WO2022247607A1 - 电子级低介电玻璃纤维布处理剂及其制备方法 - Google Patents

电子级低介电玻璃纤维布处理剂及其制备方法 Download PDF

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WO2022247607A1
WO2022247607A1 PCT/CN2022/091363 CN2022091363W WO2022247607A1 WO 2022247607 A1 WO2022247607 A1 WO 2022247607A1 CN 2022091363 W CN2022091363 W CN 2022091363W WO 2022247607 A1 WO2022247607 A1 WO 2022247607A1
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coupling agent
glass fiber
fiber cloth
electronic
dielectric glass
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PCT/CN2022/091363
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English (en)
French (fr)
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李伟
肖华青
张莹莹
刘东锋
付海波
牛思齐
刘余
相博文
魏麟
王筱琛
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泰山玻璃纤维邹城有限公司
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Priority to JP2022563229A priority Critical patent/JP7344431B2/ja
Priority to KR1020227037735A priority patent/KR102506702B1/ko
Publication of WO2022247607A1 publication Critical patent/WO2022247607A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/5135—Unsaturated compounds containing silicon atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated

Definitions

  • the invention belongs to the technical field of glass fiber treatment agents, and in particular relates to an electronic-grade low-dielectric glass fiber cloth treatment agent and a preparation method thereof.
  • the patent CN103556461B discloses a surface treatment agent for electronic-grade glass fiber cloth.
  • the treatment agent includes a silane coupling agent with a general formula of Y(CH 2 ) n SiX 3 , acetic acid and deionized water, wherein Y represents an organic functional group, is vinyl, amino, epoxy, methacryloxy, mercapto or ureido, etc.; X represents a hydrolyzable group, which is chloro, methoxy, ethoxy, methoxyethoxy or Acetoxy, etc.
  • the formula of the treatment agent is combined with the pretreatment process, and the electronic grade glass fiber cloth produced has the advantages of high heat resistance, ion migration resistance, and faster resin infiltration.
  • Patent CN107119455A discloses a post-treatment agent for glass fiber cloth, which consists of the following components, vinyl-containing silane coupling agent A, epoxy-containing silane coupling agent B, pH regulator, surfactant and Deionized water; wherein the content of the silane coupling agent A is 1.1 to 1.5 times the content of the silane coupling agent B.
  • the post-treatment agent has good storage stability, strong binding force with resin, and certain crispness.
  • Patent CN105401423B discloses a post-treatment agent for electronic-grade glass fiber cloth, which is made of the following components: pH regulator, aminosilane coupling agent, fluorocarbon surfactant and deionized water.
  • the electronic-grade glass fiber cloth treated with this treatment agent has the advantages of high mechanical strength, good heat resistance, and high product yield.
  • the coupling agent hydrolysis process involved in the above-mentioned patent belongs to the conventional hydrolysis method of the coupling agent, and the surface active agent is used to reduce the surface tension of the solution and reduce the problem of foaming during use.
  • the surface active agent is used to reduce the surface tension of the solution and reduce the problem of foaming during use.
  • adding fluorine Carbon-based surfactants or hydrocarbon-based surfactants will adsorb salt ions and affect the electronic distribution performance. Therefore, it is necessary to solve the problem of selection and coordination of treatment agent and resin type, especially solve the problem of combination with low dielectric resin (such as PPO).
  • the technical problem to be solved by the present invention is to provide an electronic-grade low-dielectric glass fiber cloth treatment agent, which can improve the bonding performance of glass fiber cloth and resin on the basis of satisfying the low dielectric performance, and at the same time strengthen the low-dielectric glass fiber cloth.
  • the mechanical properties and heat resistance of the fiber cloth; the invention also provides its preparation method.
  • the electronic-grade low-dielectric glass fiber cloth treatment agent of the present invention includes the following raw materials in weight percentage: 0.6-1.2% of coupling agent A, 0.3-0.8% of coupling agent B, and 0.01-1.5% of coupling agent auxiliary agent , alcohol 0.1-0.5%, acid 0.1-0.5%, and the balance is water.
  • the coupling agent A is a coupling agent containing vinyl groups.
  • the general structural formula of the coupling agent A is CH 2 ⁇ CH(CH 2 ) n SiX 3 , where n is an integer between 0 and 3, and X is a hydrolyzable group, preferably methoxy, ethoxy methoxyethoxy, acetoxy or peroxy.
  • the coupling agent A is one of vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, propenyltrimethoxysilane, vinyltriisopropoxysilane one or more species.
  • the content of coupling agent A is 0.6-1.2%, preferably 0.8-1.1%. If the amount of coupling agent A is too low and the non-polar groups are small, the addition reaction with the resin will be slowed down; if the amount is too high, it will lead to the ineffective accumulation of the coupling agent on the surface of the glass fiber cloth. , the coupling agent will be further polycondensed to form ineffective components, thereby increasing the cost.
  • the coupling agent B is a coupling agent containing vinylbenzyl.
  • the general structural formula of the coupling agent B is CH 2 ⁇ CH(C 6 H 4 )CH 2 (CH 2 ) n SiX 3 , wherein n is an integer between 0 and 3, X is a hydrolyzable group, Preference is given to methoxy, ethoxy, methoxyethoxy, acetoxy or peroxy.
  • the coupling agent B is vinylbenzyltriethoxysilane, ⁇ -(vinylbenzyl)propyltriethoxysilane, vinylbenzyltrimethoxysilane, vinylbenzylisopropoxysilane one or more of .
  • the content of coupling agent B is 0.3-0.8%, preferably 0.4-0.6%. If the amount of coupling agent B is too low, it will provide less free radicals, which will reduce the reaction rate between the coupling agent and the resin; if the amount is too high, it will cause ineffective accumulation of the coupling agent on the surface of the glass fiber cloth. The coupling agent will be further polycondensed to form ineffective components, thereby increasing the cost.
  • the content ratio of coupling agent A and coupling agent B is (1.2-2.3):1. If the ratio of the amount of coupling agent A to coupling agent B is too high, the efficiency of vinylbenzyl in coupling agent B to provide stable electrons will decrease; if the ratio is too low, the non-polar groups in coupling agent A will participate in the reaction of the resin Reduced efficacy.
  • the coupling agent is compounded with coupling agent A and coupling agent B.
  • the coupling agent A is a non-polar group, which can not only reduce the surface tension, but more importantly, it can be added to the low dielectric resin system (such as PPO resin).
  • reaction and choose a small molecule short-chain coupling agent, which has small molecular weight, strong capillary force, and strong permeability, and can penetrate into the glass fiber better;
  • coupling agent B contains vinylbenzyl, which has heat resistance and lubricity. Electronically stable, it can quickly generate free radicals, speed up the reaction with low-dielectric resins, and enhance its heat resistance.
  • the coupling agent auxiliary agent is a salt of maleic anhydride graft modified copolymer.
  • the coupling agent auxiliary agent is the sodium salt of butadiene and maleic anhydride copolymer, the ammonium salt of butadiene and maleic anhydride copolymer, the sodium salt of dimethyldiallyl and maleic anhydride copolymer One or more of amine salts of dimethyl diallyl and maleic anhydride copolymers.
  • the content of the coupling agent auxiliary agent is 0.01-1.5%, preferably 0.05-1.0%. If the amount of coupling agent auxiliary agent is too much, it will inhibit the coupling effect of coupling agent A and B and increase the cost of raw materials; if the amount is too small, the strengthening effect of coupling agent and resin will be weakened.
  • the acid anhydride group contained in the coupling agent can undergo a broad dehydration reaction with polar groups (-NH 2 , -OH) and form chemical bonds, thereby chemically coupling incompatible polar and non-polar substances. Coupled to further strengthen the combination of coupling agent and resin.
  • the acid is a small molecule organic acid with 1-5 carbon atoms; preferably formic acid or acetic acid.
  • the pH of the treatment agent is adjusted to an appropriate range with an acid.
  • the alcohol is a small molecule organic alcohol with 1-5 carbon atoms; preferably methanol, ethanol or glycerol.
  • Alcohols are used as co-solvents, which can increase the solubility of the coupling agent, reduce the surface tension of the solution, and promote the combination of the treatment agent and the glass fiber compared with the traditional addition of surfactants, and the alcohols are volatilized in the subsequent drying step , to reduce the interference of coupling agent and resin reaction.
  • the preparation method of electronic grade low dielectric glass fiber cloth treatment agent of the present invention comprises the following steps:
  • the pH of the electronic-grade low-dielectric glass fiber cloth treatment agent is 4-6. After preparation, keep stirring at a low speed and store it for later use.
  • the present invention uses vinyl-containing coupling agent A and vinylbenzyl-containing coupling agent B to compound, wherein coupling agent A is a non-polar group, which can not only reduce surface tension, but more importantly Addition reaction with low dielectric resin system (such as PPO resin), coupling agent B contains vinylbenzyl, has heat resistance and lubricity, stable electrons, can quickly generate free radicals, and speed up the reaction with low dielectric resin, At the same time, its heat resistance is enhanced.
  • the coupling agent A is a small-molecule short-chain coupling agent with small molecular weight, large capillary force, and strong permeability, which can better penetrate into the glass fiber. The viscosity of the stage resin is low, which is conducive to the penetration of glass fiber;
  • the present invention adopts alcohols as cosolvents, which can increase the solubility of the coupling agent, not only reduces the surface tension of the solution, and promotes the combination of the treatment agent and the glass fiber, and the alcohols It is volatilized in the subsequent drying step to reduce the interference on the reaction between the coupling agent and the resin;
  • the present invention adds the salt of the maleic anhydride graft as a coupling agent auxiliary agent, wherein the acid anhydride group can undergo a generalized dehydration reaction with the polar group (-NH 2 ,-OH) and form a chemical bond, thereby Incompatible polar and non-polar substances are chemically coupled to further strengthen the combination of coupling agent and resin.
  • the present invention does not use fluorocarbon surfactants or hydrocarbon surfactants, which can reduce the problem of foam generation during use, avoid adding defoamer ineffective components, and avoid the adsorption of salt ions at the same time, thereby affecting electronic performance. Electrical performance.
  • the present invention uses alcohols as solvents. Alcohols can form a large number of hydrogen bonds to ensure the relatively stable existence of silanols formed by hydrolysis of the coupling agent and reduce the probability of condensation reaction of silanol hydroxyl groups.
  • the preparation method is as follows:
  • the preparation method is as follows:
  • the preparation method is as follows:
  • the preparation method is as follows:
  • the preparation method is as follows:
  • the preparation method is as follows:
  • this comparative example is only different in that the sodium salt of the coupling agent auxiliary butadiene and maleic anhydride copolymer is not added.
  • this comparative example is only different in that no coupling agent A vinyltriethoxysilane is added.
  • this comparative example is only different in that no coupling agent B vinylbenzyltriethoxysilane is added.
  • this comparative example is only different in that the coupling agent B is replaced with an equal mass of amino coupling agent Dynasylan 1161 (Evonik).
  • Example 1 Compared with Example 1, this comparative example is only different in that methanol is replaced by equal-quality surfactant CapstoneFS-63 (Dupont).
  • this comparative example is only different in that the percentage of coupling agent A vinyltriethoxysilane is 1.3%, and the percentage of coupling agent B vinylbenzyltriethoxysilane is 1.0%.
  • this comparative example is only different in that the percentage of coupling agent A vinyltriethoxysilane is 0.8%, and the percentage of coupling agent B vinylbenzyltriethoxysilane is 0.8%.
  • the treatment agents prepared in Examples and Comparative Examples were respectively treated with electronic-grade low-dielectric glass fiber cloth (2116 cloth), as follows: the low-dielectric glass fiber cloth was first immersed in the treatment agent (normal temperature) at a speed of 30m/min. and then dried at 120°C.
  • the performance test of the processed electronic grade low dielectric glass fiber cloth is as follows:
  • the surface-treated electronic-grade glass fiber cloth is sampled by a circular punching machine, and one sample is taken from the left, middle, and right sides of the cloth surface, and each sample is placed horizontally with a viscosity of 20 ⁇ ls (the laboratory temperature is fixed at 25°C) in the glue, at the same time use a stopwatch to observe the changes of the white lines on the surface of the electronic grade glass fiber cloth until the resin completely soaks the surface of the electronic grade glass fiber cloth, and when the white line disappears, press the stopwatch to record the time.
  • Resin content sample reduction/sample original weight.

Abstract

一种电子级低介电玻璃纤维布处理剂及其制备方法。所述电子级低介电玻璃纤维布处理剂，包括以下重量百分数的原料：偶联剂A0.6-1.2％，偶联剂B 0.3-0.8％，偶联剂助剂0.01-1.5％，醇0.1-0.5％，酸0.1-0.5％，余量为水；所述偶联剂A为含有乙烯基的偶联剂；偶联剂B为含有乙烯苄基的偶联剂；偶联剂助剂为马来酸酐接枝改性共聚物的盐。该处理剂在满足低介电性能的基础上，提高了玻纤布与低介电客户树脂的结合性能，同时增强了低介电玻璃纤维布的力学性能和耐热性。

Description

电子级低介电玻璃纤维布处理剂及其制备方法 技术领域
本发明属于玻纤处理剂技术领域，具体涉及一种电子级低介电玻璃纤维布处理剂及其制备方法。
背景技术
随着5G技术的迅速发展，在高频高速应用领域对PCB板材的要求也越来越高，这势必对作为CCL重要的组成材料之一电子级玻璃纤维布处理剂有更高的要求。目前大多数板材都是环氧树脂体系，对介电常数和介电损耗的要求没那么高，但是对于一些超薄布IC封装载板、高频高速板等，现有的处理剂配方无法满足低介电树脂体系匹配性能的要求，因此开发一种电子级低介电玻璃纤维布处理剂配方具有重要的意义。目前的低介电玻璃纤维布处理剂配方在使用过程中含浸性比较差，存在浸透时间长、客户产品有气泡等问题。
例如专利CN103556461B中公开了一种电子级玻璃纤维布表面处理剂，其处理剂包括通式为Y(CH 2) nSiX 3的硅烷偶联剂、醋酸和去离子水，其中Y代表有机官能团，是乙烯基、氨基、环氧基、甲基丙烯酰氧基、巯基或脲基等；X代表可水解的基团，是氯基、甲氧基、乙氧基、甲氧基乙氧基或乙酰氧基等。该处理剂配方结合预处理工艺，生产的电子级玻璃纤维布具有高耐热性、耐离子迁移性、更快的树脂浸润性等优点。
专利CN107119455A中公开了一种玻璃纤维布用后处理剂，由以下组分组成，含乙烯基的硅烷偶联剂A，含环氧基的硅烷偶联剂B，PH调节剂，表面活性剂和去离子水；其中硅烷偶联剂A的含量为硅烷偶联剂B的含量的1.1～1.5倍。该后处理剂储存稳定性好，与树脂结合力强，并且有一定的挺括性。
专利CN105401423B中公开了一种电子级玻璃纤维布用后处理剂，如下组分制成：pH调节剂、氨基硅烷偶联剂、氟碳表面活性剂和去离子水。经该处理剂处理过的电子级玻璃纤维布具有机械强度高、耐热性好、产品成品率高等优点。
但是上述专利涉及的偶联剂水解工艺属于偶联剂的常规水解方法，且使用表面活性剂降低溶液的表面张力，减少使用过程中产生泡沫的问题，但是对于低介电玻璃纤维布，加入氟碳类表面活性剂或碳氢类表面活性剂，会吸附盐离子，影响电子布电性能。因此需要解决处理剂与树脂类型选择、协配的问题，尤其是解决与低介电树脂(如PPO)结合性方面的难题。发明内容
本发明要解决的技术问题是：提供一种电子级低介电玻璃纤维布处理剂，在满足低介电性能的基础上，提高玻璃玻纤布与树脂的结合性能，同时增强低介电玻璃纤维布的力学性能 和耐热性；本发明还提供其制备方法。
本发明所述的电子级低介电玻璃纤维布处理剂，包括以下重量百分数的原料：偶联剂A 0.6-1.2％，偶联剂B 0.3-0.8％，偶联剂助剂0.01-1.5％，醇0.1-0.5％，酸0.1-0.5％，余量为水。
所述偶联剂A为含有乙烯基的偶联剂。
优选地，偶联剂A的结构通式为CH 2＝CH(CH 2) nSiX 3，其中n为0-3之间的整数，X为可水解基团，优选为甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基或过氧基。
进一步优选地，偶联剂A为乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、丙烯基三甲氧基硅烷、乙烯基三异丙氧基硅烷中的一种或多种。
偶联剂A的含量为0.6-1.2％，优选为0.8-1.1％。如果偶联剂A用量过低，非极性基团少，会导致与树脂的加成反应速度减慢；若用量过高，会导致玻纤布表面偶联剂的无效堆积，经过长时间放置，偶联剂会进一步缩聚，形成无效组份，从而增加成本。
所述偶联剂B为含有乙烯苄基的偶联剂。
优选地，偶联剂B的结构通式为CH 2＝CH(C 6H 4)CH 2(CH 2) nSiX 3，其中n为0-3之间的整数，X为可水解基团，优选为甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基或过氧基。
进一步优选地，偶联剂B为乙烯苄基三乙氧基硅烷、β-(乙烯苄基)丙基三乙氧基硅烷、乙烯苄基三甲氧基硅烷、乙烯苄基异丙氧基硅烷中的一种或多种。
偶联剂B的含量为0.3-0.8％，优选为0.4-0.6％。如果偶联剂B用量过低，则提供的自由基少，会降低偶联剂与树脂的反应速率；若用量过高，会导致玻纤布表面偶联剂的无效堆积，经过长时间放置，偶联剂会进一步缩聚，形成无效组份，从而增加成本。
偶联剂A和偶联剂B的含量比值为(1.2-2.3)：1。如果偶联剂A和偶联剂B的用量比值过高，偶联剂B中乙烯苄基提供稳定电子的功效降低；若比值过低，偶联剂A中非极性基团参与树脂反应的功效降低。
偶联剂使用偶联剂A和偶联剂B复配，偶联剂A为非极性基团，不仅可以降低表面张力，更重要的是与低介电树脂体系(如PPO树脂)发生加成反应，并选择小分子短链偶联剂，分子量小，毛细管力大，渗透性强，可以更好地渗透到玻纤里；偶联剂B含有乙烯苄基，具有耐热和润滑性，电子稳定，能够快速产生自由基，加快与低介电树脂的反应，同时增强其耐热性。
所述偶联剂助剂为马来酸酐接枝改性共聚物的盐。
优选地，偶联剂助剂为丁二烯和马来酸酐共聚物的钠盐、丁二烯和马来酸酐共聚物的铵盐、二甲基二烯丙基和马来酸酐共聚物的钠盐、二甲基二烯丙基和马来酸酐共聚物的胺盐的一种或多种。
偶联剂助剂的含量为0.01-1.5％，优选为0.05-1.0％。如果偶联剂助剂用量过多，会抑制偶联剂A和B发挥偶联作用，增加原料成本；若用量过少，偶联剂与树脂结合的加强作用则会减弱。
偶联剂助剂所含的酸酐基团能够与极性基团(-NH 2、-OH)发生广义的脱水反应并形成化学键，从而将不相容的极性和非极性物质进行化学偶联，进一步加强偶联剂与树脂的结合。
所述酸为碳原子数为1-5的小分子有机酸；优选为甲酸或醋酸。通过酸将处理剂的pH调节至合适的范围内。
所述醇为碳原子数为1-5的小分子有机醇；优选为甲醇，乙醇或丙三醇。
醇类作为助溶剂，与传统加入表面活性剂相比，可以增加偶联剂的溶解度，同时降低溶液的表面张力，促进处理剂与玻璃纤维的结合，而且醇类在后续烘干步骤中挥发出去，减少对偶联剂与树脂反应的干扰。
本发明所述的电子级低介电玻璃纤维布处理剂的制备方法，包括以下步骤：
(1)向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将酸与醇混合均匀后，加入到配制罐中；
(3)将偶联剂A和偶联剂B依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将偶联剂助剂加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂。
所述电子级低介电玻璃纤维布处理剂的pH为4-6，配置好后，保持低速搅拌状态，保存待用。
与现有技术相比，本发明的有益效果如下：
(1)本发明采用含乙烯基的偶联剂A和含乙烯苄基的偶联剂B进行复配，其中偶联剂A为非极性基团，不仅可以降低表面张力，更重要的是与低介电树脂体系(如PPO树脂)发生加成反应，偶联剂B含有乙烯苄基，具有耐热和润滑性，电子稳定，能够快速产生自由基，加快与低介电树脂的反应，同时增强其耐热性，此外偶联剂A选择小分子短链偶联剂，分子量小，毛细管力大，渗透性强，可以更好地渗透到玻纤里，在下游客户半固化片生产时，低温阶段树脂粘度低，利于玻纤的渗透；
(2)本发明与传统加入表面活性剂相比，采用醇类作为助溶剂，可以增加偶联剂的溶解度，不仅降低了溶液的表面张力，促进了处理剂与玻璃纤维的结合，而且醇类在后续烘干步骤中挥发出去，减少对偶联剂与树脂反应的干扰；
(3)本发明添加马来酸酐接枝物的盐作为偶联剂助剂，其中酸酐基团能够与极性基团(-NH 2、-OH)发生广义的脱水反应并形成化学键，从而将不相容的极性和非极性物质进行化学偶联，进一步加强偶联剂与树脂的结合。
(4)本发明未采用氟碳类表面活性剂或碳氢类表面活性剂，可以减少使用过程中产生泡沫的问题，避免添加消泡剂无效组份，同时避免盐离子的吸附，从而影响电子布电性能。
(5)本发明使用醇类作为溶剂，醇可形成大量的氢键，保证偶联剂水解形成的硅醇比较稳定的存在，降低硅醇羟基发生缩合反应的概率。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1
按以下原料配比制备电子级低介电玻璃纤维布处理剂：乙烯基三乙氧基硅烷1.0％，乙烯苄基三乙氧基硅烷0.7％，丁二烯和马来酸酐共聚物的钠盐(丁二烯和马来酸酐摩尔比为6：4，分子量4000)1.5％，甲醇0.15％，醋酸0.25％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将甲醇与醋酸混合均匀后，加入到配制罐中；
(3)将乙烯基三乙氧基硅烷和乙烯苄基三乙氧基硅烷依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将丁二烯和马来酸酐共聚物的钠盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.3，配置好后，保持低速搅拌状态，保存待用。
实施例2
按以下原料配比制备电子级低介电玻璃纤维布处理剂：乙烯基三(β-甲氧基乙氧基)硅烷0.65％，β-(乙烯苄基)丙基三乙氧基硅烷0.3％，丁二烯和马来酸酐共聚物的胺盐(丁二烯和马来酸酐摩尔比为6：4，分子量7000)0.4％，甲醇0.10％，醋酸0.50％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将甲醇与醋酸混合均匀后，加入到配制罐中；
(3)将乙烯基三(β-甲氧基乙氧基)硅烷和β-(乙烯苄基)丙基三乙氧基硅烷依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将丁二烯和马来酸酐共聚物的胺盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.6，配置好后，保持低速搅拌状态，保存待用。
实施例3
按以下原料配比制备电子级低介电玻璃纤维布处理剂：乙烯基三乙氧基硅烷0.6％，乙烯苄基三乙氧基硅烷0.3％，二甲基二烯丙基和马来酸酐共聚物的钠盐(二甲基二烯丙基和马来酸酐摩尔比为6：4，分子量5500)0.8％，乙醇0.1％，醋酸0.3％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将乙醇与醋酸混合均匀后，加入到配制罐中；
(3)将乙烯基三乙氧基硅烷和乙烯苄基三乙氧基硅烷依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将二甲基二烯丙基和马来酸酐共聚物的钠盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.5，配置好后，保持低速搅拌状态，保存待用。
实施例4
按以下原料配比制备电子级低介电玻璃纤维布处理剂：丙烯基三甲氧基硅烷0.8％，β-(乙烯苄基)丙基三乙氧基硅烷0.6％，二甲基二烯丙基和马来酸酐共聚物的胺盐(二甲基二烯丙基和马来酸酐摩尔比为5：4，分子量5500)0.01％，乙醇0.15％，醋酸0.1％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将乙醇与醋酸混合均匀后，加入到配制罐中；
(3)将丙烯基三甲氧基硅烷和β-(乙烯苄基)丙基三乙氧基硅烷依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将二甲基二烯丙基和马来酸酐共聚物的胺盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.7，配置好后，保持低速搅拌状态，保存待用。
实施例5
按以下原料配比制备电子级低介电玻璃纤维布处理剂：丙烯基三甲氧基硅烷1.2％，β-(乙烯苄基)丙基三乙氧基硅烷0.8％，二甲基二烯丙基和马来酸酐共聚物的胺盐(二甲基二烯丙基和马来酸酐摩尔比为5：4，分子量5500)0.05％，丙三醇0.5％，醋酸0.25％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将丙三醇与醋酸混合均匀后，加入到配制罐中；
(3)将丙烯基三甲氧基硅烷和β-(乙烯苄基)丙基三乙氧基硅烷依次加入配制罐中， 搅拌至水溶液澄清透明；
(4)将二甲基二烯丙基和马来酸酐共聚物的胺盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.8，配置好后，保持低速搅拌状态，保存待用。
实施例6
按以下原料配比制备电子级低介电玻璃纤维布处理剂：丙烯基三甲氧基硅烷0.8％，β-(乙烯苄基)丙基三乙氧基硅烷0.5％，二甲基二烯丙基和马来酸酐共聚物的胺盐(二甲基二烯丙基和马来酸酐摩尔比为5：4，分子量4500)1.0％，乙二醇0.15％，醋酸0.45％，余量为纯水。
制备方法如下：
(1)按配方量准确称量原料，向配制罐中加入纯水，并开启搅拌；
(2)用搅拌器将乙二醇与醋酸混合均匀后，加入到配制罐中；
(3)将丙烯基三甲氧基硅烷和β-(乙烯苄基)丙基三乙氧基硅烷依次加入配制罐中，搅拌至水溶液澄清透明；
(4)将二甲基二烯丙基和马来酸酐共聚物的胺盐加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂，pH值为4.5，配置好后，保持低速搅拌状态，保存待用。
对比例1
本对比例与实施例1相比，不同点仅在于不添加偶联剂助剂丁二烯和马来酸酐共聚物的钠盐。
对比例2
本对比例与实施例1相比，不同点仅在于不添加偶联剂A乙烯基三乙氧基硅烷。
对比例3
本对比例与实施例1相比，不同点仅在于不添加偶联剂B乙烯苄基三乙氧基硅烷。
对比例4
本对比例与实施例1相比，不同点仅在于将偶联剂B替换为等质量的氨基偶联剂Dynasylan 1161(赢创)。
对比例5
本对比例与实施例1相比，不同点仅在于将甲醇替换为等质量的表面活性剂CapstoneFS-63(杜邦)。
对比例6
本对比例与实施例1相比，不同点仅在于偶联剂A乙烯基三乙氧基硅烷的百分比为1.3％，偶联剂B乙烯苄基三乙氧基硅烷的百分比为1.0％。
对比例7
本对比例与实施例1相比，不同点仅在于偶联剂A乙烯基三乙氧基硅烷的百分比为0.8％，偶联剂B乙烯苄基三乙氧基硅烷的百分比为0.8％。
对比例8
常规处理剂：冰醋酸：0.35％，氨基偶联剂Dynasylan 1161：0.85％，表面活性剂CapstoneFS-63：0.015％，余量为水。
将实施例和对比例制备的处理剂分别对电子级低介电玻璃纤维布(2116布)进行处理，方法如下：将低介电玻璃纤维布以30m/min的速度先浸入处理剂(常温)中，再在120℃温度下烘干。将处理后的电子级低介电玻璃纤维布进行性能测试，测试方法如下：
(1)布面拉伸断裂强度测试：
用取样器分别从样品中裁取6条50mm*250mm的长条试样。将上下夹具钳口放松至适当宽度，将试样的一端放入夹具中，使试样的纵向中心线通过夹具前边的中心，试样下端用同样的方法放入夹具。试样在最终夹紧前，在试样整个宽度上均匀地加予张力，该张力大致相当于断裂力的(1±0.25)％。点击试验开始选项，试验开始。仪器自动计算、显示最终的试验结果。
(2)板材热应力测试：
将样品放入温度为288℃的锡炉中进行耐热性测试，同时按秒表计时，在锡液中持续浸泡10秒，观察样品是否爆板(起泡)，记录放入锡液中的次数，如果有爆板(起泡)，说明板材已经分层失效。
(3)板材耐热性测试：
将经过PCT高压蒸煮锅蒸煮4小时的样品放入温度为288℃的锡炉中进行耐热性测试，同时按秒表计时，在锡液中持续浸泡300秒，观察样品是否爆板(起泡)，记录放入锡液中的次数，如果有爆板(起泡)，说明板材已经分层失效。
(4)含浸性测试方法：
将经过表面处理的电子级玻璃纤维布采用圆冲模机取样，布面左、中、右各取一个样品，将取好的每块样品水平地放入粘度为20±ls(实验室温度固定为25℃)的胶水中，同时用秒表计时，观察电子级玻璃纤维布表面白线的变化，直到树脂完全浸透电子级玻璃纤维布表面，白线消失时，按下秒表，记录时间。
(5)板材树脂含量测试：
将样品放入马弗炉中550±50℃闷烧20min，称重，计算样品减少量。树脂含量＝样品减少量/样品原始重量。
测试结果如表1和表2所示。
表1实施例测试结果
Figure PCTCN2022091363-appb-000001
表2对比例测试结果
Figure PCTCN2022091363-appb-000002

Claims (10)

  1. 一种电子级低介电玻璃纤维布处理剂，其特征在于：包括以下重量百分数的原料：偶联剂A 0.6-1.2％，偶联剂B 0.3-0.8％，偶联剂助剂0.01-1.5％，醇0.1-0.5％，酸0.1-0.5％，余量为水；偶联剂A和偶联剂B的含量比值为(1.2-2.3)：1；
    所述偶联剂A为含有乙烯基的偶联剂；偶联剂B为含有乙烯苄基的偶联剂；偶联剂助剂为马来酸酐接枝改性共聚物的盐。
  2. 根据权利要求1所述的电子级低介电玻璃纤维布处理剂，其特征在于：偶联剂A的结构通式为CH 2＝CH(CH 2) nSiX 3，其中n为0-3之间的整数，X为甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基或过氧基。
  3. 根据权利要求2所述的电子级低介电玻璃纤维布处理剂，其特征在于：偶联剂A为乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、丙烯基三甲氧基硅烷、乙烯基三异丙氧基硅烷中的一种或多种。
  4. 根据权利要求1所述的电子级低介电玻璃纤维布处理剂，其特征在于：偶联剂B的结构通式为CH 2＝CH(C 6H 4)CH 2(CH 2) nSiX 3，其中n为0-3之间的整数，X为甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基或过氧基。
  5. 根据权利要求4所述的电子级低介电玻璃纤维布处理剂，其特征在于：偶联剂B为乙烯苄基三乙氧基硅烷、β-(乙烯苄基)丙基三乙氧基硅烷、乙烯苄基三甲氧基硅烷、乙烯苄基异丙氧基硅烷中的一种或多种。
  6. 根据权利要求1所述的电子级低介电玻璃纤维布处理剂，其特征在于：偶联剂助剂为丁二烯和马来酸酐共聚物的钠盐、丁二烯和马来酸酐共聚物的铵盐、二甲基二烯丙基和马来酸酐共聚物的钠盐、二甲基二烯丙基和马来酸酐共聚物的胺盐的一种或多种。
  7. 根据权利要求1所述的电子级低介电玻璃纤维布处理剂，其特征在于：酸为碳原子数为1-5的小分子有机酸。
  8. 根据权利要求1所述的电子级低介电玻璃纤维布处理剂，其特征在于：醇为碳原子数为1-5的小分子有机醇。
  9. 一种权利要求1-8任一项所述的电子级低介电玻璃纤维布处理剂的制备方法，包括以下步骤：
    (1)向配制罐中加入纯水，并开启搅拌；
    (2)用搅拌器将酸与醇混合均匀后，加入到配制罐中；
    (3)将偶联剂A和偶联剂B依次加入配制罐中，搅拌至水溶液澄清透明；
    (4)将偶联剂助剂加入配制罐内，搅拌均匀，得到电子级低介电玻璃纤维布处理剂。
  10. 根据权利要求9所述的电子级低介电玻璃纤维布处理剂的制备方法，其特征在于： 步骤(4)得到的处理剂pH为4-6，配置好后，保持低速搅拌状态，保存待用。
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