WO2023000316A1 - Encre conductrice composite présentant une conductivité élevée et procédé pour sa préparation - Google Patents

Encre conductrice composite présentant une conductivité élevée et procédé pour sa préparation Download PDF

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Publication number
WO2023000316A1
WO2023000316A1 PCT/CN2021/108196 CN2021108196W WO2023000316A1 WO 2023000316 A1 WO2023000316 A1 WO 2023000316A1 CN 2021108196 W CN2021108196 W CN 2021108196W WO 2023000316 A1 WO2023000316 A1 WO 2023000316A1
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WO
WIPO (PCT)
Prior art keywords
parts
graphene
conductive ink
resin
epoxy resin
Prior art date
Application number
PCT/CN2021/108196
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English (en)
Chinese (zh)
Inventor
熊圣东
Original Assignee
宁波先锋新材料股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁波先锋新材料股份有限公司 filed Critical 宁波先锋新材料股份有限公司
Priority to PCT/CN2021/108196 priority Critical patent/WO2023000316A1/fr
Publication of WO2023000316A1 publication Critical patent/WO2023000316A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks

Definitions

  • the invention belongs to the technical field of conductive ink, and relates to a composite conductive ink with high conductivity and a preparation method thereof.
  • Conductive ink is mainly used in printing conductive points and conductive lines, and it is widely used in keyboard electronic circuits, printed circuits, electrodes, electroplating bottom layers, etc. With the development of science and technology and the rapid development of the microelectronics industry, the prospects for conductive inks to be applied to printed circuits are extremely broad.
  • the main conductive inks used are gold-based conductive inks, silver-based conductive inks, copper-based conductive inks, and carbon-based conductive inks. Ink etc. According to statistics, the output value of silver-based conductive ink alone reached 2 billion US dollars in 2014, and it will further increase in the future.
  • Print electronics is a strategic emerging industry that applies traditional printing technology to the manufacture of electronic products. Its products are characterized by flexibility, portability, environmental protection, low cost, and large-area production. As a supplement and expansion of silicon-based electronics, the development The prospects are very bright.
  • Conductive ink is the basic material for the preparation of printed electronic devices.
  • the composition and performance of conductive ink depend on the performance requirements of printed electronic products, and the performance of conductive ink determines the development direction of the preparation and processing technology of printed electronic conductive materials.
  • the development of printed electronic products and conductive ink technology is characterized by technology integration. The market forecast is growing year by year, and the compound annual growth rate in many fields exceeds 45%, showing a rapid upward trend.
  • Printed electronic products require conductive coatings with good conductivity, thin thickness and strong adhesion, so it is necessary to develop high-performance conductive inks.
  • the present invention provides a composite conductive ink, which uses graphene to replace part of the nano-silver, so as to improve the conductivity of the conductive graphite and reduce the cost of the conductive ink.
  • One aspect of the present invention provides a composite conductive ink with high conductivity, comprising the following components in parts by weight:
  • Resin 100 parts; nano silver: 15-35 parts; graphene: 2-10 parts; solvent: 50-70 parts; curing agent: 1-5 parts; auxiliary agent: 1-4 parts.
  • nano-silver with excellent conductivity is added to the conductive ink, and the charge mobility of the nano-silver material is much higher than that of organic electronic materials, thereby effectively improving the conductivity of the conductive ink.
  • adding a small amount of graphene instead of nano-silver as a conductive filler can not only ensure good conductivity of the ink, but also reduce the consumption of silver powder and reduce costs.
  • the resin is one or more of epoxy resin, polyurethane resin, alkyd resin, acrylic resin and photosensitive resin.
  • the resin is epoxy resin.
  • Epoxy resins contain epoxy groups, which can form three-dimensional cross-linked curing compounds under the action of curing agents and certain temperature conditions. It has the characteristics of high connection performance, small shrinkage rate, strong connection force, shrinkage rate, good stability, and excellent processing performance.
  • the resin is bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, acrylic modified epoxy resin, polyurethane modified epoxy resin and organosilicon One or more of epoxy resins.
  • Modification of epoxy resin such as acrylic modified epoxy resin has the characteristics of acrylic plumpness, gloss, and good weather resistance; polyurethane modified epoxy resin has a good network structure, thereby improving the toughness of epoxy resin; Silicone modified epoxy resin can not only reduce the internal stress of epoxy resin, but also improve the toughness and high temperature resistance of epoxy resin, so that the resin has good toughness, compression molding performance, connection performance and impact resistance. Therefore, the conductive ink based on modified epoxy resin has good adhesion, heat resistance, flexibility, etc.
  • the curing agent is preferably one or more of dicyandiamide, polyamide, diethylenetriamine, ethylenediamine, diaminodiphenylmethane, maleic anhydride, and phenolic resin.
  • the curing agent undergoes a ring-opening or ring-closing reaction with the epoxy group of the epoxy resin to form a network-like three-dimensional polymer, so that some composite materials are wrapped in the network to improve the conductivity and adhesion of the conductive ink.
  • the curing of the primary amine is a nucleophilic addition reaction with the epoxy resin, and each active wave hydrogen can open an epoxy group to make it cross-linked and cured.
  • Anhydride curing is the reaction of the carboxyl group on the epoxy resin with the acid anhydride to form an ester bond and carboxylic acid.
  • the carboxylic acid adds to the epoxy group to form a carboxyl group.
  • the generated carboxyl group continues to react with other anhydride groups. This reaction is repeated to form a body shape. polymer.
  • the mass ratio of the resin to the total amount of nano-silver and graphene is 100:(25-35).
  • the mass ratio of the total amount of nano-silver and graphene to the resin is controlled as (25-35):100, the conductive ink has excellent conductivity and good comprehensive performance, which can meet the basic requirements of the flexible circuit of the membrane switch.
  • the mass ratio of nano-silver and graphene is 1:(0.2-0.3). Nano-silver and graphene are mixed in this mass ratio, which effectively reduces the amount of silver used and costs on the basis of excellent electrical conductivity.
  • the particle size range of the nano-silver is 20-100 nm.
  • the graphene is one or more of unmodified graphene, chemically doped graphene, chemically modified graphene, and coupling agent modified graphene.
  • Chemically doped graphene is one or more doped graphene of polyaniline, polyacetylene, polythiophene, polyparaphenylene and polypyrrole, and the chemically modified functional groups of chemically modified graphene are aniline, imidazole, One or more of benzenesulfonic acid group, thienyl group, furyl group and phenyl group.
  • the present invention is not particularly limited to the solvent in the conductive ink, and the conventional organic solvents used in conductive inks known to those skilled in the art can be used, such as methanol, ethanol, isopropanol, dimethylformamide, ethylene glycol, etc. Alcohol, propylene glycol, glycerin, toluene, xylene, ethyl acetate, propyl acetate, methyl formate, ethyl formate, ethyl lactate, ethyl valerate, acetone, methyl ethyl ketone, n-butanol, N, N -Dimethylformamide, N,N-dimethylacetamide, etc.
  • the conventional organic solvents used in conductive inks known to those skilled in the art can be used, such as methanol, ethanol, isopropanol, dimethylformamide, ethylene glycol, etc.
  • Alcohol propylene glycol, glycerin
  • the auxiliary agent includes: coupling agent, leveling agent, defoamer, accelerator and the like.
  • the coupling agent can be listed as silane coupling agent or titanate coupling agent;
  • the leveling agent can be listed as acrylic leveling agent, fluorine leveling agent, organosilicon leveling agent;
  • the defoamer can be listed as organosiloxane defoamer, polyether defoamer;
  • the accelerator can be listed as imidazole accelerator, including methylimidazole, 1-benzyl-2-methylimidazole and the like.
  • Another aspect of the present invention provides a method for preparing the highly conductive composite conductive graphite, comprising the following steps:
  • step (3) Add the coupling agent-modified graphene of step (3) to the connecting material of step (2), stir evenly, and grind 3 to 8 times with a three-roller machine to obtain the conductive ink.
  • the present invention has the following beneficial effects:
  • nano-silver and graphene are added as conductive fillers in the conductive ink, which can not only ensure the good conductivity of the ink but also reduce the consumption of silver powder and reduce the cost;
  • the present invention controls the mass ratio of nano-silver and graphene to 1: (0.2-0.3), on the basis of excellent electrical conductivity, effectively reduces the amount of silver used, and realizes the improvement of electrical conductivity and the reduction of cost;
  • the mass ratio of the total amount of nano-silver and graphene to the resin of the present invention is controlled to be (25-35): 100, and the conductive ink prepared has excellent conductivity and good overall performance, which can meet the basic requirements of the flexible circuit of the membrane switch;
  • the conductive graphite prepared by graphene/nano-silver also has the characteristics of good chemical stability and is not easy to be oxidized. Even if its surface is partially oxidized due to the preparation process or environmental factors, the generated oxide can also conduct electricity. Silver conductive ink is easy to prepare, stable in operation, and does not require additional anti-oxidation measures;
  • the graphene/nano-silver conductive ink of the present invention has a low sintering temperature, and the sintering temperature can be reduced to 70°C to 150°C. It can be deposited not only on PI, but also on plastics and flexible plates with low cost and low Tg. superior.
  • the composite conductive ink of this embodiment includes the following components by weight: bisphenol A epoxy resin: 100 parts, nano silver with a particle size range of 20-50 nm: 20 parts, graphene: 6 parts, organosiloxane defoamer: 2 parts, accelerator methylimidazole: 0.2 parts, dicyandiamide curing agent: 1.8 parts, solvent: 64.2 parts.
  • step (3) Add the coupling agent-modified graphene obtained in step (2) to the connecting material obtained in step (1), and after fully stirring evenly, grind 3 times at a uniform speed with a three-roller machine to obtain conductive ink.
  • the obtained conductive ink was screen-printed on the PI film with a film thickness of about 10 microns, and the properties of the cured conductive film were measured as shown in Table 1.
  • the composite conductive ink of this embodiment includes the following components by weight: bisphenol A epoxy resin: 100 parts, nano-silver with a particle size ranging from 20 to 50 nm: 25 parts, graphene: 5 parts, polyether defoamer: 2.2 parts , accelerator 1-benzyl-2-methylimidazole: 0.3 parts, maleic anhydride curing agent: 2 parts, solvent: 69 parts.
  • step (3) Add the coupling agent-modified graphene obtained in step (2) to the connecting material obtained in step (1), and after fully stirring, grind 4 times at a uniform speed with a three-roller machine to obtain conductive ink.
  • the obtained conductive ink was screen-printed on the PI film with a film thickness of about 10 microns, and the properties of the cured conductive film were measured as shown in Table 1.
  • the composite conductive ink of this embodiment includes the following components by weight: polyurethane modified epoxy resin: 100 parts, nano-silver with a particle size ranging from 20 to 50 nm: 28 parts, graphene: 7 parts, polyether defoamer: 2.5 parts , accelerator methylimidazole: 0.2 parts, diethylenetriamine curing agent: 2.5 parts, solvent: 57 parts.
  • step (3) Add the coupling agent-modified graphene obtained in step (2) to the connecting material obtained in step (1), and after fully stirring, grind 4 times at a uniform speed with a three-roller machine to obtain conductive ink.
  • the obtained conductive ink was screen-printed on the PI film with a film thickness of about 10 microns, and the properties of the cured conductive film were measured as shown in Table 1.
  • the composite conductive ink of Example 4 includes the following components by weight: bisphenol A epoxy resin: 100 parts, nano-silver with a particle size ranging from 20 to 50 nm: 22 parts, graphene: 4 parts, organosiloxane defoamer: 2 parts, accelerator methylimidazole: 0.2 parts, dicyandiamide curing agent: 1.8 parts, solvent: 64.2 parts. Others are the same as in Example 1.
  • the composite conductive ink of Example 5 includes the following components by weight: bisphenol A epoxy resin: 100 parts, nano silver with a particle size ranging from 20 to 50 nm: 18 parts, graphene: 8 parts, organosiloxane defoamer: 2 parts, accelerator methylimidazole: 0.2 parts, dicyandiamide curing agent: 1.8 parts, solvent: 64.2 parts. Others are the same as in Example 1.
  • the composite conductive ink of comparative example 1 comprises the following components by weight: bisphenol A epoxy resin: 100 parts, nano-silver with a particle size range of 20 to 50 nm: 26 parts, organosiloxane defoamer: 2 parts, accelerator A Kiimidazole: 0.2 parts, dicyandiamide curing agent: 1.8 parts, solvent: 64.2 parts.
  • the obtained conductive ink was screen-printed on the PI film with a film thickness of about 10 microns, and the properties of the cured conductive film were measured as shown in Table 1.
  • the composite conductive ink of comparative example 2 includes the following components by weight: bisphenol A epoxy resin: 100 parts, nano silver with a particle size ranging from 20 to 50 nm: 20 parts, graphene: 6 parts, organosiloxane defoamer: 2 parts, accelerator methylimidazole: 0.2 parts, dicyandiamide curing agent: 1.8 parts, solvent: 64.2 parts.
  • step (1) 6 parts of graphene are joined in the connecting material that step (1) obtains, and after fully stirring, grind 3 times at a constant speed with a three-roller machine, obtain conductive ink.
  • the obtained conductive ink was screen-printed on the PI film with a film thickness of about 10 microns, and the properties of the cured conductive film were measured as shown in Table 1.
  • Adhesion test GB/T9286-88 national standard, 100-grid knife plus 3M glue, full inspection, 0-5 grades.
  • Example 1 uses nano-silver and graphene in a suitable ratio as the conductive filler, and the conductivity may be comparable to that of using nano-silver as the conductive filler.
  • the ink see comparative example 1
  • the cost of embodiment 1 reduces greatly.
  • the graphene in the conductive graphite of Comparative Example 2 was not treated in any way, which resulted in poor compatibility between the graphene and the matrix resin, which affected the adhesion and conductivity of the conductive ink.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention concerne une encre conductrice composite présentant une conductivité élevée, comprenant les constituants suivants, en parties en poids : 100 parties d'une résine ; 15-35 parties de nanoargent ; 2-10 parties de graphène ; 50-70 parties d'un solvant ; 1-5 parties d'un agent de durcissement ; et 1-4 parties d'un additif. Par l'ajout de nanoargent et de graphène en tant que charges conductrices, une bonne conductivité de l'encre peut être assurée, la consommation de poudre d'argent peut être réduite et le coût peut être réduit.
PCT/CN2021/108196 2021-07-23 2021-07-23 Encre conductrice composite présentant une conductivité élevée et procédé pour sa préparation WO2023000316A1 (fr)

Priority Applications (1)

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PCT/CN2021/108196 WO2023000316A1 (fr) 2021-07-23 2021-07-23 Encre conductrice composite présentant une conductivité élevée et procédé pour sa préparation

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Application Number Priority Date Filing Date Title
PCT/CN2021/108196 WO2023000316A1 (fr) 2021-07-23 2021-07-23 Encre conductrice composite présentant une conductivité élevée et procédé pour sa préparation

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WO2023000316A1 true WO2023000316A1 (fr) 2023-01-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104650652A (zh) * 2013-11-22 2015-05-27 苏州冷石纳米材料科技有限公司 一种纳米银导电油墨及其制备方法
CN105001716A (zh) * 2015-06-30 2015-10-28 中国科学院山西煤炭化学研究所 一种石墨烯基低电阻导电油墨及其制备方法
CN107502066A (zh) * 2017-06-14 2017-12-22 厦门信达光电物联科技研究院有限公司 一种石墨烯/金属纳米带复合导电油墨及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104650652A (zh) * 2013-11-22 2015-05-27 苏州冷石纳米材料科技有限公司 一种纳米银导电油墨及其制备方法
CN105001716A (zh) * 2015-06-30 2015-10-28 中国科学院山西煤炭化学研究所 一种石墨烯基低电阻导电油墨及其制备方法
CN107502066A (zh) * 2017-06-14 2017-12-22 厦门信达光电物联科技研究院有限公司 一种石墨烯/金属纳米带复合导电油墨及其制备方法和应用

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