CN105206350A - Preparing method for silver conductive thin film resisting water and oil - Google Patents

Abstract

The invention discloses a method for preparing a water-resistant and oil-resistant silver conductive film. The preparation steps are as follows: cleaning, drying and plasma treatment of the substrate; coating a layer of adhesive on the substrate and drying; The line conductive ink is coated on the adhesive layer, and after drying, a silver conductive network is obtained; the polyfluoroacrylate protective agent is coated on the conductive network, and a water-resistant and oil-resistant conductive film is obtained after drying. The conductive film uses a water-repellent and oil-repellent polyfluorinated acrylate protective agent, so the prepared conductive film has good water and oil resistance. At the same time, the film also has excellent electrical conductivity, light transmission and small haze, and is suitable for use in the field of electronic information.

Description

A kind of preparation method of water-resistant and oil-resistant silver conductive film

technical field

The invention belongs to the technical field of transparent conductive films, and in particular relates to the preparation of a water-resistant and oil-resistant silver conductive film.

Background technique

In the current consumer electronics information field, graphene, carbon nanotubes, metal oxides, nanometal wires, conductive polymers, etc. can be used as electrode materials. Among them, indium tin oxide (ITO) among metal oxides is currently the most commonly used electrode material. However, the scarcity of indium content, the complexity of ITO film preparation and the brittleness of ITO itself make it unsuitable for the construction of low-cost flexible electrodes. Among the above-mentioned materials, silver nanowires are the flexible conductive material most likely to break through because of their best electrical conductivity and the most mature technology. When preparing a silver conductive film, people often cover a layer of top coating protective layer on the silver conductive network to increase the protection of the silver conductive film. For example, patent CN104658700A, which is protected by UV glue; patent CN102522145A, which is protected by polyester, polyurethane, epoxy resin and other resins; patent CN102522145B, which is protected by conductive polymer PEDOT:PSS; and other materials such as optical glue. But these top coating materials have a common disadvantage: they are only resistant to one of water or oil. This is due to the certain solubility of these top coating materials in water or organic solvents. This is unfavorable for thin film applications, because the entry of water or organic solvents will lead to a sharp decrease in film performance and life. Therefore, it is necessary to develop a transparent conductive film capable of water and oil resistance. Unfortunately, there is very little work in this area.

Therefore, the development of water-resistant and oil-resistant high-performance silver conductive films is an urgent problem to be solved in the field of transparent conductive films.

Contents of the invention

The purpose of the present invention is to provide a preparation of a water and oil resistant silver conductive film, so as to solve the current problem of poor water and oil resistance of the film. The film has the advantages of good water and oil resistance, high electrical conductivity, high light transmittance, good combination with a substrate, etc., is simple to prepare, and can be widely used in the field of electronic information. Its concrete implementation scheme is:

(1) The substrate is cleaned, dried and plasma treated;

(2) Coating a layer of adhesive on the substrate and drying;

(3) Silver nanowire conductive ink is coated on the bonding layer, and silver conductive network is obtained after drying;

(4) Coating the polyfluoroacrylate protective agent on the conductive network, and drying to obtain a water-resistant and oil-resistant silver conductive film.

The substrate used in the present invention is one of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polycarbonate, polyimide (PI) or glass;

(1) The cleaning, drying and plasma treatment process of the substrate is as follows: tear off the protective film on the newly purchased substrate, put it into acetone and ethanol for 5 minutes respectively. The substrate was then baked for 5 minutes with an infrared bake lamp. Take out the substrate, put it into a plasma cleaner, and vacuum clean it for 5 minutes. Among them, the power of the infrared baking lamp used is 800W, and the drying area is 1000cm2; the frequency/power of the plasma cleaning machine used is 13.56MHz/300W;

A bonding layer is coated with a 5% concentration of bonding agent on the substrate treated in (1), and the thickness is about 300nm. The binder used is epoxy resin, acrylate resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, polyimide resin, polyvinyl alcohol resin, polyketone resin, phenolic resin, silane coupling agent, One or a mixture of titanate coupling agents. Coating used GardcoAutomaticDrawdownMachineDP8301 sheet coating machine, also including other coating machines. After the coating is completed, first bake it with an infrared baking lamp for 5 minutes, and then dry it in a vacuum oven at 100°C for 10 minutes in a vacuum;

Coating a layer of silver nanowire coating solution on the basis of (2). Then, first bake with an infrared baking lamp for 3 minutes. Then vacuum dry in a vacuum oven at 110° C. for 10 minutes to obtain a silver nanowire network with a thickness of about 200 nm. The silver nanowire ink is homemade. The diameter of the silver nanowire is between 30-50nm, and the length is between 10-20μm. The ink silver thread content is about 0.5%. In addition to the silver line, the ink also contains additives such as dispersants, surfactants, leveling agents, humectants and binders;

The polyfluorinated acrylate protecting agent used in step (4) is polyfluorinated (trifluoromethyl) acrylate, (meth)acrylic acid perfluoroalkyl ester polymer, (meth)acrylic acid perfluoroalkylamide One or more of fluorinated acrylic polymers such as ester polymers, perfluoroalkylsulfonamide (meth)acrylate polymers, etc. For solubility reasons, emulsions of polyfluoroacrylate-based protectants are used for coating. Control the coating amount so that the final top coat thickness is 150nm;

After coating the polyfluoroacrylate protective agent, bake it with an infrared baking lamp for 3 minutes, and then bake it in a vacuum oven at 100°C for 10 minutes under vacuum to obtain the final water-resistant and oil-resistant silver conductive film;

The polyfluoroacrylate protective agent used in the present invention is a kind of water-repellent and oil-repellent adhesive, which can effectively prevent water and organic substances from infiltrating and corroding the film, and greatly extend the film life. service life;

The present invention has following advantages: (1) the use of the polyfluoroacrylic ester protective agent of water-repellent and oil-repellent makes film allow the water and organic matter that fall on it to be unable to stay and erode, and keep the high performance of film all the time; (2) ) The top coat and primer make the conductive film have a good bonding force with the substrate, and its protective function makes the film have a long life; (2) The filling between the silver wire network reduces the scattering of light, so the haze of the product is low; (4) The film has high conductivity and light transmittance, and has broad application prospects.

Description of drawings

Fig. 1: structural representation of the present invention;

1-substrate; 2-adhesive layer; 3-silver conductive network; 4 polyfluoroacrylate protective layer; among them, layers 3 and 4 partially overlap.

specific embodiment

Example:

PET was used as the substrate. Tear off the protective film on the new substrate, put it into acetone and ethanol and sonicate it for 5 minutes respectively. Then dry it with an infrared oven lamp. Then put it into the plasma cleaner and vacuum clean it for 5 minutes;

GardcoAutomaticDrawdownMachineDP8301 sheet coating machine was used to coat a layer of polyacrylic acid resin with a concentration of 5% on the treated substrate. Then, it was first baked with an infrared baking lamp for 5 minutes, and then dried in a vacuum oven at 100° C. for 10 minutes under vacuum. Obtain a bonding layer with a thickness of about 300nm;

Coat a layer of silver nanowire solution on the bonding layer, first bake it with an infrared baking lamp for 3 minutes, and then vacuum dry it in a vacuum oven at 110°C for 10 minutes to obtain a silver nanowire network with a thickness of about 200nm;

A perfluoroalkylethyl(meth)acrylate polymer emulsion was coated on the silver conductive network. Baking with an infrared baking lamp for 3 minutes, and then baking in a vacuum oven at 100°C for 10 minutes under vacuum to obtain a 150nm thick protective layer. The above steps are combined to obtain the final water-resistant and oil-resistant silver transparent conductive film.

The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make many modifications and changes according to the concept of the present invention without creative effort. All experiments and technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art shall be within the scope of protection defined by the claims.

Claims (9)

1. a kind of preparation method of water-resistant and oil-resistant silver conductive film is characterized in that, concrete preparation steps are: (1) The substrate is cleaned, dried and plasma treated; (2) Coating a layer of adhesive on the substrate and drying; (3) Silver nanowire conductive ink is coated on the bonding layer, and silver conductive network is obtained after drying; (4) Coating the polyfluoroacrylate protective agent on the conductive network, and drying to obtain a water-resistant and oil-resistant conductive film. 2. The preparation method according to claim 1, characterized in that: the substrate is polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polycarbonate, polyimide (PI) or one of glass. 3. The preparation method according to claim 1, characterized in that: (1) the cleaning of the substrate is to tear off the protective film on the substrate, and then put the substrate into acetone and ethanol for ultrasonication for 5 minutes; Drying is to bake the cleaned substrate under an infrared baking lamp for 5 minutes. 4. The preparation method according to claim 1, characterized in that: the plasma treatment process in step (1) is: placing the substrate flat in a plasma treatment machine, and turning on the machine to process the substrate for 5 minutes. 5. The preparation method according to claim 1, characterized in that: the binder used in step (2) is epoxy resin, acrylate resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, polyamide One or a mixture of imine resins, polyvinyl alcohol resins, polyketone resins, phenolic resins, silane coupling agents, and titanate coupling agents. 6 . The preparation method according to claim 1 , characterized in that: the drying in step (2) is firstly baking with an infrared baking lamp for 5 minutes, and then drying in a vacuum oven at a vacuum temperature of 100° C. for 10 minutes. 7. The preparation method according to claim 1, characterized in that: the silver nanowires used in step (3) are self-made, with a diameter between 30-50nm and a length between 10-20 μm; the ink silver wire content is between About 0.5%; In addition to the silver line, the ink also contains dispersants, surfactants, leveling agents, humectants and binders; after the ink is coated, it is first baked with an infrared baking lamp for 3 minutes; then the lining Put the bottom into a vacuum oven, heat and bake under vacuum at 110°C for 10 minutes. 8. The preparation method according to claim 1, characterized in that: the polyfluoroacrylate protecting agent used in step (4) is polyfluoro(trifluoromethyl)acrylate, (meth)acrylic acid perfluorinated Alkyl ester polymers, (meth)acrylic acid perfluoroalkylamide ester polymers, (meth)acrylic acid perfluoroalkylsulfonamide ester polymers and other fluoroacrylic polymers or a mixture of several, I use its lotion. 9. The preparation method according to claim 1, characterized in that: in step (4), after coating the polyfluoroacrylate protective agent emulsion, bake for 3 minutes with an infrared baking lamp, and then use a vacuum oven 100 °C under vacuum for 10 minutes to obtain the final water- and oil-resistant silver conductive film.