WO2023124282A1 - 一种低温固化导电浆料及电子器件 - Google Patents

一种低温固化导电浆料及电子器件 Download PDF

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Publication number
WO2023124282A1
WO2023124282A1 PCT/CN2022/120124 CN2022120124W WO2023124282A1 WO 2023124282 A1 WO2023124282 A1 WO 2023124282A1 CN 2022120124 W CN2022120124 W CN 2022120124W WO 2023124282 A1 WO2023124282 A1 WO 2023124282A1
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conductive paste
low
resin
temperature curing
paste according
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PCT/CN2022/120124
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English (en)
French (fr)
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亢佳萌
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北京梦之墨科技有限公司
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Publication of WO2023124282A1 publication Critical patent/WO2023124282A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder

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  • the present application relates to the technical field of new materials, in particular to a low-temperature curing conductive paste and electronic devices.
  • the curing temperature of most conductive pastes is usually high, so that it can only be limited to the coating on the surface of some high-temperature resistant materials such as PET and PI. Therefore, it cannot be directly applied to the surface of the substrate that is sensitive to temperature, let alone printed on the surface of the epoxy and polyurethane prefabricated film with thermal reactivity, and when the conductive paste is baked and cured at high temperature, it is often easy to cause thermosetting adhesive
  • the cross-linking reaction of the film fails prematurely and cannot meet the subsequent process requirements; in addition, although some low-temperature curing conductive pastes have appeared on the market, these conductive pastes still have long curing time at low temperature, poor high temperature resistance, and low adhesion. , easy to fall off and other problems.
  • the present application provides a low-temperature curing conductive paste and an electronic device.
  • the conductive paste has the characteristics of low-temperature curing, short curing time, and excellent performance of high temperature resistance after curing.
  • the present application provides a low-temperature curing conductive paste, which adopts the following technical solution:
  • the conductive paste includes: 5%-20% base resin carrier, 10%-20% organic solvent, 60%-76% conductive powder, 8%-17% functional resin mixture , 0.1% to 3% defoamer and 0.1% to 3% adhesion promoter.
  • the base resin carrier includes phenolic resin and/or epoxy resin.
  • the phenolic resin is barium phenolic resin.
  • the barium phenolic resin is barium phenolic resin modified by polycyclic aromatic compounds, and the modification process includes: (1) weak base organic ammonia linear catalysis step, and (2) strong base barium hydroxide catalysis step .
  • the molecular weight of the base resin carrier is 3000-60000; and/or, the softening point temperature is between 60°C and 100°C.
  • the functional resin mixture is at least used as a modified toughening filler for the slurry, and includes polyethylene glycol and isocyanate, wherein the weight ratio of polyethylene glycol to isocyanate is 0.4:1 to 1.75:1 , preferably, the weight ratio of the two can be 0.5:1 ⁇ 1:1.
  • the functional resin mixture further includes a macromolecular epoxy resin, and the molecular weight of the macromolecular epoxy resin is 30,000-50,000.
  • the isocyanate is toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate, polyphenylmethane polyisocyanate A mixture of one or at least two components.
  • the defoamer is one or at least two of polysiloxane defoamers, silicone defoamers, polyether defoamers; and/or, the adhesion promoter is Silane coupling agent adhesion promoter.
  • the present application provides an electronic device, adopting the following technical solution:
  • the electronic device includes: a substrate, a conductive circuit on the substrate, and an electronic component, wherein the conductive circuit is made of the low-temperature curing conductive paste described in any one of the above.
  • the low-temperature curing conductive paste of this application can achieve low-temperature curing at 120°C.
  • the modified barium phenolic resin is used. Compared with other common resins, it has a lower curing temperature and faster curing speed, which can effectively reduce the curing rate. temperature, shorten the curing time, the curing time is 10-20 minutes;
  • the low-temperature curing conductive paste of the present application has excellent high temperature resistance, can withstand high temperatures of 500°C after curing at low temperature, and has stable and reliable temperature resistance;
  • the low-temperature curing conductive paste of the present application has good printability and good adhesion to the substrate;
  • the low-temperature curing conductive paste of the present application has excellent flexibility and can be applied not only to hard substrates, but also to flexible substrates.
  • FIG. 1 is a schematic structural diagram of an electronic device provided by an embodiment of the present application.
  • Fig. 2 is a flow chart of the preparation method of the conductive paste provided by the embodiment of the present application.
  • the application provides a low temperature curing, high temperature resistant conductive paste, which includes 5% to 20% of the basic resin carrier, 10% to 20% of the organic solvent , 60% to 76% conductive powder, 8% to 17% functional resin mixture, 0.1% to 3% defoamer and 0.1% to 3% adhesion promoter.
  • the low-temperature curing and high-temperature-resistant conductive paste of the present application can be cured at a low temperature of 120°C, the curing time is short, and it can withstand a high temperature of 500°C after curing, and has good temperature resistance stability; in addition, the conductive paste of the present application also has good Flexibility, strong adhesion to the substrate, etc.
  • An embodiment of the present application provides a low-temperature curing conductive paste, specifically, by weight percentage, the conductive paste includes:
  • the weight percentage of the base resin carrier can be: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16% , 17%, 18%, 19% or 20%;
  • the weight percentage of solvent can be: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%;
  • the weight percentage of conductive filler can be: 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%.
  • the base resin carrier may be polyester resin, polyurethane resin, epoxy resin, acrylic resin, phenolic resin, alkyd resin, silicone resin, vinyl resin, polyimide resin A mixture of one or at least two components.
  • the base resin carrier can be formed by mixing one or more of the above-mentioned resins in a suitable ratio. For example, it can be prepared by mixing at any ratio between 1:10 and 10:1, which is not particularly limited in the present application.
  • the base resin carrier may include one or both of phenolic resin and epoxy resin.
  • the base resin carrier contains both phenolic resin and epoxy resin, wherein the weight ratio of phenolic resin and epoxy resin can be any value between 2:1 and 1:2, for example, 1: 1 ratio to mix. If the content of the phenolic resin is too much, the adhesion of the conductive paste will be poor and the paste will be too brittle, and if the content of the epoxy resin is too large, the temperature resistance of the conductive paste will be affected.
  • the basic resin carrier provided by this application can ensure that the conductive paste has low-temperature curing characteristics, good printability, wettability and excellent high-temperature resistance.
  • the phenolic resin is preferably a barium phenolic resin; further, the barium phenolic resin is a barium phenolic resin modified by polycyclic aromatic compounds, and the modification process includes: (1) weak base organic ammonia linear catalysis step, And (2) strong base barium hydroxide catalysis step.
  • the modification process includes: (1) weak base organic ammonia linear catalysis step, And (2) strong base barium hydroxide catalysis step.
  • the curing time of the conductive paste involved in this application is 10 to 20 minutes, such as 15 minutes; on the other hand,
  • the addition of the barium phenolic resin can also reduce the curing temperature of the paste, and the low-temperature curing temperature of the conductive paste of the present application can be 120°C.
  • the molecular weight of the base resin carrier may be between 3000-60000, and the softening point is within the range of 60°C-100°C.
  • the resin with the molecular weight and softening point in the above range can make the conductive paste have good wettability and printability while maintaining storage stability.
  • the weight percentage of the functional resin mixture may be: 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16% or 17%, And it includes at least polyethylene glycol and isocyanate, and is used as a modified toughening filler for conductive paste, wherein the weight ratio of polyethylene glycol to isocyanate is 0.4:1 to 1.75:1, preferably 0.5:1 to 1:1, such as 0.4:1, 0.5:1, 0.7:1, 1:1, 1.75:1 or other arbitrary ratios within the above range; or, by weight ratio, preferably, the low-temperature curing conductive paste It contains at least 4%-7% polyethylene glycol and 4%-10% isocyanate.
  • this application can use phenolic resin as the base resin carrier. Considering that the phenolic resin material is relatively brittle, it cannot directly form a flexible conductive paste and be applied to a flexible substrate. Therefore, in order to increase the conductive paste system
  • a functional resin mixture such as polyethylene glycol and isocyanate, is added to the conductive paste to at least act as a toughening modification to meet the flexibility requirements and the applicability of flexible substrates.
  • the isocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate, polyphenylmethane polyisocyanate or A mixture of at least two components.
  • the addition ratio of each substance can be any ratio that meets the toughening requirements of the conductive paste, which is not particularly limited in the present application.
  • the functional resin mixture of the present application also contains a macromolecular epoxy resin, wherein the The molecular weight of the macromolecular epoxy resin is between 30000 and 50000, and, optionally, the weight ratio of the macromolecular epoxy resin in the functional resin mixture is 10% to 20%.
  • the basic resin carrier such as phenolic resin
  • the basic resin carrier tends to produce many small molecular bubbles overflowing from the surface of the slurry during the curing process, thereby forming a plurality of micro-bubble holes, in order to effectively eliminate the micro-bubble holes, improve the cured conductive paste.
  • Surface morphology a certain proportion of defoamer is also added to the conductive paste of the present application.
  • the defoamer can be one or at least two of polysiloxane defoamers, silicone defoamers, polyether defoamers, and the weight percentage can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, or any value within the above range.
  • the adhesion promoter is preferably a silane coupling agent adhesion promoter, and the weight percentage can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% , 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, or any value within the above range.
  • the weight percentage of the solvent can be any value between 10% and 20%, and can be selected from ethanol, isopropanol, n-propanol, ethylene glycol, propylene glycol, glycerol, n-butanol , ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, Dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol acetate, propy
  • the conductive filler is one or at least two of gold, silver, iron, nickel, aluminum, graphene, silver-coated copper powder, etc.; and/or, the shape of the conductive filler is flake, One or more of spherical, linear, cubic, etc. Moreover, the size of the conductive filler may be 0.1 ⁇ m ⁇ 6 ⁇ m. Preferably, the conductive filler used in the embodiment of the present application is spherical silver powder with a particle size of 300-600 nm.
  • the conductive paste in the embodiments of the present application can be applied to forming processes such as screen printing, flexographic printing, pad printing, extrusion dispensing, and stencil printing, and the conductive lines can be obtained by heating and curing after forming.
  • a method for preparing a low-temperature curing conductive paste is provided, as shown in FIG. 2 , which may include the following steps:
  • Step S1 preparing an organic vehicle: heating and dissolving the base resin carrier, solvent, polyethylene glycol, isocyanate, defoamer, and adhesion promoter to obtain an organic vehicle;
  • the process may be heated by means of an oil bath and stirred while heating.
  • the temperature of the oil bath may be 70° C. to 120° C., and the stirring speed may be 300 rpm to 800 rpm.
  • Step S2 preparation of conductive paste: Stir and disperse the conductive filler and organic carrier in a mixing tank, then place it for half an hour (it can enhance the wetting effect of the organic carrier on the conductive filler and improve the effect of subsequent rolling), and then carry out three-roll rolling system to finally obtain a conductive paste with a viscosity ranging from 10 to 40 Pa ⁇ s.
  • the stirring speed can be selected from 500rpm to 2500rpm.
  • the conductive paste prepared by the above method is heated and sintered to solidify, wherein the heating and sintering temperature is preferably 120-180° C., and the sintering time is 10-80 minutes, so as to form a conductive layer with good adhesion and good flexibility.
  • the embodiment of the present application also provides an electronic device. Specifically, as shown in FIG. The above-mentioned conductive paste is made.
  • the electronic device further includes an electronic component 3 formed on the conductive circuit 2 .
  • the electronic components may be switches, power supplies, light emitting devices, sensors, chips, etc., which are not limited in this embodiment of the present application.
  • the conductive paste is molded on the base material by means of extrusion dispensing, and then placed in a blast drying oven for heating and sintering to solidify.
  • the heating and sintering temperature of the conductive paste is 120° C. to 180° C., and the sintering time is 10 minutes to 80 minutes.
  • the substrate of the embodiment of the present application can be a flexible substrate or a rigid substrate, and the flexible substrate can be polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate One of the films such as ethylene glycol formate (PEN), polyimide (PI), polyamide (PA), etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN ethylene glycol formate
  • PI polyimide
  • PA polyamide
  • a low-temperature curing conductive paste which comprises the following components in weight percent: 3% barium phenolic resin, 3% epoxy resin, 14% diethylene glycol ethyl ether acetate, 70% spherical silver powder, poly Ethylene Glycol 4%, Hexamethylene Diisocyanate 4.5%, Defoamer 0.5% and Adhesion Promoter 1%.
  • the preparation method of the low-temperature curing conductive paste in the above-mentioned embodiment 1 is as follows:
  • Preparation of conductive paste Weigh the spherical silver powder of estimated weight and mix it with the organic carrier prepared in S1 in a stirring tank at a speed of 1000rpm to disperse, then place it for half an hour, and then carry out three-roll rolling to finally obtain the viscosity Conductive paste in the range of 10-20Pa ⁇ s.
  • the test results show that the conductive paste obtained by the above-mentioned component ratio and preparation method has good printability, the paste curing temperature is 120°C, the high temperature resistance temperature is 500°C, and the adhesion to the substrate reaches 5B. excellent.
  • a low-temperature curing conductive paste in terms of weight percentage, the conductive paste comprises the following components: 4% barium phenolic resin, 3% epoxy resin, 14% diethylene glycol ethyl ether acetate, 55% spherical silver powder, flakes Silver powder 14%, polyethylene glycol 4%, hexamethylene diisocyanate 4%, defoamer 1% and adhesion promoter 1%.
  • the preparation process of the low-temperature curing conductive paste in the above-mentioned embodiment 2 is:
  • the test results show that the curing temperature of the conductive paste obtained by the above-mentioned component ratio and preparation method is 120°C, the high temperature resistance temperature is 500°C, and the adhesion to the substrate reaches 5B, with excellent comprehensive performance.
  • a low-temperature curing conductive paste in terms of weight percentage, the conductive paste comprises the following components: 4% epoxy resin, 2% barium phenolic resin, 14% diethylene glycol ethyl ether acetate, 70% flake silver powder, Polyethylene glycol 4%, hexamethylene diisocyanate 4%, defoamer 1%, adhesion promoter 1%.
  • Preparation of conductive paste Weigh flake silver powder of estimated weight and stir and disperse it with an organic carrier at a speed of 1000rpm in a stirring tank, then place it for half an hour, and then perform three-roll rolling to finally obtain a viscosity range of 10 -30Pa ⁇ s conductive paste.
  • the test results show that the conductive paste obtained by the above component ratio and preparation method has a curing temperature of 150°C, a high temperature resistance temperature of 500°C, and an adhesion to the substrate of 5B, with excellent comprehensive performance.

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Abstract

本申请提供一种低温固化导电浆料及电子器件，涉及新材料技术领域。按重量百分比计，本申请提供的低温固化导电浆料包括：5％～20％的基础树脂载体、10％～20％的有机溶剂、60％～76％的导电粉体、8％～17％的功能树脂混合体、0.1％～3％的消泡剂以及0.1％～3％的附着力促进剂。本申请的低温固化导电浆料具有低温固化、固化时间短的特性，并且固化后耐高温性能优异。

Description

一种低温固化导电浆料及电子器件
本申请要求于2021年12月30日提交中国专利局，申请号为2021116451580，申请名称为“一种低温固化导电浆料及电子器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及新材料技术领域，尤其涉及一种低温固化导电浆料及电子器件。
背景技术
近年来，随着电子信息技术的迅猛发展，市场对作为电子信息技术的基础和先导的电子信息材料的特异性和功能性要求愈来愈苛刻。而作为电子信息材料的重要组成部分的导电浆料尤为值得关注。
在现有的用于印刷电子产品制备的导电浆料领域中，大部分的导电浆料的固化温度通常较高，使得其只能局限于在一些例如PET、PI等耐高温材料表面的涂布印刷，因而无法直接应用于对温度较为敏感的基材表面，更无法在具有热反应活性的环氧、聚氨酯预制胶膜表面印刷，并且在高温烘烤固化导电浆料时，往往容易造成热固性胶膜过早发生交联反应失效而无法满足后续工艺要求；此外，虽然目前市场上出现了一些低温固化导电浆料，但这些导电浆料还存在低温固化时间长、耐高温性能差、附着力低下、易脱落等问题。
申请内容
为解决上述技术问题，本申请提供了一种低温固化导电浆料及电子器件，该导电浆料具有低温固化、固化时间短的特性，以及固化后具备耐高温的优异性能。
第一方面，本申请提供一种低温固化导电浆料，采用如下技术方案：
按重量百分比计，所述导电浆料包括：5％～20％的基础树脂载体、10％～20％的有机溶剂、60％～76％导电粉体、8％～17％的功能树脂混合体、0.1％～3％的消泡剂以及0.1％～3％的附着力促进剂。
可选地，所述基础树脂载体包括酚醛树脂和/或环氧树脂。
可选地，其中，所述酚醛树脂为钡酚醛树脂。
可选地，所述钡酚醛树脂为采用多环芳香化合物改性的钡酚醛树脂，并且改性过程包括：(1)弱碱有机氨线性催化步骤，以及(2)强碱氢氧化钡催化步骤。
可选地，所述基础树脂载体的分子量为3000～60000；和/或，软化点温度在60℃～100℃之间。
可选地，所述功能树脂混合物至少用作浆料的改性增韧填料，并且包括聚乙二醇和异氰酸酯，其中，所述聚乙二醇与异氰酸酯的重量比为0.4:1～1.75:1，优选地，两者的重量比可以为0.5:1～1:1。
可选地，所述功能树脂混合体中还包括大分子环氧树脂，所述大分子环氧树脂的分子量为30000～50000。
可选地，其中，所述异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基异氰酸酯、多苯基甲烷多异氰酸酯中的一种或者至少两种组成的混合物。
可选地，所述消泡剂为聚硅氧烷消泡剂、有机硅消泡剂、聚醚类消泡剂中的一种或者至少两种；和/或，所述附着力促进剂为硅烷偶联剂类附着力促进剂。
第二方面，本申请提供一种电子器件，采用如下技术方案：
所述电子器件包括：基材，位于所述基材上的导电线路，以及电子元件，其中，所述导电线路由以上任一项所述的低温固化导电浆料制成。
与现有技术相比，本申请具有如下有益效果：
(1)本申请的低温固化导电浆料，可以实现120℃低温固化，采用改性钡酚醛树脂，相较于其它普通树脂，具有更低的固化温度和更快的固化速度，能够有效降低固化温度，缩短固化时间，固化时间为10～20分钟；
(2)本申请的低温固化导电浆料，具备优异的耐高温性能，在低温下固化后能够耐500℃的高温，并且耐温性能稳定、可靠；
(3)本申请的低温固化导电浆料，具有良好的印刷性，以及对基材的附着力佳；
(4)本申请的低温固化导电浆料，具有优良的柔韧性，不仅能够应用于硬质基材，而且还适用于柔性基底。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的电子器件的结构示意图；
图2为本申请实施例提供的导电浆料的制备方法流程图。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
需要说明的是，在不冲突的情况下本申请实施例中的各技术特征均可以相互结合。
前文提及，现有的导电浆料大多固化温度较高，无法用于对温度敏感或具有热反应活性的环氧、聚氨酯预制胶膜等的基材表面印刷；此外，目前一些低温固化浆料还存在固化时间长、耐高温性差，附着力低下等缺陷。
为解决上述技术问题，本申请提供了一种低温固化、耐高温的导电浆料，按重量百分比计，该导电浆料包括5％～20％的基础树脂载体、10％～20％的有机溶剂、60％～76％导电粉体、8％～17％的功能树脂混合体、0.1％～3％的消泡剂以及0.1％～3％的附着力促进剂。本申请的低温固化耐高温导电浆料，能够实现120℃低温固化，固化时间短，并且固化后能够耐500℃的高温，耐温稳定性佳；此外，本申请的导电浆料还具有良好的柔韧性、对基材强的附着力等。
本申请一实施例提供了一种低温固化导电浆料，具体地，按重量百分比计，该导电浆料包括：
5％～20％的基础树脂载体；
10％～20％的有机溶剂；
60％～76％导电粉体；
8％～17％的功能树脂混合体；
0.1％～3％的消泡剂；以及
0.1％～3％的附着力促进剂。
该导电浆料中，基础树脂载体的重量百分比可以为：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％或者20％；溶剂的重量百分比可以为：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％或者20％；导电填料的重量百分比可以为：70％、71％、72％、73％、 74％、75％、76％、77％、78％、79％、80％、81％、82％、83％、84％、85％、86％、87％、88％、89％或者90％。
根据本申请的实施例，所述基础树脂载体可以为聚酯树脂、聚氨酯树脂、环氧树脂、丙烯酸树脂、酚醛树脂、醇酸树脂、有机硅树脂、氯醋树脂、聚酰亚胺树脂中的一种或者至少两种组成的混合物。根据实际应用需要，所述基础树脂载体可以由上述树脂中的一种或多种以合适的比例混合而成。例如1：10～10：1之间的任意比例混合制备得到，本申请对此不作特别限制。
作为本申请的优选技术方案，所述基础树脂载体可以包括酚醛树脂、环氧树脂中的一者或两者。优选地，当所述基础树脂载体包含酚醛树脂和环氧树脂两者时，其中，酚醛树脂和环氧树脂的重量占比可以为2：1～1：2之间的任意值，例如1：1配比混合。若酚醛树脂含量过多，则会导致导电浆料附着力不佳，并且浆料过脆，而若环氧树脂过多，则会影响导电浆料的耐温性能。本申请提供的基础树脂载体能够保证导电浆料具备低温固化特性、良好的印刷性、浸润性以及优良的耐高温性能。
其中，所述酚醛树脂优选为钡酚醛树脂；进一步地，所述钡酚醛树脂为采用多环芳香化合物改性的钡酚醛树脂，并且改性过程包括：(1)弱碱有机氨线性催化步骤，以及(2)强碱氢氧化钡催化步骤。该钡酚醛树脂经上述两步催化改性后，能够有效提高酚醛树脂的邻对位比例，改善树脂的最终固化后的交联密度，从而提升耐温性能；另外，钡酚醛树脂相较于其它普通树脂或酚醛树脂的固化速度更快，并且固化温度更低，一方面，可缩短固化所需时间，本申请所涉及的导电浆料的固化时间为10～20min，例如15min；另一方面，钡酚醛树脂的加入同时也可降低浆料的固化温度，本申请的导电浆料的低温固化温度可以在120℃。
该导电浆料中，所述基础树脂载体的分子量可以为3000～60000之间，软化点在60℃～100℃范围内。上述区间范围的分子量及软化点的树脂可使得导电浆料具备良好的浸润性及印刷性，同时保持贮存稳定性。
根据本申请的实施例，其中，所述功能树脂混合物的重量百分比可以为：8％、9％、10％、11％、12％、13％、14％、15％、16％或17％，并且至少包括聚乙二醇和异氰酸酯，被用作导电浆料的改性增韧填料，其中，所述聚乙二醇与异氰酸酯的重量比为0.4:1～1.75:1，优选为0.5:1～1:1，例如0.4:1、0.5:1、0.7:1、1:1、1.75:1或者上述区间范围内的其它任意比值；或者，按重量比计，优选地，该低温固化导电浆料至少包括4％～7％的聚乙二醇、4％～10％的异氰酸酯。
由前所述，本申请可以采用酚醛树脂作为基础树脂载体，考虑到酚醛树脂材料性质较脆，不能很好的直接形成柔性导电浆料而应用于柔性基材中，因此为了增加导电浆料体系的柔韧性，本申请通过在导电浆料中添加至少起增韧改性作用的功能树脂混合物，例如聚乙二醇和异氰酸酯，以满足柔韧性要求以及柔性基材的适用性。
优选地，所述异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基异氰酸酯、多苯基甲烷多异氰酸酯中的一种或者至少两种组成的混合物。当上述聚乙二醇或异氰酸酯由两种以上的物质混合而成时，各物质之间的添加比例可以是满足导电浆料增韧性要求的任意比例，本申请对此不作特别限制。
需要说明的是，为了进一步地改善导电浆料的柔韧度，同时提高其对基材的可印刷性和附着力，本申请的功能树脂混合体中还包含有大分子环氧树脂，其中，所述大分子环氧树脂的分子量为30000～50000之间，并且，可选地，大分子环氧树脂在所述功能树脂混合体中的重量占比为10％～20％。
此外，由于基础树脂载体，例如酚醛树脂在固化过程中容易产生许多小分子气泡从浆料表面溢出，从而形成多个微气泡孔，为了有效消除该微气泡孔，改善导电浆料的固化后的表面形貌，本申请的导电浆料中还添加一定比例的消泡剂。优选地，所述消泡剂可以为聚硅氧烷消泡剂、有机硅消泡剂、聚醚类消泡剂中的一种或者至少两种，并且重量百分比可以为0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、1.5％、2％、2.5％、3％或上述区间范围内的任意值。
根据本申请的实施例，所述附着力促进剂优选为硅烷偶联剂类附着力促进剂，并且重量百分比可以为0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、1.5％、2％、2.5％、3％或上述区间范围内的任意值。
下面对本申请实施例的导电浆料中的其它组分进行举例说明：
溶剂
本申请实施例中，溶剂的重量百分比可以为10％～20％之间的任意值，并且可选为乙醇、异丙醇、正丙醇、乙二醇、丙二醇、丙三醇、正丁醇、乙二醇丙醚、乙二醇丁醚、二乙二醇乙醚、二乙二醇丙醚、二乙二醇丁醚、丙二醇丙醚、丙二醇丁醚、二丙二醇乙醚、二丙二醇丙醚、二丙二醇丁醚、乙二醇丙醚醋酸酯、乙二醇丁醚醋酸酯、二乙二醇乙醚醋酸酯、二乙二醇丙醚醋酸酯、二乙二醇丁醚醋酸酯、丙二醇丙醚醋酸酯、丙二醇丁醚醋酸酯、二丙二醇乙醚醋酸酯、二丙二醇丙醚醋酸酯、二丙二醇丁醚醋酸酯、异佛尔酮和松油醇中的一种或者至少两种组成的混合物。
导电填料
本申请实施例中，导电填料为金、银、铁、镍、铝、石墨烯、银包铜粉等中的一种或者至少两种；和/或，所述导电填料的形状为片状、球状、线性、立方体等中的一种或几种。并且，所述导电填料的尺寸大小可以为0.1μm～6μm。优选地，本申请实施例中采用导电填料为粒径为300～600nm的球状银粉。
本申请实施例中的导电浆料可以适用于丝网印刷、柔版印刷、移印、挤出式点胶、钢网印刷等成型工艺，成型后加热固化即可得到导电线路。
根据本申请另一实施例，提供一种低温固化导电浆料的制备方法，如图2所示，可包括以下步骤：
步骤S1、制备有机载体：将基础树脂载体、溶剂、聚乙二醇、异氰酸酯、消泡剂、附着力促进剂加热溶解，得到有机载体；
在此过程中，可以通过油浴的方式加热，并在加热的同时进行搅拌，油浴温度可选为70℃～120℃，搅拌速度可选为300rpm～800rpm。
步骤S2、制备导电浆料：将导电填料和有机载体于搅拌罐中搅拌分散，然后放置半小时(可以增强有机载体对导电填料的润湿效果，提高后续辊轧效果)，而后进行三辊轧制，最终得到粘度范围为10～40Pa·s的导电浆料。
在此过程中，搅拌速度可选为500rpm～2500rpm。
对上述方法制得的导电浆料进行加热烧结固化，其中加热烧结温度优选为120～180℃，烧结时间为10～80分钟，从而可形成附着力佳，并具有良好柔韧性的导电层。
此外，本申请实施例还提供一种电子器件，具体地，如图1所示，该电子器件包括：基材1，位于基材1上的导电线路2，导电线路2由以上任一项所述的导电浆料制成。
可选地，如图1所示，电子器件还包括电子元件3，电子元件3形成于导电线路2上。根据实际需要，电子元件可以为开关、电源、发光器件、传感器、芯片等，本申请实施例对此不进行限定。
例如，将导电浆料通过挤出点胶的方式成型在基材上，然后将其置于鼓风干燥箱中加热烧结固化。导电浆料的加热烧结温度为120℃～180℃，烧结时间为10min～80min。
本申请实施例的基材可以为柔性基底，也可以为硬质基底，柔性基底可以为聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚酰胺(PA)等薄膜中的一种。
下面本申请实施例以多个具体实施例对本申请的导电浆料的优势进行说明，但并不因此限制本申请的保护范围。
实施例1
一种低温固化导电浆料，以重量百分比计，该导电浆料包括以下组分：钡酚醛树脂3％、环氧树脂3％、二乙二醇乙醚醋酸酯14％、球状银粉70％、聚乙二醇4％、六亚甲基二异氰酸酯4.5％、消泡剂0.5％和附着力促进剂1％。
上述实施例1中的低温固化导电浆料的制备方法如下：
S1、制备有机载体：按上述重量百分比分别称取钡酚醛树脂、环氧树脂、二乙二醇乙醚醋酸酯、聚乙二醇、六亚甲基二异氰酸酯、消泡剂、附着力促进剂，混合后于油浴中70℃加热搅拌溶解得到有机载体；
S2、制备导电浆料：称取预计重量的球状银粉并将其与S1制得的有机载体于搅拌罐中以1000rpm的速度搅拌分散，然后放置半小时，而后进行三辊轧制，最终获得粘度范围为10-20Pa·s的导电浆料。
经测试结果表明，经上述组分配比及制备方法得到的导电浆料的印刷性良好，浆料固化温度为120℃，耐高温温度为500℃，并且对基材的附着力达到5B，综合性能优异。
实施例2
一种低温固化导电浆料，以重量百分比计，该导电浆料包括以下组分：钡酚醛树脂4％、环氧树脂3％、二乙二醇乙醚醋酸酯14％、球状银粉55％、片状银粉14％、聚乙二醇4％、六亚甲基二异氰酸酯4％、消泡剂1％和附着力促进剂1％。
上述实施例2中的低温固化导电浆料的制备过程为：
S1、制备有机载体：按上述重量百分比分别称取钡酚醛树脂、环氧树脂、二乙二醇乙醚醋酸酯、聚乙二醇、六亚甲基二异氰酸酯、消泡剂、附着力促进剂于油浴中70℃加热搅拌溶解得到有机载体；
S2、制备导电浆料：称取预计重量的球状银粉、片状银粉并将其与有机载体于搅拌罐中以1000rpm的速度搅拌分散，然后放置半小时，而后进行三辊轧制，最终获得粘度范围为10-20Pa·s的导电浆料。
经测试结果表明，经上述组分配比及制备方法得到的导电浆料的固化温度为120℃，耐高温温度为500℃，并且对基材的附着力达到5B，综合性能优异。
实施例3
一种低温固化导电浆料，以重量百分比计，该导电浆料包括以下组分：环氧树脂4％、钡酚醛树脂2％、二乙二醇乙醚醋酸酯14％、片状银粉70％、聚乙二醇4％、六亚甲基二异氰酸4％、消泡剂1％、附着力促进剂1％。
上述实施例3中的低温固化导电浆料的制备过程为：
S1、制备有机载体：按上述重量百分比分别称取钡酚醛树脂、环氧树脂、二乙二醇乙醚醋酸酯、聚乙二醇、六亚甲基二异氰酸酯、消泡剂、附着力促进剂于油浴中90℃加热搅拌溶解得到有机载体；
S2、制备导电浆料：称取预计重量的片状银粉并将其与有机载体于搅拌罐中以1000rpm的速度搅拌分散，然后放置半小时，而后进行三辊轧制，最终获得粘度范围为10-30Pa·s的导电浆料。
经测试结果表明，经上述组分配比及制备方法得到的导电浆料的固化温度为150℃，耐高温温度为500℃，并且对基材的附着力达到5B，综合性能优异。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种低温固化导电浆料，其特征在于，按重量百分比计，包括：5％～20％的基础树脂载体、10％～20％的有机溶剂、60％～76％的导电粉体、8％～17％的功能树脂混合体、0.1％～3％的消泡剂以及0.1％～3％的附着力促进剂。
  2. 根据权利要求1所述的低温固化导电浆料，其特征在于，所述基础树脂载体包括酚醛树脂和/或环氧树脂。
  3. 根据权利要求2所述的低温固化导电浆料，其特征在于，所述酚醛树脂为钡酚醛树脂。
  4. 根据权利要求3所述的低温固化导电浆料，其特征在于，所述钡酚醛树脂为采用多环芳香化合物改性的钡酚醛树脂，并且改性过程包括：弱碱有机氨线性催化步骤，以及强碱氢氧化钡催化步骤。
  5. 根据权利要求1～4任一项所述的低温固化导电浆料，其特征在于，所述基础树脂载体的分子量为3000～60000；和/或，所述基础树脂载体的软化点温度在60℃～100℃之间。
  6. 根据权利要求1～4任一项所述的低温固化导电浆料，其特征在于，所述功能树脂混合体至少用作浆料的改性增韧填料，包括聚乙二醇和异氰酸酯，其中，所述聚乙二醇与异氰酸酯的重量比为0.4:1～1.75:1。
  7. 根据权利要求6所述的低温固化导电浆料，其特征在于，所述功能树脂混合体中还包括大分子环氧树脂，所述大分子环氧树脂的分子量为30000～50000。
  8. 根据权利要求6所述的低温固化导电浆料，其特征在于，
    所述异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基异氰酸酯、多苯基甲烷多异氰酸酯中的一种或者至少两种组成的混合物。
  9. 根据权利要求1～4、7～8任一项所述的低温固化导电浆料，其特征在于：所述消泡剂为聚硅氧烷消泡剂、有机硅消泡剂、聚醚类消泡剂中的一种或者至少两种；和/或，所述附着力促进剂为硅烷偶联剂类附着力促进剂。
  10. 一种电子器件，其特征在于，包括：基材、位于所述基材上的导电线路、以及电子元件，其中，所述导电线路由权利要求1～9任一项所述的低温固化导电浆料制成。
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