CN113689972A - Preparation method of conductive silver-clad copper paste for flexible circuit - Google Patents

Preparation method of conductive silver-clad copper paste for flexible circuit Download PDF

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Publication number
CN113689972A
CN113689972A CN202110847958.4A CN202110847958A CN113689972A CN 113689972 A CN113689972 A CN 113689972A CN 202110847958 A CN202110847958 A CN 202110847958A CN 113689972 A CN113689972 A CN 113689972A
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China
Prior art keywords
silver
copper paste
conductive silver
carbon nanotubes
nanotubes comprises
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CN202110847958.4A
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Chinese (zh)
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李正刚
刘海敏
来琳斐
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Nanjing Nawei New Material Technology Co ltd
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Nanjing Nawei New Material Technology Co ltd
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Priority to CN202110847958.4A priority Critical patent/CN113689972A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/24Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Conductive Materials (AREA)

Abstract

The application provides a preparation method of low-temperature conductive silver copper paste for a flexible circuit. The silver copper paste formula comprises: 20-80 wt% of micron/submicron silver-copper powder, 1-20 wt% of thermoplastic polyurethane, 1-20 wt% of curing agent, 10-50 wt% of solvent, 0.1-10 wt% of carbon nano tube, 0.1-20 wt% of auxiliary agent and the like. The formula is mixed according to a certain proportion, and then the uniform composite conductive silver-copper slurry is formed through the processes of double-paddle stirring, three-roller shaft dispersion and the like. Through the compounding mode, the conductive silver-copper paste shows excellent conductive characteristic and bending resistance after being printed and cured on the flexible base material, and can be widely applied to various flexible electronic components.

Description

Preparation method of conductive silver-clad copper paste for flexible circuit
Technical Field
The application relates to the field of low-temperature conductive paste, in particular to a preparation method and application of low-temperature conductive silver-coated copper paste for screen printing of a flexible circuit.
Background
With the rapid development of the electronic industry, the fields of flexible electronic devices, including OLED displays, flexible sensors, organic solar cells, etc., are gaining popularity and growing rapidly. Advanced electronic material technology is a key technology for flexible electronic devices. The full-printed electronic technology is a method for manufacturing circuits and electronic devices by utilizing the traditional printing technology, and the printing technology is organically combined with an electronic manufacturing process, so that the environment-friendly, efficient and low-cost production of electronic products is realized. The materials used in the full-printed electronic technology mainly comprise electronic paste and various substrates, wherein more and more substrates mainly comprise organic films and have the characteristics of lightness, thinness and flexibility. The conductive paste is of great interest as a key functional material in various electronic products.
The low-temperature conductive slurry is viscous slurry formed by uniformly dispersing micron/nano metal powder in an organic resin phase. Its conductive function is mainly achieved by free electron carriers provided by the metal phase. In addition to the particle size and purity of the metal powder, the choice of the resin carrier also affects the properties of the conductive paste. At present, most of the commonly used resins are epoxy resin and vinyl chloride-vinyl acetate resin, but the cured resins have poor mechanical properties and poor impact resistance, so that polyurethane is selected as a carrier of silver-coated copper paste to enhance the flexibility and bending resistance of the paste after curing.
Carbon Nanotubes (CNTs) are a novel one-dimensional functional nanomaterial, formed by crimping single-or multi-layer graphite flakes, and have excellent mechanical, electrical, and thermal properties. The graphite sheet layer of the carbon nano tube is mainly a C-C covalent bond, has very stable chemical property and strong bonding force, the Young modulus of the graphite sheet layer is as high as 1.0TPa, the tensile strength of the graphite sheet layer can reach 45GPa, and the tensile strength of the graphite sheet layer is 20 times that of high-strength steel. Therefore, carbon nanotubes have great potential in the field of composite materials. The CNT with a certain proportion is added into the prepared silver-coated copper paste, so that the advantages of the silver-coated copper paste and the CNT are hopefully combined, and the conductive property, the bending resistance and the like of the silver-coated copper paste are improved.
Disclosure of Invention
1. The application provides a preparation method and application of low-temperature conductive silver-coated copper paste for a screen printing flexible circuit, the silver-copper paste can be applied to a membrane switch, a keyboard and a flexible sensor, has excellent conductivity and bending resistance, and is bent for 10 times in a positive and negative 180 degrees, and the resistance change rate is less than 300%.
A conductive silver copper paste doped with carbon nanotubes comprises the following components:
20-80 wt% of silver-coated copper powder;
0.1-10 wt% of Carbon Nanotube (CNT);
1-20 wt% of Thermoplastic Polyurethane (TPU);
1-20 wt% of curing agent
10-50 wt% of a solvent;
0.1-20 wt% of an auxiliary agent;
wherein, the components of the slurry are mixed and dispersed in modes of full stirring, three-roller grinding and the like to form uniform slurry.
2. The carbon nanotube doped conductive silver copper paste according to claim 1, wherein: the silver-coated copper powder is in one or more of flake, spherical, dendritic and irregular shapes.
3. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the particle size distribution of the silver-coated copper powder is D100.1-2 μm, D501-5 μm and D903-20 μm.
4. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the silver content (mass ratio) of the silver-coated copper powder is between 1% and 50%.
5. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the carbon nano tube is one or two of a single-wall carbon nano tube and a multi-wall carbon nano tube.
6. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the particle size distribution of the carbon nano tube is 2 nm-10 mu m of tube diameter and 100 nm-100 mu m of tube length.
7. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the thermoplastic resin includes, but is not limited to, one or more of basf 1170A, bayer 192X, lubol 61083, tabasheer WHT-6232B.
8. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the low-temperature curing agent is selected from one or more of modified dicyandiamide, phthalate ester, a silane coupling agent and amino resin.
9. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the solvent is ester, ether or alcohol solvent with higher boiling point.
10. The carbon nanotube doped conductive silver-clad copper paste according to claim 1, wherein: the auxiliary agent comprises an adhesion promoter, a thickening agent, a flatting agent, a defoaming agent and the like.
Drawings
FIG. 1: scanning Electron Microscope (SEM) picture of silver-coated copper powder
FIG. 2: energy spectrometer (EDS) element distribution diagram of silver-coated copper powder
FIG. 3: CNT Scanning Electron Microscope (SEM) image
FIG. 4: thermogravimetric analysis data of CNT silver coated copper paste
FIG. 5: CNT silver coated copper paste and printed test pattern
FIG. 6: bending test resistance data
FIG. 7: electron micrographs before and after bending
Detailed Description
In order to illustrate the invention more clearly, the invention is further described below with reference to the accompanying drawings and specific examples, which should not be construed as limiting the scope of the invention.
The preparation method of the carbon nano tube silver-coated copper slurry comprises the following steps: respectively weighing silver-coated copper powder, thermoplastic polyurethane resin, CNT powder, a solvent and an auxiliary agent, adding the silver-coated copper powder, the thermoplastic polyurethane resin, the CNT powder, the solvent and the auxiliary agent into a slurry tank, stirring for 1 hour by using a double-paddle stirrer until the powder is uniform and fully infiltrated, then dispersing the CNT silver-copper slurry composite slurry to the fineness of less than 10 mu m by using a three-roller shaft grinding machine, and collecting to obtain the uniformly dispersed silver-copper slurry.
Example 1
The formula and the preparation process of the silver-copper paste comprise the following steps:
adding 51 wt% of flaky silver-coated copper powder (with silver content of 20%), 8 wt% of thermoplastic polyurethane, 1 wt% of CNT powder, 31 wt% of solvent and 9 wt% of auxiliary agent into a slurry tank, stirring for 10 minutes by using a stainless steel spatula to fully soak the silver-copper powder, stirring for 1 hour by using a slurry stirrer until the mixture is uniform, then grinding the CNT silver-coated copper composite slurry for six times by using a three-roll-shaft grinding machine, and collecting to obtain uniformly dispersed silver-copper slurry.
FIG. 1 is a Scanning Electron Microscope (SEM) image of silver-coated copper powder with the silver powder morphology being flake. Fig. 2 is an Energy Dispersive Spectroscopy (EDS) elemental distribution diagram of silver-coated copper powder with silver uniformly distributed on the surface of the copper. Fig. 3 is a Scanning Electron Microscope (SEM) image of CNTs, which appear as nanowires.
Fig. 4 shows thermogravimetric analysis data of the CNT-silver coated copper paste. Specifically, the temperature rise rate of the thermogravimetry is 2 ℃/min, the temperature is raised from room temperature 25 ℃ to 200 ℃, as shown in fig. 1, 59.78% of mass remains when the silver-copper slurry is further raised to 200 ℃, which indicates that the solid content of the slurry is close to 60%.
The printing was done using a manual screen printing station, 200 mesh stainless steel screen, with the pattern shown in fig. 5 printed on a Polyimide (Polyimide) PI substrate, and then cured in an oven at 120 ℃ for 10 minutes.
And testing the fine line resistance condition of the CNT silver-coated copper paste after printing and curing by using a multimeter. Wherein, the length of the thin line is 5cm, and the line width is 1mm, 2mm and 3mm respectively. Through measurement, the average resistance of the 1mm wire is 2.1 omega, the average resistance of the 2mm wire is 1.4 omega, the average resistance of the 3mm wire is 1.0 omega, and the slurry has good conductivity.
And in addition, the obtained CNT silver-coated copper paste is printed with patterns, and 3mm lines after solidification are selected for carrying out bending resistance test on the CNT silver-coated copper paste. The specific test method is to bend the 3mm silver-copper paste after printing and curing at 180 degrees, and then place a 1000 g weight at the crease and keep for 1 minute. It was then bent in the opposite direction at 180 ° and a 1000 gram weight was placed at the fold again for 1 minute, and this was repeated 10 times. Fig. 6 shows the resistance change after bending for 3 samples. FIG. 7 is a scanning electron microscope image of the surface before and after bending, with no apparent cracks in the surface after bending, suitable for flexible circuit printing and applications.
Example 2
The formula and the preparation process of the CNT silver-coated copper paste comprise the following steps:
adding 60 wt% of silver-coated copper powder, 8 wt% of thermoplastic polyurethane, 0.2 wt% of CNT powder, 25 wt% of solvent and 6.8 wt% of auxiliary agent into the slurry, stirring for 10 minutes by using a stainless steel spatula to fully soak the silver-copper powder, stirring for at least 1 hour by using a double-paddle stirrer until the mixture is uniform, dispersing the CNT silver-coated copper slurry composite slurry for six times by using a three-roll shaft, and collecting to obtain uniformly dispersed conductive slurry. Printing, curing and testing were the same as in example 1.

Claims (10)

1. The preparation method of the conductive silver-copper paste doped with the carbon nano tube can be applied to a film switch, a keyboard and a flexible sensor, has excellent conductivity and bending resistance, and has a resistance change rate of less than 300% after being bent for 10 times in a positive and negative 180 degrees manner;
a conductive silver copper paste doped with carbon nanotubes comprises the following components:
20-80 wt% of silver-coated copper powder;
0.1-10 wt% of Carbon Nanotube (CNT);
1-20 wt% of Thermoplastic Polyurethane (TPU);
1-20 wt% of curing agent
10-50 wt% of a solvent;
0.1-20 wt% of an auxiliary agent;
wherein, the components of the slurry are mixed and dispersed in modes of full stirring, three-roller grinding and the like to form uniform slurry.
2. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the silver-coated copper powder is in one or more of flake, spherical, dendritic and irregular shapes.
3. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the particle size distribution of the silver-coated copper powder is D100.1-2 μm, D501-5 μm and D903-20 μm.
4. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the silver content (mass ratio) of the silver-coated copper powder is between 1% and 50%.
5. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the carbon nano tube is one or two of a single-wall carbon nano tube and a multi-wall carbon nano tube.
6. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the particle size distribution of the carbon nano tube is 2 nm-10 mu m of tube diameter and 100 nm-100 mu m of tube length.
7. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the thermoplastic resin includes, but is not limited to, one or more of basf 1170A, bayer 192X, lubol 61083, tabasheer WHT-6232B.
8. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the low-temperature curing agent is selected from one or more of modified dicyandiamide, phthalate ester, a silane coupling agent and amino resin.
9. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the solvent is ester, ether or alcohol solvent with higher boiling point.
10. The method of claim 1, wherein the conductive silver-copper paste doped with carbon nanotubes comprises: the auxiliary agent comprises an adhesion promoter, a thickening agent, a flatting agent, a defoaming agent and the like.
CN202110847958.4A 2021-07-27 2021-07-27 Preparation method of conductive silver-clad copper paste for flexible circuit Withdrawn CN113689972A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115274213A (en) * 2022-04-26 2022-11-01 南京纳纬新材料科技有限公司 Preparation method of bending-resistant resistance carbon paste
CN115458233A (en) * 2022-09-26 2022-12-09 苏州思尔维纳米科技有限公司 Conductive paste, preparation method thereof and electronic device
CN117690634A (en) * 2023-12-13 2024-03-12 深圳市绚图新材科技有限公司 Composite conductive paste of carbon network and metal and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115274213A (en) * 2022-04-26 2022-11-01 南京纳纬新材料科技有限公司 Preparation method of bending-resistant resistance carbon paste
CN115458233A (en) * 2022-09-26 2022-12-09 苏州思尔维纳米科技有限公司 Conductive paste, preparation method thereof and electronic device
CN115458233B (en) * 2022-09-26 2026-01-30 苏州思尔维纳米科技有限公司 Conductive paste, its preparation method and electronic devices
CN117690634A (en) * 2023-12-13 2024-03-12 深圳市绚图新材科技有限公司 Composite conductive paste of carbon network and metal and preparation method thereof

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Application publication date: 20211123