h，具体可以是2h、4h、6h等，此处不做具体限定。Further, the preset hot-pressing pressure range is 5Mpa-20Mpa, specifically 5Mpa, 12.5Mpa, 20Mpa, etc. In a preferred embodiment of the present invention, the preset hot-pressing pressure range can be selected 8Mpa-15Mpa, specifically 8Mpa , 11.5Mpa, 15Mpa, etc., which are not specifically limited here. And in the present invention, the sintering time range is 1-8h, specifically 1h, 4.5h, 8h, etc., and in the preferred embodiment of the present invention, the sintering time can be 2-6h, specifically 2h, 4h, 6h, etc., There is no specific limitation here.
可选地，采用本发明制备方法制备的复合介质覆铜板具有优异的介电性能（介电常数从2.1以上可调，介电损耗tanδ=0.002, 1GHz），吸水率低（<0.03%），导热系数较高（>0.5 W/mk）。Optionally, the composite dielectric copper clad laminate prepared by the preparation method of the present invention has excellent dielectric properties (dielectric constant can be adjusted from above 2.1, dielectric loss tanδ=0.002, 1GHz), low water absorption (<0.03%), High thermal conductivity (>0.5 W/mk).
上述实施方式中，通过调整复合材料中陶瓷填充材料的含量以及复合介质覆铜板的烧结工艺，能够有效的降低复合介质覆铜板的热膨胀系数，使其和铜箔的热膨胀系数相当。In the above embodiment, by adjusting the content of ceramic filler in the composite material and the sintering process of the composite dielectric copper clad laminate, the thermal expansion coefficient of the composite dielectric copper clad laminate can be effectively reduced to be equivalent to that of the copper foil.
进一步结合本发明具体实施方式详细介绍。Further detailed description will be given in conjunction with the specific embodiments of the present invention.
实施例1。Example 1.
复合介质覆铜板的制备，称量38重量份的四氟乙烯（PTFE）乳液加入容器中，搅拌20-60min，称量2重量份的TiO2和60重量份的SiO2粉末，加入PTFE乳液中，搅拌2-5h至均匀，然后滴加10-20重量份的乙醇使其破乳，对该破乳面团状物料在100-120℃下的烘箱中烘烤，去除部分水份和乙醇。对烘烤到一定程度的物料进行压延成具有较薄厚度的基板生坯薄片，对该基板生坯在260-290℃下预烧3-8h得到复合基板，对预烧后的复合基板上下覆盖铜箔放进热压机中，调节烧结温度至380℃、烧结的热压压力为15Mpa以及调节烧结时间为2-4h对复合基板进行真空烧结以得到复合介质覆铜板1。For the preparation of composite medium copper clad laminate, weigh 38 parts by weight of tetrafluoroethylene (PTFE) emulsion into the container, stir for 20-60 min, weigh 2 parts by weight of TiO2 and 60 parts by weight of SiO2 powder, add it to the PTFE emulsion, stir 2-5h until uniform, then dropwise add 10-20 parts by weight of ethanol to make it demulsification, bake the demulsification dough-like material in an oven at 100-120°C to remove part of the water and ethanol. Calender the material baked to a certain extent into a green substrate sheet with a thinner thickness, pre-sinter the green substrate at 260-290 ° C for 3-8 hours to obtain a composite substrate, and cover the pre-fired composite substrate up and down The copper foil is put into a hot press, the sintering temperature is adjusted to 380° C., the sintering hot pressing pressure is 15Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 1 .
实施例2。Example 2.
复合介质覆铜板的制备，称量48重量份的四氟乙烯（PTFE）乳液加入容器中，搅拌20-60min，称量4重量份的TiO2和48重量份的SiO2粉末，加入PTFE乳液中，搅拌2-5h至均匀，然后滴加10-20重量份的乙醇使其破乳，对该破乳面团状物料在100-130℃下的烘箱中烘烤，去除部分水份和乙醇。对烘烤到一定程度的物料进行压延成具有较薄厚度的基板生坯薄片，对该基板生坯在260-290℃下预烧3-8h得到复合基板，对预烧后的复合基板上下覆盖铜箔放进热压机中，调节烧结温度至380℃、烧结的热压压力为10Mpa以及调节烧结时间为2-4h对复合基板进行真空烧结以得到复合介质覆铜板2。For the preparation of composite medium copper clad laminate, weigh 48 parts by weight of tetrafluoroethylene (PTFE) emulsion into the container, stir for 20-60min, weigh 4 parts by weight of TiO2 and 48 parts by weight of SiO2 powder, add it to the PTFE emulsion, stir 2-5h until uniform, then dropwise add 10-20 parts by weight of ethanol to make it demulsification, bake the demulsification dough-like material in an oven at 100-130°C to remove part of the water and ethanol. Calender the material baked to a certain extent into a green substrate sheet with a thinner thickness, pre-sinter the green substrate at 260-290 ° C for 3-8 hours to obtain a composite substrate, and cover the pre-fired composite substrate up and down The copper foil is put into a hot press, the sintering temperature is adjusted to 380° C., the sintering hot pressing pressure is 10Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 2 .
实施例3。Example 3.
复合介质覆铜板的制备，称量38重量份的四氟乙烯（PTFE）乳液加入容器中，搅拌20-60min，称量2重量份的TiO2和60重量份的SiO2粉末，加入PTFE乳液中，搅拌2-5h至均匀，然后滴加10-20重量份的乙醇使其破乳，对该破乳面团状物料在100-130℃下的烘箱中烘烤，去除部分水份和乙醇。对烘烤到一定程度的物料进行压延成具有较薄厚度的基板生坯薄片，对该基板生坯在260-290℃下预烧3-8h得到复合基板，对预烧后的复合基板上下覆盖铜箔放进热压机中，调节烧结温度至360℃、烧结的热压压力为10Mpa以及调节烧结时间为2-4h对复合基板进行真空烧结以得到复合介质覆铜板3。For the preparation of composite medium copper clad laminate, weigh 38 parts by weight of tetrafluoroethylene (PTFE) emulsion into the container, stir for 20-60 min, weigh 2 parts by weight of TiO2 and 60 parts by weight of SiO2 powder, add it to the PTFE emulsion, stir 2-5h until uniform, then dropwise add 10-20 parts by weight of ethanol to make it demulsification, bake the demulsification dough-like material in an oven at 100-130°C to remove part of the water and ethanol. Calender the material baked to a certain extent into a green substrate sheet with a thinner thickness, pre-sinter the green substrate at 260-290 ° C for 3-8 hours to obtain a composite substrate, and cover the pre-fired composite substrate up and down The copper foil is put into a hot press, and the sintering temperature is adjusted to 360° C., the sintering hot pressing pressure is 10Mpa, and the sintering time is adjusted to 2-4h, and the composite substrate is vacuum sintered to obtain a composite dielectric copper clad laminate 3 .
请结合表1，表1为本发明实施例1-实施例3的制备方式得到的复合介质覆铜板热膨胀系数（Coefficient of Thermal Expansion，CTE）的对比示意，其中TD表示横向，MD表示纵向。Please refer to Table 1. Table 1 is a comparison diagram of the Coefficient of Thermal Expansion (CTE) of the composite dielectric copper clad laminates obtained by the preparation methods of Examples 1 to 3 of the present invention, where TD represents the transverse direction and MD represents the longitudinal direction.
表1。Table 1.
Figure 849850dest_path_image001
。
Figure 849850dest_path_image001
.
其中，由表1可知实施例1-3制备的复合介质覆铜板的横向热膨胀系数CTE和纵向热膨胀系数CTE均较小。且实施例1中制备的复合介质覆铜板其热膨胀系数与铜箔的热膨胀系数相当接近。Among them, it can be seen from Table 1 that the transverse thermal expansion coefficient CTE and the longitudinal thermal expansion coefficient CTE of the composite dielectric copper clad laminates prepared in Examples 1-3 are both small. And the thermal expansion coefficient of the composite dielectric copper clad laminate prepared in Example 1 is quite close to that of the copper foil.
实施例1-2的基板性能请参见图4-图5，图4为本发明第一实施例中热膨胀系数曲线的示意图，图5为本发明第二实施例中热膨胀系数曲线的示意图。The performance of the substrate of Embodiment 1-2 is shown in FIGS. 4-5 . FIG. 4 is a schematic diagram of the thermal expansion coefficient curve in the first embodiment of the present invention, and FIG. 5 is a schematic diagram of the thermal expansion coefficient curve in the second embodiment of the present invention.
上述实施方式中，通过调整复合材料中陶瓷填充材料的含量以及复合介质覆铜板的烧结工艺，能够有效的降低复合介质覆铜板的热膨胀系数，使其和铜箔的热膨胀系数相当。In the above embodiment, by adjusting the content of ceramic filler in the composite material and the sintering process of the composite dielectric copper clad laminate, the thermal expansion coefficient of the composite dielectric copper clad laminate can be effectively reduced to be equivalent to that of the copper foil.
可选地，本发明还提供一种印刷线路板，该印刷电路板包括本发明实施例中制备方法制备的复合介质覆铜板，且该复合介质覆铜板的详细制备过程以及强度剥离测试详见上述实施方式的具体描述，此处不再赘述。Optionally, the present invention also provides a printed circuit board, the printed circuit board includes the composite dielectric copper clad laminate prepared by the preparation method in the embodiment of the present invention, and the detailed preparation process and strength peeling test of the composite dielectric copper clad laminate are detailed above. The specific description of the implementation manner will not be repeated here.
区别于现有技术，本发明提供一种复合介质覆铜板的制备方法及印刷线路板，通过调整复合材料中陶瓷填充材料的含量以及复合介质覆铜板的烧结工艺，能够有效的降低复合介质覆铜板的热膨胀系数，使其和铜箔的热膨胀系数相当。Different from the prior art, the present invention provides a method for preparing a composite dielectric copper clad laminate and a printed circuit board. By adjusting the content of the ceramic filling material in the composite material and the sintering process of the composite dielectric copper clad laminate, the composite dielectric copper clad laminate can be effectively reduced. The thermal expansion coefficient is equivalent to that of copper foil.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above descriptions are only the embodiments of the present invention, and are not intended to limit the scope of the present invention. Any equivalent structure or equivalent process transformation made by using the contents of the description and drawings of the present invention, or directly or indirectly applied to other related technologies Fields are similarly included in the scope of patent protection of the present invention.

Claims (9)

  1. 一种复合介质覆铜板的制备方法，其特征在于，所述制备方法包括：A preparation method of a composite dielectric copper clad laminate, characterized in that the preparation method comprises:
    通过含氟材料的乳液及至少两种陶瓷填充材料形成基板生坯，所述含氟材料和所述至少两种陶瓷填充材料的份量之和为100重量份，其中，所述含氟材料为20-60重量份，所述至少两种陶瓷填充材料包括第一陶瓷填充材料及第二陶瓷填充材料，所述第一陶瓷填充材料为1-5重量份，所述第二陶瓷填充材料为40-70重量份；A green substrate is formed by an emulsion of a fluorine-containing material and at least two kinds of ceramic filling materials, the sum of the weight of the fluorine-containing material and the at least two kinds of ceramic filling materials is 100 parts by weight, wherein the fluorine-containing material is 20 parts by weight -60 parts by weight, the at least two ceramic filling materials include a first ceramic filling material and a second ceramic filling material, the first ceramic filling material is 1-5 weight parts, and the second ceramic filling material is 40- 70 parts by weight;
    对所述基板生坯进行预烧处理以形成复合基板；pre-firing the green substrate to form a composite substrate;
    以预设烧结温度及预设热压压力对所述复合基板进行真空烧结，以形成所述复合介质覆铜板；vacuum sintering the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate;
    其中，所述预设烧结温度大于所述含氟材料的熔点且小于所述含氟材料的分解温度，所述预设热压压力范围为5Mpa-20Mpa。Wherein, the preset sintering temperature is greater than the melting point of the fluorine-containing material and less than the decomposition temperature of the fluorine-containing material, and the preset hot pressing pressure range is 5Mpa-20Mpa.
  2. 根据权利要求1所述的制备方法，其特征在于，所述第一陶瓷填充材料的介电常数大于30，所述第二陶瓷填充材料的介电常数小于30。The preparation method according to claim 1, wherein the dielectric constant of the first ceramic filling material is greater than 30, and the dielectric constant of the second ceramic filling material is less than 30.
  3. 根据权利要求2所述的制备方法，其特征在于，所述通过含氟材料的乳液及至少两种陶瓷填充材料形成基板生坯包括：The preparation method according to claim 2, wherein the forming of the green substrate by using an emulsion of a fluorine-containing material and at least two ceramic filling materials comprises:
    将预设份量的含氟材料的乳液加入容器中进行搅拌；Add a preset amount of the emulsion of the fluorine-containing material into the container and stir;
    分别将预设份量的第一陶瓷填充材料及第二陶瓷填充材料加入所述含氟材料的乳液中，以形成混合乳液；respectively adding a preset amount of the first ceramic filling material and the second ceramic filling material into the emulsion of the fluorine-containing material to form a mixed emulsion;
    对所述混合乳液进行破乳处理；performing demulsification treatment on the mixed emulsion;
    对破乳后的所述混合乳液进行烘烤以形成面团状物料；baking the mixed emulsion after demulsification to form a dough-like material;
    对所述面团状物料进行成型处理，以形成所述基板生坯。The dough-like material is shaped to form the green substrate.
  4. 根据权利要求1所述的制备方法，其特征在于，所述以预设烧结温度及预设热压压力对所述复合基板进行真空烧结，以形成所述复合介质覆铜板包括：The preparation method according to claim 1, wherein the vacuum sintering of the composite substrate at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate comprises:
    在所述复合基板的相对上表面和下表面上覆盖预设厚度的铜箔；Covering the opposite upper and lower surfaces of the composite substrate with copper foils of a preset thickness;
    将覆盖铜箔的所述复合基板放入的模具或热压机中；Putting the composite substrate covered with copper foil into a mold or a hot press;
    以预设烧结温度及预设热压压力对所述覆盖铜箔的复合基板进行真空烧结，以形成所述复合介质覆铜板。The composite substrate covered with copper foil is vacuum sintered at a preset sintering temperature and a preset hot pressing pressure to form the composite dielectric copper clad laminate.
  5. 根据权利要求3所述的制备方法，其特征在于，所述预设烧结温度的范围为360℃-400℃。The preparation method according to claim 3, wherein the preset sintering temperature ranges from 360°C to 400°C.
  6. 根据权利要求1所述的制备方法，其特征在于，所述含氟材料为聚四氟乙烯、六氟丙烯、四氟乙烯及全氟烷基乙烯基醚中的一种。The preparation method according to claim 1, wherein the fluorine-containing material is one of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether.
  7. 根据权利要求1所述的制备方法，其特征在于，所述陶瓷填充材料至少为二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的两种或组合。The preparation method according to claim 1, wherein the ceramic filling material is at least two of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide species or combination.
  8. 根据权利要求1所述的制备方法，其特征在于，所述对所述基板生坯进行预烧的温度范围为240℃～320℃，所述预烧的时间范围为2h-12h。The preparation method according to claim 1, wherein the temperature range for pre-firing the green substrate is 240°C to 320°C, and the time range for the pre-firing is 2h-12h.
  9. 一种印刷线路板，其特征在于，所述印刷线路板包括采用权利要求1-8中任一制备方法制备的复合介质覆铜板。A printed circuit board, characterized in that the printed circuit board comprises a composite dielectric copper clad laminate prepared by any one of the preparation methods of claims 1-8.
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