CN110577770A - water-soluble graphene conductive ink and preparation method thereof - Google Patents
water-soluble graphene conductive ink and preparation method thereof Download PDFInfo
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- CN110577770A CN110577770A CN201910841890.1A CN201910841890A CN110577770A CN 110577770 A CN110577770 A CN 110577770A CN 201910841890 A CN201910841890 A CN 201910841890A CN 110577770 A CN110577770 A CN 110577770A
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- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- 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
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides water-soluble graphene conductive ink and a preparation method thereof. The water-based graphene conductive ink composite material comprises water-soluble graphene powder, a connecting resin material, an auxiliary agent and a solvent. According to the experimental method provided by the invention, the water-soluble graphene conductive ink can be prepared in a large batch. According to the invention, deionized water is used as a solvent to replace the traditional organic solvent, and the water-soluble graphene conductive ink which has good conductivity, good toughness, good compression molding performance and impact resistance and meets the requirement of adhesive force is obtained by selecting and blending the connecting resin. The graphene component improves the stable conductivity of the product by virtue of the excellent conductivity, and the resistivity is improved. The invention overcomes the defects of environmental pollution and high cost of the traditional conductive ink, and is expected to be applied to large-scale commercial production.
Description
Technical Field
The invention relates to water-soluble conductive ink, in particular to water-soluble graphene conductive ink and a preparation method thereof.
background
the conductive ink is used as a key material used in printed electronic technologies such as a radio frequency identification technology, a flexible printed circuit, a sensor, electromagnetic shielding, a membrane switch and an electronic book, and the application advantages and the research and development results of the conductive ink are widely concerned by people. At present, many large-scale companies at home and abroad research and develop conductive ink, and the traditional conductive ink taking inorganic powder material as conductive material is gradually replaced by composite ink taking nano/micron-scale powder as conductive material, wherein the conductive material is as follows: nano silver powder, nano copper-coated silver powder, novel two-dimensional materials, graphene and the like.
At present, the solvents used in conductive inks are mainly classified into two types, one is water, and the other is an organic solvent, such as alcohol, ketone, ether, and ester. Research shows that various mixed solvents can effectively improve the solubility of the ink. Water is a non-toxic, environmentally friendly material with high earth crust abundance, and is one of the most commonly used solvents in many research fields. However, the use of water as an ink solvent is largely limited because some conductive fillers used to prepare conductive inks are not water soluble. And the toxicity to organic solvents also limits the use of organic solvents. Therefore, water-soluble conductive inks are currently the focus of research.
In terms of conductive fillers, carbon-based nanomaterials represented by carbon nanotubes and graphene are increasingly attracting attention for application in conductive inks. Researchers have recently looked at graphene because graphene conductive inks have a significant cost advantage, better conductivity, and compatibility with inkjet printing methods compared to nano-metal conductive inks.
the Geim group at Manchester university, UK, used graphene exfoliated from highly oriented pyrolytic graphite in a monoatomic layer thickness, driving the graphene to study new hot trends. Graphene is hybridized into a honeycomb-shaped two-dimensional crystal by virtue of sp2 carbon atoms, wherein each carbon atom is connected with adjacent 3 carbon atoms to form sigma bonds, and the C-C bonds endow the graphene with excellent mechanical properties. Each carbon atom contributes an unbound pi electron, and they can move freely in the graphene crystal plane, so that graphene has good conductivity, high electron mobility (2 × 105 cm2(/ V · s)), and high thermal conductivity (5 × 103W (/ m · K)) [10 ]. The graphene has the characteristics of high conductivity, intrinsic stability of carbon materials, a nano-sheet structure and the like, and has wide application prospects in the fields of transparent conductive films, supercapacitors, organic field effect transistors, composite materials and the like. The graphene is used as a conductive filler of a core component of the conductive ink, is a functional phase determining the conductivity of the ink, and directly determines the application prospect of the conductive ink.
Disclosure of Invention
The invention aims to provide a water-soluble graphene conductive ink material which is prepared by processing water-soluble graphene as a conductive filler, a water-soluble resin material as a connecting material and an auxiliary agent and deionized water as solvents through a composite grinding process.
In order to achieve the purpose, the invention provides the following technical scheme that the water-soluble graphene conductive ink comprises, by mass, 5 ~ 20 wt% of water-soluble graphene powder, 40 ~ 70 wt% of water-soluble connecting resin material, 1 ~ 7 wt% of auxiliary agent and 20 ~ 60 wt% of deionized water as a solvent.
the resin in the resin-based connecting material can be one or more of water-soluble resin including water-soluble acrylate, water-soluble polyurethane, water-soluble epoxy resin, water-soluble alkyd resin, modified synthetic resin and natural resin. The resin re-conductive ink is a main film forming substance, and the physical and chemical properties of the resin re-conductive ink directly determine the basic properties of the conductive ink, such as mechanical property, rheological property, acid and alkali resistance, adhesive force and the like.
The invention relates to graphene-modified graphene oxide. The graphene dominates the conductivity of the finally obtained conductive ink, so that the larger the specific surface area of the graphene in the conductive graphite is, the better the dispersibility is, and the better the conductivity of the conductive ink is.
The solvent required in the present invention is water. The solvent mainly dissolves the resin and performs dispersion on the conductive components graphene and the auxiliary agent in the invention. The dissolution also determines the viscosity and drying speed of the conductive ink.
The auxiliary agents used in the present invention include thickeners, dispersants, coupling agents, plasticizers, leveling agents, colorants, lubricants, stabilizers, antioxidants, and the like. The auxiliary agents used in the invention are common agents in the field of printing ink, the main function of the auxiliary agents is to improve the stability and the printing performance of the printing ink, and part of the auxiliary agents can also properly improve and promote the conductivity of the conductive printing ink. For example, the thickener may be used to increase the viscosity of the conductive paste, cover and disperse the solid particles, and prevent agglomeration of the solid particles. In addition, it may also have the effect of changing the viscosity of the conductive ink. In addition, an epoxy silane coupling agent is particularly added to improve the bonding force between the printing film and the substrate.
In the present invention, the selection and adjustment of the component ratio of the resin binder, the solvent and the auxiliary agent can be performed according to the conditions such as conductivity, viscosity, rheological property, printing method and substrate required for the water-soluble conductive ink.
the invention provides a preparation method of the water-soluble graphene conductive ink composite material, which mainly comprises the following four steps:
Preprocessing graphene: taking graphene oxide as a raw material, carrying out hydrothermal reaction treatment on the graphene oxide at 80-85 ℃ for 12 hours by using hydrazinobenzenesulfonic acid or soluble hydrazinobenzenesulfonic acid salt (the ratio is 1: 4), and then filtering, repeatedly washing and drying to obtain water-soluble reduced graphene oxide powder rich in sulfonic acid groups;
Weighing raw materials: weighing each component material according to the mass percentage of the water-soluble graphene conductive ink, wherein the specific mass ratio of each component material can be regulated and controlled according to the performance requirements of the conductive ink such as conductivity, viscosity, rheological property and the like;
Thirdly, mixing materials, namely guiding the weighed materials into a dispersion kettle to be stirred at the room temperature at the speed of 100 ~ 5000 rpm, so that the materials of all components are uniformly dispersed and mixed to obtain conductive ink slurry, wherein the stirring speed in the dispersion kettle depends on the granularity and the shape of the initial components, the uniformity of dispersion and the like;
Grinding and packaging: grinding the obtained conductive ink slurry by using a grinder, wherein the grinding time is adjustable according to slurry components, initial granularity and shape; and filtering and packaging the ground product (the particle size is less than 10 mu m) to obtain the commercial graphene conductive ink.
Compared with the prior art, the invention has the following advantages:
1. After the water-soluble graphene conductive ink obtained by the invention is printed into a film, the conductivity is as high as 105S/cm and is far higher than that of the commercially available carbon-based conductive ink;
2. the volume of the water-soluble graphene conductive ink is water, the water-soluble graphene conductive ink can be directly diluted or cleaned by water, and volatile organic matters cannot be generated in the whole preparation and printing processes of the conductive ink, so that the environment is protected, and the personal health of a printing operator or a user can be ensured;
3. The water-soluble conductive ink prepared by the invention can be solidified into a film only through a low-temperature drying process of not higher than 90 ℃ after being printed and formed, thereby simplifying the high-temperature sintering process of the traditional ink, saving the cost and reducing the high-temperature resistant requirement on a printing substrate.
The graphene conductive ink prepared by the invention is suitable for processes such as brushing, screen printing and rinsing of a concavo-convex plate, spraying, offset printing, flexographic printing, roll printing and the like, and the base material of the graphene conductive ink can be paper, glass, ceramics, plastics, rubber, fiber, cloth and the like. The conductive ink prepared by the invention has excellent conductivity, good printing adaptability, mild curing conditions and low cost, can be widely applied to thin electronic products and flexible electronic products such as film switches, transparent conductive films, plasma displays, flexible circuit boards, chemical or biological sensors, light-emitting diodes and the like, and has wide potential markets.
The specific implementation mode is as follows:
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the following examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1. water-soluble acrylic resin 45 parts, water-soluble graphene powder 15 parts, deionized water 35 parts, and auxiliary agent 5 parts (colorant 1 part, dispersant 0.5 part, defoamer 0.5 part, plasticizer 0.5 part, advection agent 0.5 part, epoxy silane coupling agent 2 parts), all in mass percent. And (3) adding the water-soluble acrylic resin into deionized water to obtain a uniform aqueous solution. Adding the water-soluble graphene powder while stirring, and uniformly stirring. Then, under the condition of stirring, gradually adding an auxiliary agent to obtain a pre-dispersing material; the stirring speed was 1000 rpm. The slurry obtained by stirring was then allowed to stand for 20 minutes and the excess water was filtered off by means of a filter press. Finally, grinding the obtained mixed slurry until the fineness of the material reaches below 10 micrometers; and filtering the ground material to obtain the water-soluble graphene conductive ink.
example 2. taking 45 parts of water-soluble polyurethane, 15 parts of water-soluble graphene powder, 35 parts of deionized water, and 5 parts of auxiliary agent (1 part of coloring agent, 0.5 part of dispersing agent, 0.5 part of defoaming agent, 0.5 part of plasticizer, 0.5 part of advection agent, and 2 parts of epoxy silane coupling agent), the materials are calculated according to mass percent. And (3) dissolving the water-soluble polyurethane into deionized water to obtain a uniform aqueous solution. Adding the water-soluble graphene powder while stirring, and uniformly stirring. Then, under the condition of stirring, gradually adding an auxiliary agent to obtain a pre-dispersing material; the stirring speed was 1000 rpm. The slurry obtained by stirring was then allowed to stand for 20 minutes and the excess water was filtered off by means of a filter press. Finally, grinding the obtained mixed slurry until the fineness of the material reaches below 10 micrometers; and filtering the ground material to obtain the water-soluble graphene conductive ink.
example 3. taking 25 parts of water-soluble polyurethane, 20 parts of water-soluble acrylic resin, 15 parts of water-soluble graphene powder, 35 parts of deionized water, and 5 parts of auxiliary agent (1 part of coloring agent, 0.5 part of dispersing agent, 0.5 part of defoaming agent, 0.5 part of plasticizer, 0.5 part of advection agent, and 2 parts of epoxy silane coupling agent), the materials are calculated according to mass percent. Respectively dissolving water-soluble acrylic resin and water-soluble polyurethane into deionized water to obtain a uniform aqueous solution, and then uniformly mixing the two solutions under the stirring condition to obtain a uniform mixed solution. And then adding the water-soluble graphene powder while stirring, and uniformly stirring. Then, under the condition of stirring, gradually adding an auxiliary agent to obtain a pre-dispersing material; the stirring speed was 1000 rpm. The slurry obtained by stirring was then allowed to stand for 20 minutes and the excess water was filtered off by means of a filter press. Finally, grinding the obtained mixed slurry until the fineness of the material reaches below 10 micrometers; and filtering the ground material to obtain the water-soluble graphene conductive ink.
The prepared water-soluble graphene nano conductive ink takes a PVC plastic film as a substrate, is printed by a flexible plate, is dried and cured for 30min at 75 ℃, finally obtains a cured composite conductive ink film with the thickness of about 3 mu m, and is tested, and the result is as follows.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The water-soluble graphene conductive ink is characterized by comprising, by mass, 5 ~ 20 wt% of water-soluble graphene powder, 40 ~ 70 wt% of water-soluble connecting resin material, 1 ~ 7 wt% of assistant and 20 ~ 60 wt% of solvent.
2. A preparation method of water-soluble graphene conductive ink is characterized by comprising the following steps:
Step 1, graphene pretreatment: taking graphene oxide as a raw material, carrying out hydrothermal reaction treatment on the graphene oxide for 12 hours by using hydrazinobenzenesulfonic acid or soluble hydrazinobenzenesulfonic acid salt (the ratio is 1: 4), and then filtering, repeatedly washing and drying to obtain water-soluble reduced graphene oxide powder rich in sulfonic acid groups;
step 2, weighing raw materials: weighing each component material according to the mass percentage of the water-soluble graphene conductive ink, wherein the specific mass ratio of each component material can be regulated and controlled according to the performance requirements of the conductive ink such as conductivity, viscosity, rheological property and the like;
Step 3, mixing materials, namely introducing the weighed materials into a dispersion kettle, stirring at room temperature at the speed of 100 ~ 5000 rpm to uniformly disperse and mix the materials of each component to obtain conductive ink slurry, wherein the stirring speed in the dispersion kettle depends on the granularity and the shape of the initial components, the dispersion uniformity and other conditions;
And 4, grinding and packaging: grinding the obtained conductive ink slurry by using a grinder, wherein the grinding time is adjustable according to slurry components, initial granularity and shape; and filtering and packaging the ground product (the particle size is less than 10 mu m) to obtain the commercial graphene conductive ink.
3. the method for preparing the water-soluble graphene conductive ink according to claim 1, wherein the water-soluble resin comprises one or more of water-soluble acrylate, water-soluble polyurethane, water-soluble epoxy resin, water-soluble alkyd resin, modified synthetic resin and natural resin.
4. The preparation method of the water-soluble graphene conductive ink according to claim 1, wherein the auxiliary agents used in the product comprise a defoaming agent, a wetting agent, a bactericide, a mildew preventive, a leveling agent and the like, the auxiliary agents are commercially available, and in addition, an epoxy silane coupling agent is specially added to increase the bonding force between a printing film and a substrate.
5. The method for preparing the water-soluble graphene conductive ink according to claim 1, wherein the solvent is deionized water.
6. The method for preparing the water-soluble graphene conductive ink according to claim 2, wherein the water temperature of the hydrothermal reaction treatment is 80-85 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910841890.1A CN110577770A (en) | 2019-09-06 | 2019-09-06 | water-soluble graphene conductive ink and preparation method thereof |
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| CN201910841890.1A CN110577770A (en) | 2019-09-06 | 2019-09-06 | water-soluble graphene conductive ink and preparation method thereof |
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| CN110577770A true CN110577770A (en) | 2019-12-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111745886A (en) * | 2020-06-24 | 2020-10-09 | 赣县洪顺工艺厂 | Resin handheld processing technology |
| CN113096850A (en) * | 2021-03-09 | 2021-07-09 | 青岛大学 | Highly conductive fabric based on graphene conductive slurry and coating process thereof |
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2019
- 2019-09-06 CN CN201910841890.1A patent/CN110577770A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111745886A (en) * | 2020-06-24 | 2020-10-09 | 赣县洪顺工艺厂 | Resin handheld processing technology |
| CN113096850A (en) * | 2021-03-09 | 2021-07-09 | 青岛大学 | Highly conductive fabric based on graphene conductive slurry and coating process thereof |
| CN113096850B (en) * | 2021-03-09 | 2023-04-11 | 青岛大学 | Highly conductive fabric based on graphene conductive slurry and coating process thereof |
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Application publication date: 20191217 |