WO2023011207A1 - Low dielectric modified glass fiber, and preparation method therefor and application thereof - Google Patents

Low dielectric modified glass fiber, and preparation method therefor and application thereof Download PDF

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Publication number
WO2023011207A1
WO2023011207A1 PCT/CN2022/107113 CN2022107113W WO2023011207A1 WO 2023011207 A1 WO2023011207 A1 WO 2023011207A1 CN 2022107113 W CN2022107113 W CN 2022107113W WO 2023011207 A1 WO2023011207 A1 WO 2023011207A1
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Prior art keywords
glass fiber
modified glass
low
dielectric
dielectric modified
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PCT/CN2022/107113
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French (fr)
Chinese (zh)
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常欢
叶南飚
李皓
刘奇祥
胡志华
王超军
陈平绪
丁超
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广东金发科技有限公司
金发科技股份有限公司
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Publication of WO2023011207A1 publication Critical patent/WO2023011207A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/0203—Cooling non-optical fibres drawn or extruded from bushings, nozzles or orifices
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/183—Stirring devices; Homogenisation using thermal means, e.g. for creating convection currents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining

Definitions

  • the invention belongs to the technical field of composite materials, and in particular relates to a low-dielectric modified glass fiber and its preparation method and application.
  • Low-dielectric glass fiber is the core material of printed circuit boards, which plays a vital role in improving the electrical insulation performance of large-scale integrated circuit boards and reducing their heat generation and power consumption.
  • Indispensable engineering material In recent years, the demand for communication has been increasing, and gradually moving towards the era of 5G networks, requiring copper clad laminates to have lower dielectric constant and dielectric loss, so as to speed up signal transmission, reduce crosstalk problems, and reduce energy loss. Therefore, for further reduction The dielectric constant of glass fibers is particularly important.
  • the method of reducing the dielectric constant is to increase the content of SiO 2 , Al 2 O 3 , MgO/CaO, reduce the content of boron element, or add specific components to reduce the dielectric constant.
  • the patent CN105439453A regulates the content of each component Use and add a specific amount of ZrO to lower the dielectric constant.
  • the dielectric constant of the obtained glass fiber is between 4.28-5.05 (1MHz), which still has a certain room for improvement, which limits its application in electronic information products with high dielectric performance requirements.
  • the purpose of the present invention is to overcome the defect or deficiency of the high dielectric constant of glass fibers in the prior art, and provide a low dielectric modified glass fiber.
  • the low-dielectric modified glass fiber provided by the invention can significantly reduce the dielectric constant by adding functional oxides of a specific composition and adjusting the dosage relationship between them and SiO2 , and can be widely used in printed circuit boards.
  • Another object of the present invention is to provide a method for preparing the above-mentioned low-dielectric modified glass fiber.
  • Another object of the present invention is to provide the application of the above-mentioned low-dielectric modified glass fiber in the preparation of printed circuit boards.
  • a low-dielectric modified glass fiber comprising the following components in parts by weight:
  • the functional oxide is a mixture of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 , and the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 is 1:0.5 ⁇ 2:0.5 ⁇ 2:0.5 ⁇ 2.
  • the inventors of the present invention have found that adding specific functional oxides to glass fibers and regulating their dosage can effectively reduce the dielectric constant of glass fibers.
  • the reasons may be as follows: adding a small amount of rare earth element ions in the glass network gaps, The surrounding anionic groups play a role in accumulation, and the glass grid becomes denser. If the content is too high, too much free oxygen will be introduced to depolymerize the glass structure. Different types of rare earth oxides have different effects on the glass structure and properties. When different doping types and doping amounts are used, the effects on the dielectric constant of glass fibers may also be positive or negative.
  • the present invention screens through a large number of experiments. And summarize the data, it is found that when using several specific functional rare earth oxides and controlling their ratio and addition amount, a suitable positive accumulation effect can be achieved and the dielectric constant can be effectively reduced.
  • the low-dielectric modified glass fiber provided by the invention has a lower dielectric constant and can be widely used in printed circuit boards.
  • MgO/CaO represents one or both of MgO and CaO.
  • the R 2 O is one or more of Li 2 O, Na 2 O or K 2 O.
  • the weight part of the R 2 O is 0.1-0.8 parts.
  • the parts by weight of the MgO/CaO are 2-8 parts.
  • the weight ratio of the functional oxide to SiO 2 is 1:40-50.
  • the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 in the functional oxide is 1:0.8 ⁇ 1:0.8 ⁇ 1:0.8 ⁇ 1.
  • the low-dielectric modified glass fiber further includes 0-2 parts of other additives, more preferably 0.2-1.2 parts.
  • the other additives are one or both of Na 2 SO 4 or CaSO 4 .
  • Na 2 SO 4 , CaSO 4 can promote glass clarification.
  • the additive is Na 2 SO 4 .
  • the particle size distribution D90 of each component in the low dielectric modified glass fiber is 50-200 ⁇ m.
  • the preparation method of the above-mentioned low-dielectric modified glass fiber comprises the following steps: SiO 2 , Al 2 O 3 , B 2 O 3 , R 2 O, MgO/CaO, TiO 2 , ZnO, functional oxides and other additives ( (if any) mixing, melting, clarifying, homogenizing, molding, and shredding to obtain the low-dielectric modified glass fiber.
  • the melting treatment is carried out in a kiln, the temperature of the melting treatment is 1450-1600° C., and the time is 0.5-1 hour.
  • the melting treatment temperature is 1450-1550° C., and the time is 0.5-0.8 hours.
  • the temperature of the clarification treatment is 1450-1600° C.
  • the time is 0.5-1 hour.
  • the temperature of the homogenization treatment is 1450-1600° C.
  • the time is 0.5-1 hour.
  • the forming process is as follows: the homogenized molten fluid flows out through a 4000-hole platinum bushing, driven by a high-speed wire drawing machine, and formed into glass fibers; the drawing temperature is 1100-1250°C.
  • the wire drawing process is: using a chopping machine to cut wires, the length of which is 5-15 mm.
  • the present invention has the following beneficial effects:
  • the low-dielectric modified glass fiber provided by the invention can significantly reduce the dielectric constant by adding functional oxides of a specific composition and adjusting the dosage relationship between them and SiO2 , and can be widely used in printed circuit boards.
  • La 2 O 3 1#, lanthanum oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90 150 ⁇ m.
  • La 2 O 3 2#, lanthanum oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90 350 ⁇ m.
  • Functional oxide A1 obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8:0.8.
  • Functional oxide A2 obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:1:1:1.
  • Functional oxide A3 obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.5:2:0.5.
  • Functional oxide A4 obtained by mixing CeO 2 2#, La 2 O 3 2#, Nd 2 O 3 2# and Y 2 O 3 2# in a weight ratio of 1:2:0.5:2.
  • Functional oxide B1 obtained by mixing CeO 2 1#, La 2 O 3 1#, and Nd 2 O 3 1# in a weight ratio of 1:0.8:0.8.
  • Functional oxide B2 obtained by mixing CeO 2 1#, La 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8.
  • Functional oxide B3 obtained by mixing CeO 2 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8.
  • Functional oxide B4 obtained by mixing La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 0.8:0.8:0.8.
  • Functional oxide B5 obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.3:2.2:0.3.
  • the glass fiber provided by each embodiment and comparative example of the present invention is prepared through the following process: put each component into the mixing chamber and mix thoroughly; send it into the pool kiln and heat it at a high temperature at 1480°C to melt the glass fiber raw material; continue to maintain At this temperature, the melt is clarified and homogenized, and the treatment time is 0.5 hours; it flows out through a 4000-hole platinum bushing, driven by a high-speed wire drawing machine, and formed into glass fibers; it is cut into strands by a chopping machine, and the length is 7mm.
  • the dielectric constants of the modified glass fibers of the various embodiments of the present invention and comparative examples are measured under the condition of 1 MHz using a Keysight E4990A precision impedance tester according to ASTM D150-2011.
  • This embodiment provides a series of low-dielectric modified glass fibers, the formula of which is shown in Table 1.
  • This comparative example provides a series of glass fibers, the formulations of which are shown in Table 2.

Abstract

The present application relates to a low dielectric modified glass fiber, and a preparation method therefor and an application thereof. The low dielectric modified glass fiber contains components such as: one or two of SiO2, Al2O3, B2O3, R2O, MgO and CaO; TiO2; ZnO; and a functional oxide. The functional oxide is a mixture of CeO2, La2O3, Nd2O3 and Y2O3. According to the low dielectric modified glass fiber provided in the preparation application, the functional oxide of specific composition is added and a usage amount relationship between the functional oxide and SiO2 is regulated, such that a dielectric constant can be significantly reduced, and the low dielectric modified glass fiber can be widely applied to a printed circuit board.

Description

一种低介电改性玻璃纤维及其制备方法和应用A kind of low dielectric modified glass fiber and its preparation method and application 技术领域technical field
本发明属于复合材料技术领域，具体涉及一种低介电改性玻璃纤维及其制备方法和应用。The invention belongs to the technical field of composite materials, and in particular relates to a low-dielectric modified glass fiber and its preparation method and application.
背景技术Background technique
低介电玻璃纤维是印刷电路板的核心材料，在提高大规模集成电路板的电绝缘性能，降低其发热量和功耗方面起着至关重要的作用，是航空航天、高阶通讯等领域不可或缺的工程材料。近年来，通讯需求日益增强，逐渐走向了5G网络时代，要求覆铜板具有更低的介电常数和介电损耗，从而加快信号的传递速度，减少串扰问题，降低能量损耗，因此，对于进一步降低玻璃纤维的介电常数尤为重要。Low-dielectric glass fiber is the core material of printed circuit boards, which plays a vital role in improving the electrical insulation performance of large-scale integrated circuit boards and reducing their heat generation and power consumption. Indispensable engineering material. In recent years, the demand for communication has been increasing, and gradually moving towards the era of 5G networks, requiring copper clad laminates to have lower dielectric constant and dielectric loss, so as to speed up signal transmission, reduce crosstalk problems, and reduce energy loss. Therefore, for further reduction The dielectric constant of glass fibers is particularly important.
目前，降低介电常数的做法为提高SiO 2、Al 2O 3、MgO/CaO的含量，降低硼元素含量，或添加特定的组分来降低介电常数，例如专利CN105439453A通过调控各组分的用量及添加特定量的ZrO来降低介电常数。但其得到的玻璃纤维的介电常数在4.28～5.05(1MHz)之间，仍具有一定的提升空间，限制了其在高介电性能要求的电子信息产品中的应用。 At present, the method of reducing the dielectric constant is to increase the content of SiO 2 , Al 2 O 3 , MgO/CaO, reduce the content of boron element, or add specific components to reduce the dielectric constant. For example, the patent CN105439453A regulates the content of each component Use and add a specific amount of ZrO to lower the dielectric constant. However, the dielectric constant of the obtained glass fiber is between 4.28-5.05 (1MHz), which still has a certain room for improvement, which limits its application in electronic information products with high dielectric performance requirements.
因此，有必要开发一种具有更低介电常数的玻璃纤维以扩展其应用。Therefore, it is necessary to develop a glass fiber with a lower dielectric constant to expand its application.
发明内容Contents of the invention
本发明的目的在于克服现有技术玻璃纤维介电常数高的缺陷或不足，提供一种低介电改性玻璃纤维。本发明提供的低介电改性玻璃纤维通过添加特定组成的功能氧化物，并调控其与SiO 2的用量关系，可显著降低介电常数，可广泛应用于印刷电路板中。 The purpose of the present invention is to overcome the defect or deficiency of the high dielectric constant of glass fibers in the prior art, and provide a low dielectric modified glass fiber. The low-dielectric modified glass fiber provided by the invention can significantly reduce the dielectric constant by adding functional oxides of a specific composition and adjusting the dosage relationship between them and SiO2 , and can be widely used in printed circuit boards.
本发明的另一目的在于提供上述低介电改性玻璃纤维的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned low-dielectric modified glass fiber.
本发明的另一目的在于提供上述低介电改性玻璃纤维在制备印刷电路板中的应用。Another object of the present invention is to provide the application of the above-mentioned low-dielectric modified glass fiber in the preparation of printed circuit boards.
为实现上述发明目的，本发明采用如下技术方案：In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种低介电改性玻璃纤维，包括如下重量份数的组分：A low-dielectric modified glass fiber, comprising the following components in parts by weight:
Figure PCTCN2022107113-appb-000001
Figure PCTCN2022107113-appb-000001
Figure PCTCN2022107113-appb-000002
Figure PCTCN2022107113-appb-000002
所述功能氧化物为CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的混合物，CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的重量比比为1:0.5～2:0.5～2:0.5～2。 The functional oxide is a mixture of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 , and the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 is 1:0.5 ~2:0.5~2:0.5~2.
本发明的发明人研究发现，向玻璃纤维中添加特定的功能氧化物，并调控其用量可有效降低玻璃纤维的介电常数，其原因可能如下：添加少量稀土元素离子在玻璃网络间隙中，对周围阴离子基团起到聚积作用，玻璃网格变致密。若含量过高，则引入过多游离氧使玻璃结构发生解聚。不同稀土氧化物种类对玻璃结构和性能的影响均有不同，在不同掺杂种类和掺杂量的时候，对玻璃纤维介电常数的影响也可能是正面或负面的，本发明通过大量实验筛选并对数据进行总结，发现采用特定几种功能稀土氧化物并控制其比例和添加量时，可实现合适的正面的聚积作用，有效降低介电常数。The inventors of the present invention have found that adding specific functional oxides to glass fibers and regulating their dosage can effectively reduce the dielectric constant of glass fibers. The reasons may be as follows: adding a small amount of rare earth element ions in the glass network gaps, The surrounding anionic groups play a role in accumulation, and the glass grid becomes denser. If the content is too high, too much free oxygen will be introduced to depolymerize the glass structure. Different types of rare earth oxides have different effects on the glass structure and properties. When different doping types and doping amounts are used, the effects on the dielectric constant of glass fibers may also be positive or negative. The present invention screens through a large number of experiments. And summarize the data, it is found that when using several specific functional rare earth oxides and controlling their ratio and addition amount, a suitable positive accumulation effect can be achieved and the dielectric constant can be effectively reduced.
本发明提供的低介电改性玻璃纤维具有较低的介电常数，可广泛应用于印刷电路板中。The low-dielectric modified glass fiber provided by the invention has a lower dielectric constant and can be widely used in printed circuit boards.
应当说明的是，MgO/CaO代表MgO、CaO中的一种或两种均可。It should be noted that MgO/CaO represents one or both of MgO and CaO.
优选地，所述R 2O为Li 2O、Na 2O或K 2O中的一种或几种。 Preferably, the R 2 O is one or more of Li 2 O, Na 2 O or K 2 O.
优选地，所述R 2O的重量份数为0.1～0.8份。 Preferably, the weight part of the R 2 O is 0.1-0.8 parts.
优选地，所述MgO/CaO的重量份数为2～8份。Preferably, the parts by weight of the MgO/CaO are 2-8 parts.
优选地，所述功能氧化物和SiO 2的重量比为1:40～50。 Preferably, the weight ratio of the functional oxide to SiO 2 is 1:40-50.
优选地，所述功能氧化物中CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的重量比为1:0.8～1:0.8～1:0.8～1。 Preferably, the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 in the functional oxide is 1:0.8˜1:0.8˜1:0.8˜1.
优选地，所述低介电改性玻璃纤维还包括其它添加剂0～2份，进一步优选为0.2～1.2份。Preferably, the low-dielectric modified glass fiber further includes 0-2 parts of other additives, more preferably 0.2-1.2 parts.
更为优选地，所述其它添加剂为Na 2SO 4或CaSO 4中的一种或两种。Na 2SO 4、 CaSO 4可促进玻璃澄清。 More preferably, the other additives are one or both of Na 2 SO 4 or CaSO 4 . Na 2 SO 4 , CaSO 4 can promote glass clarification.
进一步优选地，所述添加剂为Na 2SO 4。 Further preferably, the additive is Na 2 SO 4 .
优选地，所述低介电改性玻璃纤维中各组分的粒径分布D90为50～200μm。Preferably, the particle size distribution D90 of each component in the low dielectric modified glass fiber is 50-200 μm.
上述低介电改性玻璃纤维的制备方法，包括如下步骤：将SiO 2、Al 2O 3、B 2O 3、R 2O、MgO/CaO、TiO 2、ZnO、功能氧化物和其它添加剂(如有)混合，熔融，澄清，均化，成型，切丝即得所述低介电改性玻璃纤维。 The preparation method of the above-mentioned low-dielectric modified glass fiber comprises the following steps: SiO 2 , Al 2 O 3 , B 2 O 3 , R 2 O, MgO/CaO, TiO 2 , ZnO, functional oxides and other additives ( (if any) mixing, melting, clarifying, homogenizing, molding, and shredding to obtain the low-dielectric modified glass fiber.
优选地，所述熔融处理在窑池中进行，熔融处理的温度为1450～1600℃，时间为0.5～1小时。Preferably, the melting treatment is carried out in a kiln, the temperature of the melting treatment is 1450-1600° C., and the time is 0.5-1 hour.
更为优选地，熔融处理的温度为1450～1550℃，时间为0.5～0.8小时。More preferably, the melting treatment temperature is 1450-1550° C., and the time is 0.5-0.8 hours.
优选地，所述澄清处理的温度为1450～1600℃，时间为0.5～1小时。Preferably, the temperature of the clarification treatment is 1450-1600° C., and the time is 0.5-1 hour.
优选地，所述均化处理的温度为1450～1600℃，时间为0.5～1小时。Preferably, the temperature of the homogenization treatment is 1450-1600° C., and the time is 0.5-1 hour.
优选地，所述成型处理的过程为：将均化处理后的熔融流体通过4000孔铂金漏板流出，高速拉丝机带动，成型为玻璃纤维；拉丝的温度为1100～1250℃。Preferably, the forming process is as follows: the homogenized molten fluid flows out through a 4000-hole platinum bushing, driven by a high-speed wire drawing machine, and formed into glass fibers; the drawing temperature is 1100-1250°C.
优选地，所述拉丝的过程为：利用短切机切丝，长度为5～15mm。Preferably, the wire drawing process is: using a chopping machine to cut wires, the length of which is 5-15 mm.
上述低介电改性玻璃纤维在制备印刷电路板中的应用也在本发明的保护范围内。The application of the above-mentioned low-dielectric modified glass fibers in the preparation of printed circuit boards is also within the protection scope of the present invention.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的低介电改性玻璃纤维通过添加特定组成的功能氧化物，并调控其与SiO 2的用量关系，可显著降低介电常数，可广泛应用于印刷电路板中。 The low-dielectric modified glass fiber provided by the invention can significantly reduce the dielectric constant by adding functional oxides of a specific composition and adjusting the dosage relationship between them and SiO2 , and can be widely used in printed circuit boards.
具体实施方式Detailed ways
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.
本发明各实施例及对比例选用的部分试剂说明如下：The partial reagents that each embodiment of the present invention and comparative examples select are described as follows:
SiO 2，二氧化硅，山东国化化学有限公司，粒径分布D90＝60μm。 SiO 2 , silicon dioxide, Shandong Guohua Chemical Co., Ltd., particle size distribution D90=60 μm.
Al 2O 3，CR10，中铝山东有限公司，粒径分布D90＝60μm。 Al 2 O 3 , CR10, Chalco Shandong Co., Ltd., particle size distribution D90=60 μm.
Li 2O，L122329，上海阿拉丁生化科技股份有限公司，粒径分布D90＝50μm。 Li 2 O, L122329, Shanghai Aladdin Biochemical Technology Co., Ltd., particle size distribution D90=50 μm.
B 2O 3，B108404，上海阿拉丁生化科技股份有限公司，粒径分布D90＝50μm。 B 2 O 3 , B108404, Shanghai Aladdin Biochemical Technology Co., Ltd., particle size distribution D90=50 μm.
MgO，氧化镁，邢台市镁神化工有限公司，粒径分布D90＝100μm。MgO, magnesium oxide, Xingtai Meishen Chemical Co., Ltd., particle size distribution D90 = 100 μm.
CaO，氧化钙，常熟市佳友粉体有限公司，粒径分布D90＝150μm。CaO, calcium oxide, Changshu Jiayou Powder Co., Ltd., particle size distribution D90 = 150 μm.
TiO 2，SR-240，山东东佳集团股份有限公司，粒径分布D90＝55μm。 TiO 2 , SR-240, Shandong Dongjia Group Co., Ltd., particle size distribution D90=55 μm.
ZnO，Z112847，上海阿拉丁生化科技股份有限公司，粒径分布D90＝60μm。ZnO, Z112847, Shanghai Aladdin Biochemical Technology Co., Ltd., particle size distribution D90=60 μm.
CeO 2 1#，氧化铈，山东德盛新材料有限公司，粒径分布D90＝100μm。 CeO 2 1#, cerium oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90=100 μm.
CeO 2 2#，氧化铈，北京华威锐科化工有限公司，粒径分布D90＝250μm。 CeO 2 2#, cerium oxide, Beijing Huawei Raycus Chemical Co., Ltd., particle size distribution D90=250 μm.
La 2O 31#，氧化镧，山东德盛新材料有限公司，粒径分布D90＝150μm。 La 2 O 3 1#, lanthanum oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90=150 μm.
La 2O 32#，氧化镧，山东德盛新材料有限公司，粒径分布D90＝350μm。 La 2 O 3 2#, lanthanum oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90=350 μm.
Nd 2O 31#，氧化钕，山东德盛新材料有限公司，粒径分布D90＝150μm。 Nd 2 O 3 1#, neodymium oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90=150 μm.
Nd 2O 32#，氧化钕，山东德盛新材料有限公司，粒径分布D90＝450μm。 Nd 2 O 3 2#, neodymium oxide, Shandong Desheng New Material Co., Ltd., particle size distribution D90=450 μm.
Y 2O 31#，氧化钇，淄博稀研纳米材料有限公司，粒径分布D90＝50μm。 Y 2 O 3 1#, yttrium oxide, Zibo Xiyan Nano Material Co., Ltd., particle size distribution D90=50 μm.
Y 2O 32#，氧化钇，淄博稀研纳米材料有限公司，粒径分布D90＝450μm。 Y 2 O 3 2#, yttrium oxide, Zibo Xiyan Nano Material Co., Ltd., particle size distribution D90=450 μm.
Na 2SO 4，硫酸钠，北京华威锐科化工有限公司，粒径分布D90＝180μm。 Na 2 SO 4 , sodium sulfate, Beijing Huawei Raycus Chemical Co., Ltd., particle size distribution D90 = 180 μm.
功能氧化物A1：CeO 2 1#、La 2O 31#、Nd 2O 31#和Y 2O 31#按照重量比为1:0.8:0.8:0.8混合得到。 Functional oxide A1: obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8:0.8.
功能氧化物A2：CeO 2 1#、La 2O 31#、Nd 2O 31#和Y 2O 31#按照重量比为1:1:1:1混合得到。 Functional oxide A2: obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:1:1:1.
功能氧化物A3：CeO 2 1#、La 2O 31#、Nd 2O 31#和Y 2O 31#按照重量比为1:0.5:2:0.5混合得到。 Functional oxide A3: obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.5:2:0.5.
功能氧化物A4：CeO 22#、La 2O 32#、Nd 2O 32#和Y 2O 32#按照重量比为1:2:0.5:2混合得到。 Functional oxide A4: obtained by mixing CeO 2 2#, La 2 O 3 2#, Nd 2 O 3 2# and Y 2 O 3 2# in a weight ratio of 1:2:0.5:2.
功能氧化物B1：CeO 2 1#、La 2O 31#、Nd 2O 31#按照重量比为1:0.8:0.8混合得到。 Functional oxide B1: obtained by mixing CeO 2 1#, La 2 O 3 1#, and Nd 2 O 3 1# in a weight ratio of 1:0.8:0.8.
功能氧化物B2：CeO 2 1#、La 2O 31#和Y 2O 31#按照重量比为1:0.8:0.8混合得到。 Functional oxide B2: obtained by mixing CeO 2 1#, La 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8.
功能氧化物B3：CeO 2 1#、Nd 2O 31#和Y 2O 31#按照重量比为1:0.8:0.8混合得到。 Functional oxide B3: obtained by mixing CeO 2 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.8:0.8.
功能氧化物B4：La 2O 31#、Nd 2O 31#和Y 2O 31#按照重量比为0.8:0.8:0.8混合 得到。 Functional oxide B4: obtained by mixing La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 0.8:0.8:0.8.
功能氧化物B5：CeO 2 1#、La 2O 31#、Nd 2O 31#和Y 2O 31#按照重量比为1:0.3:2.2:0.3混合得到。 Functional oxide B5: obtained by mixing CeO 2 1#, La 2 O 3 1#, Nd 2 O 3 1# and Y 2 O 3 1# in a weight ratio of 1:0.3:2.2:0.3.
本发明各实施例和对比例提供的玻璃纤维通过如下过程制备得到：将各组分加入混合仓中，充分混合；送入池窑中于1480℃下高温加热，使玻璃纤维原材料融化；继续保持该温度，熔体经过澄清、均化处理，处理时长均为0.5小时；通过4000孔铂金漏板流出，高速拉丝机带动，成型为玻璃纤维；经短切机切丝，长度为7mm。The glass fiber provided by each embodiment and comparative example of the present invention is prepared through the following process: put each component into the mixing chamber and mix thoroughly; send it into the pool kiln and heat it at a high temperature at 1480°C to melt the glass fiber raw material; continue to maintain At this temperature, the melt is clarified and homogenized, and the treatment time is 0.5 hours; it flows out through a 4000-hole platinum bushing, driven by a high-speed wire drawing machine, and formed into glass fibers; it is cut into strands by a chopping machine, and the length is 7mm.
本发明各实施例及对比例的改性玻璃纤维的介电常数是按照ASTM D150-2011，使用KeysightE4990A精密阻抗测试仪在1MHz的条件下测得。The dielectric constants of the modified glass fibers of the various embodiments of the present invention and comparative examples are measured under the condition of 1 MHz using a Keysight E4990A precision impedance tester according to ASTM D150-2011.
实施例1～10Examples 1-10
本实施例提供一系列低介电改性玻璃纤维，其配方如表1。This embodiment provides a series of low-dielectric modified glass fibers, the formula of which is shown in Table 1.
表1实施例1～10的配方(份)The formula (part) of table 1 embodiment 1～10
Figure PCTCN2022107113-appb-000003
Figure PCTCN2022107113-appb-000003
对比例1～8Comparative example 1-8
本对比例提供一系列的玻璃纤维，其配方如表2。This comparative example provides a series of glass fibers, the formulations of which are shown in Table 2.
表2对比例1～8的配方(份)The formula (part) of table 2 comparative examples 1～8
Figure PCTCN2022107113-appb-000004
Figure PCTCN2022107113-appb-000004
由上述测试结果可知，相对于对比例1中未改性的玻璃纤维，实施例1～10中的改性玻璃纤维具有较低的介电常数，其中以实施例1的介电常数最低。对比例2～5中缺少特定某一特定组分，得到的功能氧化物对玻璃纤维的介电性能改善有限，均具有较高的介电常数。对比例6中功能氧化物与SiO 2的配比过小，介电常数较高；对比例7中功能氧化物与SiO 2的配比过大，介电常数较高。对比例8中功能氧化物配比不合适，介电常数较高。 From the above test results, it can be seen that compared with the unmodified glass fiber in Comparative Example 1, the modified glass fibers in Examples 1-10 have lower dielectric constants, and the dielectric constant of Example 1 is the lowest. In Comparative Examples 2-5, a specific component is lacking, and the obtained functional oxides have limited improvement on the dielectric properties of glass fibers, and all have relatively high dielectric constants. In comparative example 6, the ratio of functional oxide to SiO 2 is too small, and the dielectric constant is high; in comparative example 7, the ratio of functional oxide to SiO 2 is too large, and the dielectric constant is high. In Comparative Example 8, the proportion of functional oxides is not suitable, and the dielectric constant is relatively high.
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。Those skilled in the art will appreciate that the embodiments herein are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.

Claims (10)

  1. 一种低介电改性玻璃纤维，其特征在于，包括如下重量份数的组分：A low-dielectric modified glass fiber is characterized in that it comprises the following components in parts by weight:
    Figure PCTCN2022107113-appb-100001
    Figure PCTCN2022107113-appb-100001
    所述功能氧化物为CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的混合物，CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的重量比为1:0.5～2:0.5～2:0.5～2。 The functional oxide is a mixture of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 , and the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 is 1:0.5 ~2:0.5~2:0.5~2.
  2. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述R 2O为Li 2O、Na 2O或K 2O中的一种或几种。 The low-dielectric modified glass fiber according to claim 1, wherein the R 2 O is one or more of Li 2 O, Na 2 O or K 2 O.
  3. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述MgO/CaO的重量份数为2～8份。The low-dielectric modified glass fiber according to claim 1, characterized in that the parts by weight of the MgO/CaO are 2-8 parts.
  4. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述功能氧化物和SiO 2的重量比为1:40～50。 The low-dielectric modified glass fiber according to claim 1, characterized in that the weight ratio of the functional oxide to SiO 2 is 1:40-50.
  5. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述功能氧化物的重量份数为1.2～1.5份。The low-dielectric modified glass fiber according to claim 1, wherein the weight part of the functional oxide is 1.2-1.5 parts.
  6. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述功能氧化物中CeO 2、La 2O 3、Nd 2O 3和Y 2O 3的重量比为1:0.8～1:0.8～1:0.8～1。 The low-dielectric modified glass fiber according to claim 1, characterized in that the weight ratio of CeO 2 , La 2 O 3 , Nd 2 O 3 and Y 2 O 3 in the functional oxide is 1:0.8-1 :0.8～1:0.8～1.
  7. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述低介电改性玻璃纤维还包括其它添加剂0～2份，所述其它添加剂为Na 2SO 4或CaSO 4中的一种或两种。 The low-dielectric modified glass fiber according to claim 1, characterized in that, the low-dielectric modified glass fiber also includes 0 to 2 parts of other additives, and the other additives are Na2SO4 or CaSO4 one or two.
  8. 根据权利要求1所述低介电改性玻璃纤维，其特征在于，所述低介电改性玻璃纤维中各组分的粒径分布D90为50～200μm。The low dielectric modified glass fiber according to claim 1, characterized in that the particle size distribution D90 of each component in the low dielectric modified glass fiber is 50-200 μm.
  9. 权利要求1～8任一所述低介电改性玻璃纤维的制备方法，其特征在于，包括如下步骤：将SiO 2、Al 2O 3、B 2O 3、R 2O、MgO/CaO、TiO 2、ZnO和功能氧化物混合，熔融，澄清，均化，成型，切丝即得所述低介电改性玻璃纤维。 The method for preparing low-dielectric modified glass fiber according to any one of claims 1 to 8, characterized in that it comprises the following steps: SiO 2 , Al 2 O 3 , B 2 O 3 , R 2 O, MgO/CaO, TiO 2 , ZnO and functional oxides are mixed, melted, clarified, homogenized, shaped and shredded to obtain the low dielectric modified glass fiber.
  10. 权利要求1～8任一所述低介电改性玻璃纤维在制备印刷电路板中的应用。The application of the low-dielectric modified glass fiber in any one of claims 1 to 8 in the preparation of printed circuit boards.
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