WO2023216490A1 - 一种环氧树脂基导电浆料及其制备方法与应用 - Google Patents

一种环氧树脂基导电浆料及其制备方法与应用 Download PDF

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Publication number
WO2023216490A1
WO2023216490A1 PCT/CN2022/120153 CN2022120153W WO2023216490A1 WO 2023216490 A1 WO2023216490 A1 WO 2023216490A1 CN 2022120153 W CN2022120153 W CN 2022120153W WO 2023216490 A1 WO2023216490 A1 WO 2023216490A1
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Prior art keywords
conductive
conductive paste
epoxy resin
modified epoxy
conductive slurry
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PCT/CN2022/120153
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English (en)
French (fr)
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姬振行
任中伟
邵竞岩
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北京梦之墨科技有限公司
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Publication of WO2023216490A1 publication Critical patent/WO2023216490A1/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
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present application relates to the technical field of new materials, and in particular to an epoxy resin-based conductive slurry and its preparation method and application.
  • circuit boards such as printed circuit boards are also developing towards flexibility and high density, which puts forward new requirements for printed circuit board materials, requiring circuit board materials to have High electrical conductivity, thermal conductivity, thermal stability and flexibility, etc.
  • epoxy conductive adhesive is widely used in microelectronic packaging, flexible circuit board manufacturing and other fields.
  • the purpose of this application is to provide a conductive paste with low resistance and high adhesion.
  • the difficulty in research and development is mainly due to the difficulty in taking into account both the resistivity and adhesion of the product (the conductive paste with low resistance has poor adhesion).
  • this application provides an epoxy resin-based conductive slurry and a preparation method thereof.
  • this application first provides a conductive paste, which includes 9.6-30wt% organic solvent;
  • the conductive paste also includes modified epoxy resin
  • the mass ratio of the modified epoxy resin to the organic solvent is (1-3): (2-6);
  • the modified epoxy resin has a viscosity of 10,000-30,000 cps at 25° C. (that is, the viscosity of the modified epoxy resin at 25° C. is between 10,000-30,000 cps).
  • epoxy resin is widely used in coatings, adhesives, pouring agents, encapsulating materials and fiberglass products due to its excellent mechanical, electrical properties and chemical corrosion resistance; however, the performance of pure epoxy resin after curing is relatively poor. Brittle, impact strength and thermal shock resistance are poor; in order to improve the above-mentioned shortcomings of epoxy resin cured products, a commonly used method in the prior art is to introduce plasticizers (such as phthalic acid) into the epoxy resin cured system. dibutyl ester, triphenyl phosphate, etc.). However, there are still certain problems with the introduction of plasticizers. For example, the resistance of epoxy resin-based conductive paste is relatively large.
  • plasticizers In order to reduce its resistance, a large amount of conductive metal powder (i.e., conductive filler) is added to the paste, which causes It is easy to cause the coating or conductive circuit formed by the slurry to crack; although plasticizers can improve the above-mentioned cracking problem to a certain extent, the stability of conductive slurries containing plasticizers is poor (over time, plasticization The agent has a tendency to segregate from the system during the curing process, causing oil and deterioration on the surface of the material); in addition, plasticizers have limited effects on plasticizing and toughening, and will also reduce the adhesion of the conductive slurry. .
  • modified epoxy resin with a viscosity of 10,000-30,000 cps at 25°C after compounding with an organic solvent, can give the conductive slurry a suitable viscosity.
  • the conductive slurry within this viscosity range is expected to have both resistance and adhesion. focus;
  • the modified epoxy resin is prepared by a method including the following steps:
  • the modified epoxy resin is obtained through cross-linking reaction.
  • step S1 when the isocyanate content in the polymerization system is 3-5 wt%, the polymerization reaction is stopped, and the polyurethane prepolymer is obtained after cooling down; preferably, the temperature of the polymerization reaction is 70-80°C.
  • step S2 the cross-linking reaction is carried out at 50-60°C for 30-60 minutes.
  • the polyether polyol is vacuum dehydrated at 105-110°C in advance; and then the above-mentioned step S1 is performed.
  • the epoxy resin is dehydrated and encapsulated in advance; and then the above-mentioned step S2 is performed.
  • the modified epoxy resin includes the following steps:
  • the method for detecting the isocyanate content in the polymerization system is preferably the di-n-butylamine method.
  • the epoxy resin is modified to introduce a flexible polyurethane segment structure into its epoxy structure, thereby enhancing its flexibility and improving its bonding strength.
  • the viscosity of the modified epoxy resin prepared by this application meets the above requirements, and its modification rate is ideal (if the polyurethane modification rate is high, the Tg of the modified epoxy resin will decrease, which will lead to the resistance of the conductive slurry. Thermal properties become worse, and its adhesion becomes worse under high temperature conditions, and it is easy to fall off from the surface of the substrate; if the polyurethane modification rate is low, the brittleness of the conductive slurry increases after curing, and its adhesion becomes worse under low temperature conditions, and it is easy to fall off. peeled off from the substrate surface).
  • the organic solvent is selected from one or more of diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, and diethylene glycol ethyl ether acetate.
  • the suitable organic solvents are as described above; the above organic solvents have better effects after being compounded with modified epoxy resin.
  • the conductive paste also includes 60-84.9wt% conductive filler
  • the conductive filler is selected from one or more of gallium, indium, tin, zinc, bismuth, gold, silver, iron, nickel, aluminum, graphene, and silver-coated copper powder.
  • the shape of the conductive filler is one or a combination of sheet, spherical, linear, cubic;
  • the particle size of the conductive filler is 0.1-10 ⁇ m (0.5-5 ⁇ m is particularly ideal); the conductive filler within the above particle size range can ensure uniform dispersion and achieve adhesion and adhesion of the conductive slurry to the substrate ( i.e. adhesion) for the best results.
  • the conductive paste further includes 0.1-5wt% curing agent
  • the curing agent is one or more of hepatitis phthalate, maleic anhydride, methylimidazole, dicyandiamide, modified dicyandiamide, tertiary amine modified phenol, and urea-based accelerator.
  • the curing agent is a tertiary amine-modified phenol and/or a urea-based accelerator selected from the group consisting of hepatitis phthalate, maleic anhydride, methylimidazole, dicyandiamide, and dicyandiamide modified products. One or a mixture of several.
  • the curing agent is a mixture of a urea-based accelerator and dicyandiamide in a mass ratio of (0.05-0.2): (0.1-0.6).
  • the suitable conductive fillers and curing agents are as described above; after compounding with organic solvents and modified epoxy resins, the above conductive fillers and curing agents not only have good resistivity and The adhesion also further improves the overall comprehensive performance of the slurry (especially the printing performance).
  • the conductive paste also includes 0-1wt% additives
  • the auxiliary agent at least includes a tackifier, and the tackifier is selected from one or more of KH550, KH560, and KH570;
  • the auxiliary agent may also include a defoaming agent, which may be a silicone defoaming agent and/or a petroleum defoaming agent, such as sxp-109, BYK-024 and other defoaming agents. agent; of course, those skilled in the art should understand that the defoaming agent can be omitted in this application, or a vacuum method can be used for defoaming, which is not particularly limited in this application.
  • a defoaming agent which may be a silicone defoaming agent and/or a petroleum defoaming agent, such as sxp-109, BYK-024 and other defoaming agents. agent; of course, those skilled in the art should understand that the defoaming agent can be omitted in this application, or a vacuum method can be used for defoaming, which is not particularly limited in this application.
  • the conductive paste includes the following components by weight:
  • modified epoxy resin 5-15 parts of modified epoxy resin, 9.6-30 parts of organic solvent, 60-84.9 parts of conductive filler, 0.1-5 parts of curing agent, and 0-1 part of additives; among which,
  • the 25°C viscosity of the modified epoxy resin is 10000-30000cps
  • the organic solvent is selected from one or more of diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, and diethylene glycol ethyl ether acetate;
  • the conductive filler is selected from one or more of gallium, indium, tin, zinc, bismuth, gold, silver, iron, nickel, aluminum, graphene, and silver-coated copper powder;
  • the curing agent is a mixture of urea-based accelerator and dicyandiamide in a mass ratio of (0.05-0.2): (0.1-0.6);
  • the auxiliary agent at least includes a tackifier, and the tackifier is selected from one or more of KH550, KH560, and KH570.
  • the conductive slurry includes the following mass percentage components:
  • the 25°C viscosity of the modified epoxy resin is 10000-30000cps
  • the organic solvent is selected from one or more of diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, and diethylene glycol ethyl ether acetate;
  • the conductive filler is selected from one or more of gallium, indium, tin, zinc, bismuth, gold, silver, iron, nickel, aluminum, graphene, and silver-coated copper powder;
  • the curing agent is a mixture of urea-based accelerator and dicyandiamide in a mass ratio of (0.05-0.2): (0.1-0.6);
  • the auxiliary agent at least includes a tackifier, and the tackifier is selected from one or more of KH550, KH560, and KH570.
  • the viscosity of the conductive slurry is 20-40 Pa ⁇ s.
  • the solid content of the conductive slurry is 65-90wt%; the conductive slurry with the above solid content, after forming a coating or conductive circuit, can not only ensure its adhesion to the substrate, but also enable the conductive particles to The amount of exposure on the surface is just enough to achieve a good combination with the coating.
  • This application also provides a method for preparing the above-mentioned conductive slurry, which includes the following steps:
  • This application also found that mixing the components in the above manner can further ensure that the product properties do not change differentially on the basis of ensuring the uniformity of the product.
  • step (3) the obtained mixture is allowed to stand and then rolled with three rollers to obtain the conductive slurry.
  • This application also provides the application of the above-mentioned conductive paste in printing.
  • the printing specifically includes printing the conductive paste on the base material and then curing.
  • the printing method can adopt screen printing, flexographic printing, pad printing, extrusion dispensing or stencil printing, etc.;
  • the substrate can be a flexible substrate or a hard substrate. , for example: it can be polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyimide (PI), poly One or more of the amides (PA).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • PA poly One or more of the amides
  • the printing thickness of the conductive paste on the substrate is 10-50 ⁇ m.
  • the curing is performed at 120-200°C for 10-80 minutes.
  • the resistance of the coating or conductive circuit formed after curing can be as low as 5m ⁇ / ⁇ , and the adhesion is ⁇ 4B.
  • the coating or conductive circuit made of this conductive slurry not only has good conductivity, but also has good flexibility, stretch resistance and wear resistance, and has excellent adhesion to the surface of the substrate to avoid It has good reliability and can better meet the requirements of flexible circuit boards when the coating or conductive lines peel off from the substrate.
  • This embodiment provides a conductive slurry, which includes the following components by mass percentage:
  • the preparation method of the modified epoxy resin includes the following steps:
  • This embodiment also provides a method for preparing the above conductive slurry, which includes the following steps:
  • the viscosity of the conductive paste in this embodiment is 20-25 Pa ⁇ s.
  • This embodiment provides a conductive slurry, which includes the following components by mass percentage:
  • This embodiment also provides a method for preparing the above conductive slurry, which includes the following steps:
  • the viscosity of the conductive paste in this embodiment is 35-40 Pa ⁇ s.
  • This embodiment provides a conductive slurry, which includes the following components by mass percentage:
  • the preparation method of the conductive paste in this embodiment is the same as that in Example 2.
  • the viscosity of the conductive paste in this embodiment is 25-35 Pa ⁇ s.
  • This comparative example provides a conductive paste, which includes the following components by mass percentage:
  • the preparation method of the conductive paste of this comparative example is the same as that of Example 2.
  • the viscosity of the conductive paste in this comparative example is 40-50 Pa ⁇ s.
  • This comparative example provides a conductive paste, which includes the following components by mass percentage:
  • Modified epoxy resin 20wt%, diethylene glycol ether acetate 22.8wt%, flake silver powder 56.4wt%, dicyandiamide ( 1400F) curing agent 0.2wt%, urea-based accelerator (AmicureUR7/10) 0.1wt%, tackifier (KH560) 0.5wt%;
  • the preparation method of the conductive paste of this comparative example is the same as that of Example 2.
  • the viscosity of the conductive paste in this comparative example is 20-25 Pa ⁇ s.
  • This comparative example provides a conductive paste, which includes the following components by mass percentage:
  • Example 2 The difference between the preparation method of the conductive slurry of this comparative example and Example 2 is that: dicyandiamide ( 1400F) curing agent and urea-based accelerator (AmicureUR7/10) were replaced with ethylenediamine.
  • the viscosity of the conductive paste in this comparative example is 25-30 Pa ⁇ s.
  • the conductive pastes of the examples and comparative examples were printed on the substrate with a printing thickness of 30 ⁇ m, and then cured at 160°C for 30 minutes to obtain several conductive lines with the same pattern; the performance of each conductive line was Carry out testing.
  • the specific testing methods are as follows:
  • the resistance measurement refers to the square resistance measurement method of GB17473.3-2008 "Test Methods for Precious Metal Slurries for Microelectronic Technology";

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

本申请涉及新材料技术领域，尤其涉及一种环氧树脂基导电浆料及其制备方法与应用。所述导电浆料包括9.6-30wt％的有机溶剂；所述导电浆料还包括改性环氧树脂；所述改性环氧树脂与所述有机溶剂的质量比为1-3：2-6；所述改性环氧树脂的25℃黏度为10000-30000cps。本申请通过对导电浆料的配方及制备工艺进行优化，得到了一种兼顾低电阻及高附着力的导电浆料，并且，该导电浆料还具备良好的印刷性能。利用该导电浆料制成的涂层或者导电线路，不仅具有良好的导电性，还具有良好的柔韧性、耐拉伸性及耐磨性，而且对基材表面具有极佳的附着力，可靠性佳，能够更好地满足柔性线路板的要求。

Description

一种环氧树脂基导电浆料及其制备方法与应用
本申请要求于2022年05月12日提交中国专利局，申请号为2022105181262，申请名称为“一种环氧树脂基导电浆料及其制备方法与应用”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，尤其涉及一种环氧树脂基导电浆料及其制备方法与应用。
背景技术
随着电子产品不断向微型化、高度集成化等方向发展，电路板如印刷电路板也向着柔性化、高密集化发展，这对印刷电路板的材料提出了新的要求，要求电路板材料具有较高的导电性、导热性、热稳定性及柔性等。而环氧导电胶作为一种代替传统锡铅焊料的绿色粘结材料，被广泛应用于微电子封装、柔性电路板制造等领域。
随着电子浆料的不断发展，环氧导电浆料的研究也不断趋向于可低温固化、可快速干燥等。新的工艺要求使电子浆料的使用更为便捷，同时可以不断降低成本，缩短生产周期等。但目前，相关现有技术中导电浆料作为涂层涂覆在基材表面时，附着力、耐磨性和强度较差，且热稳定性、耐高低温性不佳，而且应用于柔性基材时，导电浆料的耐弯折性不良，往往容易造成涂层脱落或开裂等缺陷。
鉴于此，特提出本申请。
申请内容
本申请的目的在于提供一种低电阻、高附着力的导电浆料，其研发难度主要在于产品的电阻性及其附着力难以同时兼顾(低电阻的导电浆料附着力较差)。在对影响上述效果的关键因素进行探究和优化后，本申请提供了一种环氧树脂基导电浆料及其制备方法。
具体而言，本申请首先提供一种导电浆料，其包括9.6-30wt％的有机溶剂；
所述导电浆料还包括改性环氧树脂；
所述改性环氧树脂与所述有机溶剂的质量比为(1-3)：(2-6)；
所述改性环氧树脂的25℃黏度为10000-30000cps(即改性环氧树脂在25℃时的黏度在10000-30000cps之间)。
作为已知技术，环氧树脂以其优异的力学、电气性能和耐化学腐蚀性能被广泛地应用于涂料、胶粘剂、浇注剂、包封料及玻璃钢制品中；但是单纯的环氧树脂固化后性能较脆、冲击强度和耐热冲击性能较差；为了改善环氧树脂固化物所存在的上述不足，现有技术中常用的方法是在环氧树脂固化体系中引入增塑剂(如邻苯二甲酸二丁酯、磷酸三苯酯等)。然而，增塑剂的引入仍然存在一定问题，比如：环氧树脂基导电浆料的电阻较大，为了降低其电阻，浆料中会添加大量的导电金属粉料(即导电填料)，这就容易造成浆料所形成的涂层或者导电线路开裂；虽然增塑剂可一定程度上改善上述开裂的问题，但包含增塑剂的导电浆料稳定性较差(随着时间的推移，增塑剂在固化过程中有从体系中离析的倾向，从而造成材料表面出油、变质)；除此之外，增塑剂对增塑、增韧的效果有限，还会降低导电浆料的附着力。
本申请发现，通过上述方案，在确保导电浆料低电阻的基础上，可进一步提高其附着力；
其中，25℃时黏度为10000-30000cps的改性环氧树脂、在与有机溶剂复配后，可赋予导电浆料适宜的粘度，在该粘度范围内的导电浆料有望同时兼顾电阻性和附着力；
进一步控制改性环氧树脂与有机溶剂的质量比在(1-3)：(2-6)之间，可确保导电浆料具备较低电阻的情况下，同时兼顾良好的附着力。
此外，本申请提供的导电浆料的柔韧性也得以提升。
本领域人员可按照公知常识设置配方中的其他功能组分和工艺中的参数，其均可以得到与本申请上述描述相当的效果。不过，关于其他组分和参数也存在更优的技术方案，为此，本申请进一步进行了探究并得到如下的优选方案。
作为优选，所述改性环氧树脂由包括如下步骤的方法制得：
S1、以聚醚多元醇和HDI(六亚甲基二异氰酸酯)为原料，经聚合反应，得到聚氨酯预聚体；
S2、以环氧树脂和所述聚氨酯预聚体为原料，经交联反应，即得所述改性环氧树脂。
进一步地，步骤S1中，待聚合体系中的异氰酸酯含量为3-5wt％时，停止聚合反应，降温后即得所述聚氨酯预聚体；优选所述聚合反应的温度为70-80℃。
进一步地，步骤S2中，所述交联反应在50-60℃下进行30-60min。
进一步地，预先将聚醚多元醇在105-110℃下进行真空脱水；而后再进行上述步骤S1的操作。
进一步地，预先将环氧树脂脱水、封装；而后再进行上述步骤S2的操作。
作为较佳的技术方案，所述改性环氧树脂包括如下步骤：
S1、将聚醚多元醇在105-110℃下进行真空脱水；
S2、将HDI升温至70-80℃后，加入溶剂，并通入N 2保护，搅拌速率为300-1000转/分，而后加入真空脱水后的聚醚多元醇、催化剂(优选为有机锡或有机铋)，反应60-120min，直至聚合体系中的异氰酸酯含量为3-5wt％时，加入阻聚剂(优选为苯甲酰氯)，降温继续搅拌10-20min，得到聚氨酯预聚体；
S3、将环氧树脂脱水、封装后，与溶剂混合，搅拌至环氧树脂完全溶解，升温至50-60℃，而后加入所述聚氨酯预聚体(优选W 聚氨酯预聚体/W 环氧树脂＝1：8-12)，反应30-60min后，即得所述改性环氧树脂。
在上述技术方案中，检测聚合体系中异氰酸酯含量的方法优选为：二正丁胺法。
如此，本申请通过对环氧树脂进行改性处理，使得其环氧结构中引入柔性的聚氨酯链段结构，从而能够增强其柔韧性，并且提高其粘结强度。
本申请制得的改性环氧树脂的黏度符合上述要求，并且，其改性率理想(若聚氨酯改性率较高，则导致改性环氧树脂的Tg降低，进而导致导电浆料的耐热性变差，高温条件下其附着力变差，容易从基材表面脱落；若聚氨酯改性率较低，则导电浆料固化后脆性增加，在低温下条件下其附着力变差，容易从基材表面脱落)。
作为优选，所述有机溶剂选自二乙二醇丁醚、丙二醇丁醚、二丙二醇乙醚、二乙二醇乙醚醋酸酯中的一种或几种。
针对本申请的浆料体系，与之相适配的有机溶剂如上所述；上述有机溶剂在与改性环氧树脂复配后，效果更佳。
作为优选，所述导电浆料还包括60-84.9wt％的导电填料；
所述导电填料选自镓、铟、锡、锌、铋、金、银、铁、镍、铝、石墨烯、银包铜粉中的一种或几种。
进一步地，所述导电填料的形状为片状、球状、线形、立方体中的一种或几种的组合；
更进一步地，所述导电填料的粒径为0.1-10μm(0.5-5μm尤为理想)；上述粒径范围内的导电填料，能够保证其分散均匀，实现导电浆料对基材吸附粘接性(即附着力)的最佳效果。
作为优选，所述导电浆料还包括0.1-5wt％的固化剂；
所述固化剂为邻苯二甲酸肝、顺丁烯二酸酐、甲基咪唑、双氰胺、双氰胺改性物、叔胺改性苯酚、脲基促进剂中的一种或几种。
进一步地，所述固化剂为叔胺改性苯酚和/或脲基促进剂与选自邻苯二甲酸肝、顺丁烯二酸酐、甲基咪唑、双氰胺、双氰胺改性物中一种或几种的混合物。
更进一步地，所述固化剂为脲基促进剂与双氰胺按质量比(0.05-0.2)：(0.1-0.6)的混合物。
针对本申请的浆料体系，与之相适配的导电填料和固化剂如上所述；上述导电填料和固化剂在与有机溶剂、改性环氧树脂复配后，不仅具有良好的电阻性和附着力，还进一步提高了浆料整体的综合性能(尤其是印刷性能)。
作为优选，所述导电浆料还包括0-1wt％的助剂；
所述助剂至少包括增粘剂，所述增粘剂选自KH550、KH560、KH570中的一种或几种；
除上述增粘剂外，所述助剂还可以包括消泡剂，所述消泡剂可以为有机硅消泡剂和/或石油类消泡剂，例如sxp-109、BYK-024等消泡剂；当然，本领域技术人员应当理解，本申请可以省略消泡剂，也可以采用真空方法脱泡，本申请对此不作特别限制。
本领域人员可依照常识对上述方案进行组合，以得到关于本申请的较优实施例。
作为本申请的优选方案，所述导电浆料包括如下重量份组分：
改性环氧树脂5-15份，有机溶剂9.6-30份，导电填料60-84.9份，固化剂0.1-5份，助剂0-1份；其中，
所述改性环氧树脂的25℃黏度为10000-30000cps；
所述有机溶剂选自二乙二醇丁醚、丙二醇丁醚、二丙二醇乙醚、二乙二醇乙醚醋酸酯中的一种或几种；
所述导电填料选自镓、铟、锡、锌、铋、金、银、铁、镍、铝、石墨烯、银包铜粉中的一种或几种；
所述固化剂为脲基促进剂与双氰胺按质量比(0.05-0.2)：(0.1-0.6)的混合物；
所述助剂至少包括增粘剂，所述增粘剂选自KH550、KH560、KH570中的一种或几种。
作为本申请的一种优选实施方案，所述导电浆料包括如下质量百分比的组分：
改性环氧树脂5-15wt％，有机溶剂9.6-30wt％，导电填料60-84.9wt％，固化剂0.1-5wt％，助剂0-1wt％；其中，
所述改性环氧树脂的25℃黏度为10000-30000cps；
所述有机溶剂选自二乙二醇丁醚、丙二醇丁醚、二丙二醇乙醚、二乙二醇乙醚醋酸酯中的一种或几种；
所述导电填料选自镓、铟、锡、锌、铋、金、银、铁、镍、铝、石墨烯、银包铜粉中的一种或几种；
所述固化剂为脲基促进剂与双氰胺按质量比(0.05-0.2)：(0.1-0.6)的混合物；
所述助剂至少包括增粘剂，所述增粘剂选自KH550、KH560、KH570中的一种或几种。
作为优选，所述导电浆料的粘度为20-40Pa·s。
作为优选，所述导电浆料的固含量为65-90wt％；上述固含量的导电浆料，在形成涂层或者导电线路后，既可以保证其与基材的附着力，又能够使得导电粒子裸露在表面的量正好与镀层实现很好的结合。
本申请还提供以上所述的导电浆料的制备方法，包括如下步骤：
(1)将改性环氧树脂和有机溶剂混合，得预混料；
(2)将所述预混料和除改性环氧树脂、有机溶剂、导电填料之外的其他组分混合，得环氧胶黏剂载体；
(3)将所述环氧胶黏剂载体和导电填料混合。
本申请还发现，采用上述方式混合各组分，可在确保产品均匀性的基础上，进一步保障产品性状不发生差异性变化。
作为优选，步骤(3)中，将所得混合物静置后进行三辊轧制，即得所述导电浆料。
本申请同时提供以上所述的导电浆料在印刷中的应用。
作为优选，所述印刷具体为：将所述导电浆料印刷在基材上，而后进行固化。
在具体的实施方式中，所述印刷的方式可采用丝网印刷、柔版印刷、移印、挤出式点胶或钢网印刷等；所述基材可为柔性基材或硬质基材，比如：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)中的一种或几种。
进一步地，所述导电浆料在所述基材上的印刷厚度为10-50μm。
更进一步地，所述固化在120-200℃下进行10-80min。
在上述技术方案中，固化后形成的涂层或者导电线路的电阻最低可达5mΩ/□，并且附着力≥4B。
基于上述方案，本申请的有益效果如下：
本申请通过对导电浆料的配方及制备工艺进行优化，得到了一种兼顾低电阻及高附着力的导电浆料，并且，该导电浆料还具备良好的印刷性能。利用该导电浆料制成的涂层或者导电线路，不仅具有良好的导电性，还具有良好的柔韧性、耐拉伸性及耐 磨性，而且对基材表面具有极佳的附着力，避免涂层或者导电线路从基材上脱落的情况，可靠性佳，能够更好地满足柔性线路板的要求。
具体实施方式
以下实施例用于说明本申请，但不用来限制本申请的范围。
实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
实施例1
本实施例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂10wt％，二乙二醇乙醚醋酸酯10.75wt％，片状银粉79.1wt％，双氰胺(
Figure PCTCN2022120153-appb-000001
1400F)固化剂0.1wt％，脲基促进剂(AmicureUR7/10)0.05wt％；
其中，所述改性环氧树脂的制备方法包括如下步骤：
S1、将聚醚多元醇加入到容器中，在110℃下真空脱水1-2小时，封装备用；
S2、将HDI升温至70℃后，加入少量溶剂，并通入N 2保护，搅拌速率为300-1000转/分，而后缓慢滴加真空脱水后的聚醚多元醇、有机锡催化剂(2滴即可)，反应60min，此时聚合体系中的异氰酸酯含量为3wt％时，加入2滴阻聚剂苯甲酰氯，降温继续搅拌10min，得到聚氨酯预聚体；
S3、将环氧树脂脱水、封装后，与溶剂混合，在800转/分下搅拌至环氧树脂完全溶解，升温至50℃，而后加入所述聚氨酯预聚体(W 聚氨酯预聚体/W 环氧树脂＝1：10)，反应30min后，即得所述改性环氧树脂。
本实施例还提供上述导电浆料的制备方法，包括如下步骤：
(1)将改性环氧树脂和二乙二醇乙醚醋酸酯投入容器中，加热搅拌至完全溶解，而后冷却至室温(25±5℃)，得预混料；
(2)向所述预混料中加入双氰胺(
Figure PCTCN2022120153-appb-000002
1400F)固化剂和脲基促进剂(AmicureUR7/10)，搅拌均匀，得环氧胶黏剂载体；
(3)向所述环氧胶黏剂载体中加入片状银粉，以1500rpm的速度分散均匀，静置半小时后进行三辊轧制，即得所述导电浆料。
本实施例的导电浆料的粘度为20-25Pa·s。
实施例2
本实施例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂10wt％，二乙二醇乙醚醋酸酯9.6wt％，片状银粉79.1wt％，双氰胺(
Figure PCTCN2022120153-appb-000003
1400F)固化剂0.6wt％，脲基促进剂(AmicureUR7/10)0.2wt％，增粘剂(KH560)0.5％；
其中，所述改性环氧树脂的制备方法同实施例1。
本实施例还提供上述导电浆料的制备方法，包括如下步骤：
(1)将改性环氧树脂和二乙二醇乙醚醋酸酯投入容器中，加热搅拌至完全溶解，而后冷却至室温(25±5℃)，得预混料；
(2)向所述预混料中加入双氰胺(
Figure PCTCN2022120153-appb-000004
1400F)固化剂、脲基促进剂(AmicureUR7/10)和增粘剂(KH560)，搅拌均匀，得环氧胶黏剂载体；
(3)向所述环氧胶黏剂载体中加入片状银粉，以1500rpm的速度分散均匀，静置半小时后进行三辊轧制，即得所述导电浆料。
本实施例的导电浆料的粘度为35-40Pa·s。
实施例3
本实施例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂10wt％，二乙二醇乙醚醋酸酯10.25wt％，片状银粉39.1wt％，球状银粉40wt％，双氰胺(
Figure PCTCN2022120153-appb-000005
1400F)固化剂0.1wt％，脲基促进剂(AmicureUR7/10)0.05wt％，增粘剂(KH560)0.5wt％；
其中，所述改性环氧树脂的制备方法同实施例1。
本实施例导电浆料的制备方法同实施例2。
本实施例的导电浆料的粘度为25-35Pa·s。
对比例1
本对比例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂10wt％，二乙二醇乙醚醋酸酯7.4wt％，片状银粉79.1wt％，双氰胺(
Figure PCTCN2022120153-appb-000006
1400F)固化剂2wt％，脲基促进剂(AmicureUR7/10)1wt％，增粘剂(KH560)0.5wt％；
其中，所述改性环氧树脂的制备方法同实施例1。
本对比例导电浆料的制备方法同实施例2。
本对比例的导电浆料的粘度为40-50Pa·s。
对比例2
本对比例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂20wt％，二乙二醇乙醚醋酸酯22.8wt％，片状银粉56.4wt％，双氰胺(
Figure PCTCN2022120153-appb-000007
1400F)固化剂0.2wt％，脲基促进剂(AmicureUR7/10)0.1wt％，增粘剂(KH560)0.5wt％；
其中，所述改性环氧树脂的制备方法同实施例1。
本对比例导电浆料的制备方法同实施例2。
本对比例的导电浆料的粘度为20-25Pa·s。
对比例3
本对比例提供一种导电浆料，其包括如下质量百分比的组分：
改性环氧树脂10wt％，二乙二醇乙醚醋酸酯10.25wt％，片状银粉79.1wt％，乙二胺0.15wt％，增粘剂(KH560)0.5wt％；
其中，所述改性环氧树脂的制备方法同实施例1。
本对比例导电浆料的制备方法与实施例2的区别在于：将双氰胺(
Figure PCTCN2022120153-appb-000008
1400F)固化剂和脲基促进剂(AmicureUR7/10)替换为乙二胺。
本对比例的导电浆料的粘度为25-30Pa·s。
试验例1
1、本试验例分别将实施例和对比例的导电浆料印刷在基材上，印刷厚度为30μm，而后在160℃下固化30min，得到若干个图案相同的导电线路；对各导电线路的性能进行检测，具体检测方法如下：
(1)电阻测定参考GB17473.3-2008《微电子技术用贵金属浆料测试方法》方阻测定方法检测；
(2)附着力测定参考GB17473.3-2008《微电子技术用贵金属浆料测试方法》附着力测定方法检测。
2、检测结果如表1所示；
表1利用实施例和对比例导电浆料形成的导电线路的性能测试结果
导电浆料 附着力(B) 电阻(mΩ/□) 外观
实施例1 5B 12 正常
实施例2 5B 38 正常
实施例3 5B 5 正常
对比例1 4B 46 正常
对比例2 5B 73 正常
对比例3 4B 16 30d后外观不正常
虽然，上文中已经用一般性说明及具体实施方案对本申请作了详尽的描述，但在本申请基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本申请精神的基础上所做的这些修改或改进，均属于本申请要求保护的范围。

Claims (17)

  1. 一种导电浆料，其特征在于，其包括9.6-30wt％的有机溶剂；
    所述导电浆料还包括改性环氧树脂；
    所述改性环氧树脂与所述有机溶剂的质量比为(1-3)：(2-6)；
    所述改性环氧树脂的25℃黏度为10000-30000cps。
  2. 根据权利要求1所述的导电浆料，其特征在于，所述改性环氧树脂由包括如下步骤的方法制得：
    S1、以聚醚多元醇和HDI为原料，经聚合反应，得到聚氨酯预聚体；
    S2、以环氧树脂和所述聚氨酯预聚体为原料，经交联反应，即得所述改性环氧树脂。
  3. 根据权利要求2所述的导电浆料，其特征在于，步骤S1中，待聚合体系中的异氰酸酯含量为3-5wt％时，停止聚合反应，降温后即得所述聚氨酯预聚体；
    和/或，步骤S2中，所述交联反应在50-60℃下进行30-60min。
  4. 根据权利要求3所述的导电浆料，其特征在于，所述聚合反应的温度为70-80℃。
  5. 根据权利要求1-4任一项所述的导电浆料，其特征在于，所述有机溶剂选自二乙二醇丁醚、丙二醇丁醚、二丙二醇乙醚、二乙二醇乙醚醋酸酯中的一种或几种。
  6. 根据权利要求1-5任一项所述的导电浆料，其特征在于，所述导电浆料还包括60-84.9wt％的导电填料；
    所述导电填料选自镓、铟、锡、锌、铋、金、银、铁、镍、铝、石墨烯、银包铜粉中的一种或几种。
  7. 根据权利要求6所述的导电浆料，其特征在于，所述导电填料的形状为片状、球状、线形、立方体中的一种或几种的组合。
  8. 根据权利要求1-7任一项所述的导电浆料，其特征在于，所述导电浆料还包括0.1-5wt％的固化剂；
    所述固化剂为邻苯二甲酸肝、顺丁烯二酸酐、甲基咪唑、双氰胺、双氰胺改性物、叔胺改性苯酚、脲基促进剂中的一种或几种。
  9. 根据权利要求8所述的导电浆料，其特征在于，所述固化剂为叔胺改性苯酚和/或脲基促进剂与选自邻苯二甲酸肝、顺丁烯二酸酐、甲基咪唑、双氰胺、双氰胺改性物中一种或几种的混合物。
  10. 根据权利要求9所述的导电浆料，其特征在于，所述固化剂为脲基促进剂与双氰胺按质量比(0.05-0.2)：(0.1-0.6)的混合物。
  11. 根据权利要求1-10任一项所述的导电浆料，其特征在于，所述导电浆料还包括0-1wt％的助剂；
    所述助剂至少包括增粘剂，所述增粘剂选自KH550、KH560、KH570中的一种或几种。
  12. 根据权利要求1-11任一项所述的导电浆料，其特征在于，所述导电浆料的粘度为20-40Pa·s；
    和/或，所述导电浆料的固含量为65-90wt％。
  13. 权利要求1-12任一项所述的导电浆料的制备方法，其特征在于，包括如下步骤：
    (1)将改性环氧树脂和有机溶剂混合，得预混料；
    (2)将所述预混料和除改性环氧树脂、有机溶剂、导电填料之外的其他组分混合，得环氧胶黏剂载体；
    (3)将所述环氧胶黏剂载体和导电填料混合。
  14. 根据权利要求13所述的导电浆料的制备方法，其特征在于，步骤(3)中，将所得混合物静置后进行三辊轧制，即得所述导电浆料。
  15. 权利要求1-12任一项所述的导电浆料在印刷中的应用，所述印刷具体为：将所述导电浆料印刷在基材上，而后进行固化。
  16. 根据权利要求15所述的导电浆料在印刷中的应用，其特征在于，所述导电浆料在所述基材上的印刷厚度为10-50μm。
  17. 根据权利要求15所述的导电浆料在印刷中的应用，其特征在于，所述固化在120-200℃下进行10-80min。
PCT/CN2022/120153 2022-05-12 2022-09-21 一种环氧树脂基导电浆料及其制备方法与应用 WO2023216490A1 (zh)

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