CN111584130A - Thermal-repair flexible transparent conductive film and preparation method thereof - Google Patents

Thermal-repair flexible transparent conductive film and preparation method thereof Download PDF

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CN111584130A
CN111584130A CN202010434714.9A CN202010434714A CN111584130A CN 111584130 A CN111584130 A CN 111584130A CN 202010434714 A CN202010434714 A CN 202010434714A CN 111584130 A CN111584130 A CN 111584130A
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transparent conductive
layer
conductive film
transparent
reaction
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CN111584130B (en
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王悦辉
赵玉珍
谢辉
马军现
林凯文
张小宾
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Dongguan Kanglong New Materials Co ltd
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University of Electronic Science and Technology of China Zhongshan Institute
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • 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
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    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
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    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract

The invention relates to the technical field of transparent conductive films, in particular to a thermal-repair flexible transparent conductive film and a preparation method thereof. The thermal-repair flexible transparent conductive film comprises a transparent conductive layer, a transparent functional layer and a thermally reversible DA reaction polyurethane substrate layer which are sequentially stacked; the transparent conducting layer is a silver nanowire conducting net; the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate. The conductive film has high transparency and good self-repairing performance, still has good light transmittance and conductivity after being repaired for many times, and has high repairing efficiency.

Description

Thermal-repair flexible transparent conductive film and preparation method thereof
Technical Field
The invention relates to the technical field of transparent conductive films, in particular to a thermal-repair flexible transparent conductive film and a preparation method thereof.
Background
In recent years, with the development of portable electronic devices and flexible wearable electronic devices, flexible transparent conductive electrodes have become a research hotspot as an important component of optoelectronic devices. However, when the electrode is used, micro cracks or micro damages are easily generated due to repeated abrasion, bending, impact or scraping, so that the device cannot normally work, even becomes electronic waste. With the improvement of environmental awareness and the continuous deepening of sustainable development concepts, the development of a flexible transparent conductive electrode with a self-repairing function is urgently needed, the intelligent repair of microcracks or micro-damage of materials is realized, and the basic functions of the material are recovered, so that the reliability of a device is improved, the service life is prolonged, the reuse rate of the device is improved, and the like.
The self-repairing material is a novel intelligent material which can simulate the self healing of organisms when being damaged, namely, the damaged part of the material can be automatically healed through a substance or energy supply mechanism. Generally, the methods are classified into buried self-repairing and intrinsic self-repairing according to the difference between the material and the energy supply method. The intrinsic self-repairing material is a material which realizes the repair by dissociation, recombination and winding of molecular chain segments under the stimulation of external light, electricity, magnetism, solvent and the like when the material is damaged. The material is mainly a macromolecule or supramolecular polymer combined by a reversible covalent bond (such as metal coordination, pi-pi action and the like) or a non-covalent bond (such as acylhydrazone bond system, disulfide bond, Diels-Alder (DA) reaction). Although the research of the self-repairing materials has made a great progress, only a few self-repairing material systems can be applied to the electronic field due to the special requirements of electronic components on electricity, heat, force, environment and the like.
At present, the self-repairing conductive film is mainly formed by dispersing conductive nano materials (such as metal nanowires, nanotubes, graphene, conductive polymers and hierarchical nano composite materials) into a self-repairing polymer or a thermoplastic elastomer and then performing processes such as tape casting and the like. Although the method has the characteristics of simple and rapid operation, low cost and the like, the self-repairing conductive film prepared by the method is generally opaque (cannot be applied to a photoelectric device needing transparency), and the popularization and application of the material on the flexible photoelectric device are greatly restricted. In order to develop a self-repairing flexible transparent conductive film, researchers have tried several schemes, such as dropping silver nanowires or surface-modified carbon nanotube suspensions onto the surface of a Layer-by-Layer (lbl) assembled polyelectrolyte multilayer film (PEM), applying polyelectrolyte hydrogel or ionic liquid-containing polymer gel, hot-pressing silver nanowire films onto the surface of a thermally reversible DA bond self-repairing polyurethane film, and applying a thermally reversible DA bond self-repairing polyurethane (PU-DA) precursor onto the surface of a metal nanowire film. Although the LbL assembled PEM conductive film and the hydrogel conductive film have certain light transmittance, the circuit is short-circuited through a water self-repairing process, and even water is deficient, so that the self-repairing performance is lost; the heat-repaired PU-DA conductive film formed by hot-pressing a near-infrared light self-repaired PEM conductive film, a silver nanowire film to the surface of a heat-reversible DA bond self-repaired polyurethane film and coating a heat-repaired PU-DA conductive film formed by coating a heat-reversible DA bond self-repaired polyurethane (PU-DA) precursor on the surface of a metal nanowire film not only has relatively poor transparency, but also has the problems that the repair efficiency is rapidly reduced along with the increase of the repair times and the like.
Disclosure of Invention
The invention aims to provide a heat-repairing flexible transparent conductive film and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a thermal-repair flexible transparent conductive film, which comprises a transparent conductive layer, a transparent functional layer and a thermally reversible DA (digital-analog) reaction polyurethane substrate layer which are sequentially stacked; the transparent conducting layer is a silver nanowire conducting net; the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate.
Preferably, the mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is 3-4: 1.
The invention provides a preparation method of the thermal-repair flexible transparent conductive film, which comprises the following steps:
spraying and printing a silver nanowire transparent conductive network pattern on the surface of the base material by adopting an ink-jet printing method to form a transparent conductive layer on the surface of the base material;
coating a functional layer solution comprising polyester acrylate oligomer and furan methyl acrylate on the surface of the transparent conductive layer, carrying out polymerization reaction, and curing to form a transparent functional layer;
coating a thermally reversible DA (polyurethane) prepolymer on the surface of the transparent functional layer, and drying to form a thermally reversible DA polyurethane substrate layer;
and peeling the transparent conductive layer, the transparent functional layer and the thermally reversible DA reaction polyurethane base layer from the base material to obtain the thermally repaired flexible transparent conductive film.
Preferably, the process of inkjet printing the silver nanowire transparent conductive network pattern on the surface of the substrate by using the inkjet printing method comprises the following steps: mixing silver nanowires, water and ethylene glycol to obtain transparent conductive ink; spraying and printing the transparent conductive ink on the surface of a substrate to form a silver nanowire transparent conductive network pattern; the mass concentration of the silver nanowires in the transparent conductive ink is 0.2-0.35%; the volume ratio of the water to the ethylene glycol is 1: 3-5.
Preferably, the jet printing is performed by a flexible electronic printer; the voltage of the jet printing is 20-36V, the number of the jet holes is 1-8, and the jet printing is carried outThe speed is 40 to 80 μm · s-1。
Preferably, the functional layer solution is obtained by mixing polyester acrylate oligomer, furan methyl acrylate and cyclopentanone; the mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is 3-4: 1.
Preferably, the preparation method of the thermally reversible DA reaction polyurethane prepolymer comprises the following steps:
mixing polytetrahydrofuran diol, anhydrous 4,4' -diphenylmethane diisocyanate and an organic solvent, and carrying out a first polymerization reaction on the obtained first mixture in a protective atmosphere to obtain an-NCO-terminated prepolymer;
adding furfuryl amine and a supplementary organic solvent into the-NCO-terminated prepolymer, and carrying out a second polymerization reaction on the obtained second mixture in a protective atmosphere to obtain furan ring-terminated isocyanate;
and adding diphenylmethane bismaleimide and a supplementary organic solvent into the furan ring-terminated isocyanate, and carrying out chain extension reaction on the obtained third mixture under a protective atmosphere to obtain the thermally reversible DA reaction polyurethane prepolymer.
Preferably, in the first mixture, the mass content of polytetrahydrofuran diol is 39.65-39.75%, and the mass content of 4,4' -diphenylmethane diisocyanate is 19.8-19.9%; the temperature of the first polymerization reaction is 50-70 ℃, and the time is 2.5-3.5 hours.
Preferably, the mass content of the furfuryl amine in the second mixture is 6.0-6.1%, and the amount of the supplemented solvent is 7.4-7.5% of the mass of the second mixture.
Preferably, in the third mixture, the mass content of the diphenylmethane bismaleimide is 9.8-9.9%, and the amount of the supplemented solvent is 11.1-11.4% of the mass of the third mixture; the temperature of the chain extension reaction is 50-70 ℃, and the time is 20-25 hours.
The invention provides a thermal-repair flexible transparent conductive film, which comprises a transparent conductive layer, a transparent functional layer and a thermally reversible DA (polyurethane-DA) substrate layer, wherein the transparent conductive layer, the transparent functional layer and the thermally reversible DA polyurethane (PU-DA for short) substrate layer are sequentially stacked; the transparent conducting layer is a silver nanowire conducting net; the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate. The PU-DA base layer has good transparency, and a conductive film structure is constructed by adopting the transparent conductive layer and the transparent functional layer, so that the conductive film is in a transparent state; the silver nanowire conductive net is used as a transparent conductive layer, so that the film has conductive performance; the transparent functional layer is introduced between the transparent conductive layer and the PU-DA substrate, has the function of fixing the silver nanowire conductive net, can be bonded with the PU-DA in the thermal repair process to improve the adhesive force between the film layers, and drives the silver nanowire net to rebuild and recover the mechanical property through crosslinking, so that the problems of rebuilding and stability of the silver nanowire conductive net after repeated self-repairing are solved, and the high-performance self-repairing silver nanowire flexible transparent conductive film is obtained.
The results of the embodiment show that the heat-repairing flexible transparent conductive film has the light transmittance of 60-85% at 550nm and the sheet resistance of 70-300 omega- □-1The transparent conductive adhesive has high transparency and conductivity, surface microcracks are self-repaired in 1-5 minutes under a 250W infrared lamp, the first repair rate is 100%, and after multiple repairs, the transparent conductive adhesive still has good transparency and conductivity, and the repair efficiency is high.
The invention provides a preparation method of a flexible transparent conductive film, which is characterized in that an ink-jet printing method is adopted to obtain a silver nanowire conductive net, so that subsequent etching and other processes are not needed, and the problems of controllability, repeatability and the like of the silver nanowire conductive net are solved.
Detailed Description
The invention provides a thermal-repair flexible transparent conductive film, which comprises a transparent conductive layer, a transparent functional layer and a thermally reversible DA (digital-analog) reaction polyurethane substrate layer which are sequentially stacked; the transparent conducting layer is a silver nanowire conducting net; the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate.
The thermal-repair flexible transparent conductive film provided by the invention comprises a transparent conductive layer, wherein the transparent conductive layer is a silver nanowire conductive net. The transparent conducting layer is preferably composed of 3-6 layers of silver nanowire conducting nets; the total thickness of the corresponding transparent conductive layer is about 30-80 nm. The invention takes the silver nanowire conductive net as the transparent conductive layer, thereby leading the film to have conductive performance.
The thermal-repair flexible transparent conductive film provided by the invention comprises a transparent functional layer arranged on the surface of the transparent conductive layer. In the invention, the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate, and the mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is preferably 3-4: 1, and more preferably 4: 1. In the invention, the thickness of the transparent functional layer is preferably 30-100 nm, and more preferably 40-80 nm. In embodiments of the invention, the thickness of the transparent functional layer is 40nm, 50nm or 70 nm.
The transparent functional layer has the function of fixing the silver nanowire conductive net, can be bonded with PU-DA in the heat treatment and thermal repair processes to improve the adhesive force between the film layers, and is melted and flows along with the polyurethane film in the self-repair process to drive the reconstruction of the silver nanowire network and recover the mechanical property in a cross-linking manner, so that the problems of the reconstruction and the stability of the silver nanowire conductive net after multiple self-repair are solved, and the high-performance self-repair silver nanowire flexible transparent conductive film is obtained.
The thermal-repair flexible transparent conductive film provided by the invention comprises a thermal reversible DA reaction polyurethane substrate layer arranged on the surface of a transparent functional layer. In the invention, the thickness of the thermal reversible DA reaction polyurethane substrate layer is preferably 20-100 μm; in the examples of the present invention, it is specifically 20 μm or 100 μm. The thermally reversible DA reactive polyurethane is transparent, and is used as a substrate, and in the processes of heat treatment and thermal repair, the thermally reversible DA reactive polyurethane is melted and flows to drive the silver nanowire conductive mesh to be reconstructed, so that the conductive film has self-repairing performance.
The invention provides a preparation method of the flexible transparent conductive film, which comprises the following steps: spraying and printing a silver nanowire transparent conductive network pattern on the surface of the base material by adopting an ink-jet printing method to form a transparent conductive layer on the surface of the base material;
coating a functional layer solution comprising polyester acrylate oligomer and furan methyl acrylate on the surface of the transparent conductive layer, carrying out polymerization reaction, and curing to form a transparent functional layer;
and coating the surface of the transparent functional layer with a thermally reversible DA reaction polyurethane prepolymer, drying, and forming a thermally reversible DA reaction polyurethane substrate layer to obtain the thermally repaired flexible transparent conductive film.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention adopts an ink-jet printing method to spray-print a silver nanowire transparent conductive network pattern on the surface of a base material, and a transparent conductive layer is formed on the surface of the base material.
In the present invention, the process of inkjet printing the silver nanowire transparent conductive network pattern on the surface of the substrate by using the inkjet printing method preferably includes: mixing silver nanowires, water and ethylene glycol to obtain transparent conductive ink; and spraying and printing the transparent conductive ink on the surface of the substrate to form a silver nanowire transparent conductive network pattern.
The transparent conductive ink is prepared by mixing silver nanowires, water and ethylene glycol. In the invention, the length of the silver nanowire is preferably 10-15 μm, and the diameter is preferably 20-30 nm; the water is preferably deionized water. In the invention, the mass concentration of the silver nanowires in the transparent conductive ink is preferably 0.2-0.35%, and more preferably 0.25-0.3%; the volume ratio of the water to the ethylene glycol is preferably 1: 3-5, and more preferably 1: 4. The invention has no special requirements on the mixing process, and any mode can be used for uniformly mixing the three components.
After the transparent conductive ink is obtained, the transparent conductive ink is jet-printed on the surface of the base material to form a silver nanowire transparent conductive network pattern. In the present invention, the substrate is preferably an EVOH (ethylene/vinyl alcohol copolymer) film, and the EVOH film is not particularly limited in the present invention, and an EVOH film known in the art may be used. The present invention preferably employs a flexible electronic printer for the jet printing. The invention has no special requirements on the specific model of the flexible electronic printer, and the flexible electronic printer known in the field can be adopted. In the invention, the voltage of the jet printing is preferably 20-36V, more preferably 21V; the number of the jet holes is preferably 1-8, and more preferably 2; the preferred spray printing speed is 40-80 μm s-1More preferably 60 μm · s-1. The invention has no special requirements on the specific shape of the silver nanowire transparent conductive network pattern, and the person skilled in the art can design the pattern according to the needs under the condition of ensuring the conductivity of the silver nanowire conductive network. The present invention preferably jet prints multilayer silver nanowire conductive network patterns to achieve a target thickness.
After the inkjet printing is completed, the invention preferably further comprises heat treatment of the inkjet printed pattern. In the present invention, the temperature of the heat treatment is preferably 80 ℃ and the time is preferably 5 hours. The invention dries the jet printed pattern by heat treatment (water and glycol are evaporated) to form a transparent conductive layer.
According to the invention, the silver nanowire conductive net is obtained by adopting an ink-jet printing method, so that subsequent etching and other processes are not needed, and the problems of controllability, repeatability and the like of the silver nanowire conductive net are solved.
After the transparent conductive layer is obtained, the surface of the transparent conductive layer is coated with a functional layer solution containing polyester acrylate oligomer and furan methyl acrylate, polymerization reaction is carried out, and the transparent functional layer is formed after curing.
In the invention, the functional layer solution is preferably obtained by mixing polyester acrylate oligomer, furan methyl acrylate and cyclopentanone. The mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is preferably 3-4: 1, and more preferably 4: 1; the mass ratio of the methyl furan acrylate to the cyclopentanone is preferably 1: 50-100, and more preferably 1: 60-80. The invention has no special requirements on the mixing process, and can completely dissolve the polyester acrylate oligomer and the furan methyl acrylate into cyclopentanone. The polyester acrylate oligomer has excellent wettability, so that the functional layer solution can be well coated on the surface of the silver nanowire.
In the invention, the coating mode is preferably spin coating, and the rotating speed of the spin coating is preferably 6000-9000 rpm, and more preferably 7000-8000 rpm.
In the present invention, the polymerization reaction is preferably carried out under irradiation of an ultraviolet lamp. The specific conditions of the ultraviolet lamp irradiation are not particularly limited, and the polyester acrylate oligomer and the furan methyl acrylate can be subjected to polymerization reaction. In the embodiment of the invention, an ultraviolet lamp with the model of GGY, the power of 250W and the wavelength of 350-450 nm is adopted for irradiating for 1 minute. In the polymerization reaction process, the organic solvent is evaporated, and the polyester acrylate oligomer and the furan methyl acrylate are subjected to polymerization reaction and solidification to form a transparent functional layer.
After the transparent functional layer is formed, the surface of the transparent functional layer is coated with the thermally reversible DA reactive polyurethane prepolymer, and a thermally reversible DA reactive polyurethane substrate layer is formed after the thermally reversible DA reactive polyurethane prepolymer is dried, so that the thermally repaired flexible transparent conductive film is obtained.
The preparation of the thermoreversible DA-reactive polyurethane prepolymer will be described below.
In the present invention, the preparation method of the thermoreversible DA reaction polyurethane prepolymer preferably includes the following steps:
mixing polytetrahydrofuran diol, anhydrous 4,4' -diphenylmethane diisocyanate and an organic solvent, and carrying out a first polymerization reaction on the obtained first mixture in a protective atmosphere to obtain an-NCO-terminated prepolymer;
adding furfuryl amine and a supplementary organic solvent into the-NCO-terminated prepolymer, and carrying out a second polymerization reaction on the obtained second mixture in a protective atmosphere to obtain furan ring-terminated isocyanate;
and adding diphenylmethane bismaleimide and a supplementary organic solvent into the furan ring-terminated isocyanate, and carrying out chain extension reaction on the obtained third mixture under a protective atmosphere to obtain the thermally reversible DA reaction polyurethane prepolymer.
According to the invention, polytetrahydrofuran diol, 4' -diphenylmethane diisocyanate and an organic solvent are mixed, and the obtained first mixture is subjected to a first polymerization reaction in a protective atmosphere to obtain an-NCO-terminated prepolymer.
In the invention, in the first mixed material, the mass content of polytetrahydrofuran diol is preferably 39.65-39.75%, the mass content of anhydrous 4,4' -diphenylmethane diisocyanate is preferably 19.8-19.9%, and the balance is solvent. In the present invention, the organic solvent is preferably N, N-dimethylformamide; the anhydrous 4,4 '-diphenylmethane diisocyanate is preferably 4,4' -diphenylmethane diisocyanate subjected to reduced pressure distillation. The invention adopts the 4,4 '-diphenylmethane diisocyanate after reduced pressure distillation to prevent the first polymerization reaction from being influenced by water mixed in the 4,4' -diphenylmethane diisocyanate.
The process of mixing polytetrahydrofuran diol, anhydrous 4,4' -diphenylmethane diisocyanate and a solvent according to the present invention preferably includes: dispersing polytetrahydrofuran diol into a liquid state by adopting ultrasound, and adding the liquid polytetrahydrofuran diol into a reaction container under a protective atmosphere; dissolving anhydrous 4,4 '-diphenylmethane diisocyanate into a solvent, and adding the obtained 4,4' -diphenylmethane diisocyanate solution into a reaction vessel containing liquid polytetrahydrofuran diol under a protective atmosphere to obtain a first mixture. In the present invention, the power of the ultrasound is preferably 300W, and the time of the ultrasound is preferably 1 hour. The protective atmosphere is preferably a nitrogen blanket.
After the first mixture is obtained, the first mixture is subjected to a first polymerization reaction under a protective atmosphere to obtain a-NCO end-capped prepolymer.
In the present invention, the protective atmosphere is preferably nitrogen gas; the temperature of the first polymerization reaction is preferably 50-70 ℃, and more preferably 60 ℃; the time is preferably 2.5 to 3.5 hours, and more preferably 3 hours. In the present invention, the first polymerization reaction is preferably carried out under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and those well known in the art may be used. In the first polymerization process of the present invention, 4,4' -diphenylmethane diisocyanate and polytetrahydrofuran diol are reacted to produce an-NCO terminated prepolymer.
After the-NCO-terminated prepolymer is obtained, furfuryl amine and a supplementary organic solvent are directly added into the-NCO-terminated prepolymer, and the obtained second mixture is subjected to a second polymerization reaction under a protective atmosphere to obtain furan ring-terminated isocyanate.
In the invention, the mass content of the furfuryl amine in the second mixture is preferably 6.0-6.1%, and the amount of the supplemented solvent is preferably 7.4-7.5% of the mass of the second mixture.
In the present invention, the process of adding furfuryl amine and replenishing the solvent to the-NCO-terminated prepolymer preferably comprises: and (3) cooling the-NCO-terminated prepolymer to 0 ℃, dropwise adding furfuryl amine and supplementing a solvent, and after dropwise adding is finished, returning the temperature to room temperature. Because the-NCO-terminated prepolymer and the furfuryl amine are very easy to react, the temperature of the-NCO-terminated prepolymer is reduced to 0 ℃, and simultaneously the furfuryl amine is added in a dropwise manner, so that the second polymerization reaction can be prevented from being too fast. The invention has no special requirement on the dropping speed, and can prevent the second reaction from generating too fast.
In the present invention, the temperature of the second polymerization reaction is preferably room temperature. The time for said second polymerization reaction is not particularly critical in the present invention, and is preferably 2270cm by infrared spectroscopy-1The disappearance of the characteristic absorption peak of-NCO at the left and right was used to determine the end point of the reaction. In the present invention, the protective atmosphere is preferably a nitrogen protective atmosphere. In the second polymerization process of the present invention, the-NCO terminated prepolymer reacts with furfuryl amine to generate furfuryl amine terminated isocyanate, i.e., furan ring terminated isocyanate (specifically, furan ring of furfuryl amine performs a capping function).
After the furan ring-terminated isocyanate is obtained, the diphenylmethane bismaleimide and the supplemented organic solvent are directly added into the furan ring-terminated isocyanate, and the obtained third mixture is subjected to chain extension reaction under a protective atmosphere to obtain the thermally reversible DA reaction polyurethane prepolymer.
In the invention, in the third mixture, the mass content of the diphenylmethane bismaleimide is preferably 9.8-9.9%, and the amount of the supplemented solvent is preferably 11.1-11.4% of the mass of the third mixture.
In the invention, the temperature of the chain extension reaction is preferably 50-70 ℃, and more preferably 60 ℃; the time is preferably 20 to 25 hours, and more preferably 24 hours. In the present invention, the protective atmosphere is preferably a nitrogen protective atmosphere. The chain extension reaction is preferably carried out under stirring conditions, and the stirring rate is not particularly required in the present invention, and a stirring rate well known in the art can be adopted. In the chain extension reaction, diphenylmethane bismaleimide serving as a chain extender reacts with furan ring end-sealed isocyanate to generate the thermally reversible DA reaction polyurethane prepolymer.
After the chain extension reaction is completed, the obtained reaction product is preferably cooled to room temperature, then the reaction product is added into ether for sedimentation and washing, and the bottom substance obtained by sedimentation is the DA reaction polyurethane prepolymer. In the present invention, the ether is preferably anhydrous ether. According to the invention, the reaction product is preferably dropwise added into ether under magnetic stirring for settling and washing for 3 times to obtain the thermally reversible DA reaction polyurethane prepolymer.
After the thermally reversible DA reaction polyurethane prepolymer is obtained, the thermally reversible DA reaction polyurethane prepolymer is coated on the surface of the transparent functional layer, and a thermally reversible DA reaction polyurethane substrate layer is formed after the thermally reversible DA reaction polyurethane prepolymer is dried.
In the invention, the coating mode is preferably spin coating, and the rotating speed of the spin coating is preferably 4000-9000 rpm, and more preferably 5000-8000 rpm.
In the invention, the drying is preferably carried out in a vacuum drying oven, the drying temperature is preferably 70 ℃, the drying time is not specially required in the invention, the drying is carried out to constant weight, the vacuum degree of the vacuum drying oven is not specially required in the invention, and the vacuum degree well known in the field can be adopted. . The drying process is the process of curing the thermally reversible DA reaction polyurethane prepolymer to form the thermally reversible DA reaction polyurethane.
After the heat reversible DA reaction polyurethane base layer is formed, the transparent conductive layer, the transparent functional layer and the heat reversible DA reaction polyurethane base layer obtained by the invention are used as a heat-repairing flexible transparent conductive film to be attached to a base material. The present invention does not require any particular peeling means, and any means capable of peeling the thermally repaired flexible transparent conductive film from the substrate can be used.
The following will describe the thermally repaired flexible transparent conductive film and the method for manufacturing the same in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Ink-jet printing of the silver nanowire conductive mesh: uniformly mixing 10mL of deionized water and 40mL of ethylene glycol, and then adding 0.15g of silver nanowires (with the length of 10-15 microns and the diameter of 20-30 nm) into the mixed solution to obtain silver nanowire conductive ink; the printing voltage was 21V, the number of orifices was 2, and the printing speed was 60 μm · s by using the Flexible Electronics Printer ink-jet printing-1Printing 3 layers on the surface of the EVOH film under the condition to obtain a silver nanowire conductive net, and then carrying out heat treatment at 80 ℃ for 5 hours to form a transparent conductive layer on the surface of the EVOH film.
4g of polyester acrylate oligomer (model CN8004) and 1g of methyl furan acrylate are added into 62.5g of cyclopentanone and stirred at 2000rpm until the polyester acrylate oligomer and the methyl furan acrylate are completely dissolved; spin-coating the solution on the surface of the transparent conductive layer at 8000 rpm; and (3) irradiating the coated sample for 1 minute under an ultraviolet lamp (the model is GGY, the power is 250W, and the wavelength is 350-450 nm) for curing to form a transparent functional layer with the thickness of 50 nm.
Preparing thermally reversible DA polyurethane: 30g of polytetrahydrofuran diol is subjected to ultrasonic treatment for 1 hour under the condition of 300W to be in a liquid state, and then the liquid polytetrahydrofuran diol is added into a dry three-neck flask under the protection of nitrogen; 30.5746g N, N-dimethylformamide subjected to reduced pressure distillation is added into a beaker, then 15.0156g of 4,4' -diphenylmethane diisocyanate is added into the beaker, the mixture is stirred at 1500rpm until the mixture is completely dissolved, then the mixture is added into a three-neck flask under the nitrogen atmosphere, and first polymerization is carried out at 60 ℃ for 3 hours at 250rpm, so as to generate a prepolymer terminated by-NCO; reducing the reaction temperature to 0 ℃ by using an ice water bath, slowly dropwise adding 5.32g of furfuryl amine, supplementing 6.5022g N, N-dimethylformamide, after dropwise adding is finished, recovering the reaction temperature to room temperature, and carrying out a second polymerization reaction in a nitrogen atmosphere to obtain furan ring-terminated isocyanate; 10.9698g of bismaleimide is added into the prepolymer system of the furan ring-terminated isocyanate, 13.4075g of solvent N, N-dimethylformamide is supplemented to be constant, and chain extension reaction is carried out for 24 hours at the temperature of 60 ℃ and the rotating speed of 250 rpm; after the reaction, the reaction solution is cooled to room temperature, and anhydrous ether is slowly dripped into the reaction solution under magnetic stirring to settle and wash for 3 times to obtain the thermally reversible DA reaction polyurethane prepolymer.
Coating the surface of the transparent functional layer with a thermally reversible DA reaction polyurethane prepolymer by adopting a spin coating process, wherein the spin coating speed is 8000rpm, and the thickness of the thermally reversible DA reaction polyurethane layer is 20 microns, and then drying the sample in a vacuum drying oven at 70 ℃ for 24 hours to constant weight; and tearing the sample from the surface of the EVOH film to obtain the heat-repairing flexible transparent conductive film.
The prepared heat-repairing flexible transparent conductive film has the light transmittance of 81 percent at the position of 550nm and the sheet resistance of 210 omega- □-1。
Scratching a flaw with the length of 3 cm and the depth of 5 mm on the surface of the conductive film by using an art designer knife, and then placing the conductive film under an infrared lamp (250W, the wavelength is 0.76-5 mu m) for heat treatment for 3 minutes, wherein the flaw disappears; the transmittance of the conductive film at 550nm after repair was determined to be 79%, and the sheet resistance was 221 Ω · □-1(ii) a The above process was repeated for the second time at the repaired scar, and the transmittance of the conductive film after repair at 550nm was determined to be 79%, and the sheet resistance was determined to be 229 Ω · □-1(ii) a The above process was repeated for the third time at the repaired scar, and the transmittance of the conductive film at 550nm after repair was measured to be 76%, and the sheet resistance was measured to be 235 Ω · □-1。
Example 2
Ink-jet printing of the silver nanowire conductive mesh: uniformly mixing 10mL of deionized water and 40mL of ethylene glycol, and then adding 0.15g of silver nanowires (with the length of 10-15 microns and the diameter of 20-30 nm) into the mixed solution to obtain silver nanowire conductive ink; the printing voltage was 21V, the number of orifices was 2, and the printing speed was 60 μm · s by using the Flexible Electronics Printer ink-jet printing-1Printing 6 layers on the surface of the EVOH film under the condition to obtain a silver nanowire conductive net, and then carrying out heat treatment at 80 ℃ for 5 hours to form a transparent film on the surface of the EVOH filmAnd a conductive layer.
4g of a polyester acrylate oligomer (model CN8004) and 1g of methyl Furanacrylate were added to 80g of cyclopentanone and stirred at 2000rpm until completely dissolved. Spin-coating the solution on the surface of the transparent conductive layer at 8000 rpm; and (3) irradiating the coated sample for 1 minute under an ultraviolet lamp (the model is GGY, the power is 250W, and the wavelength is 350-450 nm) for curing to form a transparent functional layer with the thickness of 40 nm.
Preparing thermally reversible DA polyurethane: 30g of polytetrahydrofuran diol is subjected to ultrasonic treatment for 1 hour under the condition of 300W to be in a liquid state, and then the polytetrahydrofuran diol is added into a dry three-neck flask under the protection of nitrogen; 30.5746g N, N-dimethylformamide after distillation under reduced pressure was added to a beaker, then 15.0156g of 4,4' -diphenylmethane diisocyanate was added to the beaker, stirred at 1500rpm until completely dissolved, and then added to a three-necked flask under nitrogen atmosphere, and first polymerized at 60 ℃ at 250rpm for 3 hours to give a prepolymer terminated with-NCO. Reducing the reaction temperature to 0 ℃ by using an ice water bath, slowly dropwise adding 5.32g of furfuryl amine, supplementing 6.5022g N, N-dimethylformamide, after dropwise adding is finished, recovering the reaction temperature to room temperature, and carrying out a second polymerization reaction in a nitrogen atmosphere to obtain furan ring-terminated isocyanate; 10.9698g of bismaleimide is added into the prepolymer system of the furan ring-terminated isocyanate, 13.4075g of solvent N, N-dimethylformamide is supplemented to be constant, and chain extension reaction is carried out for 24 hours at the temperature of 60 ℃ and the rotating speed of 250 rpm; after the reaction, the reaction solution is cooled to room temperature, and anhydrous ether is slowly dripped into the reaction solution under magnetic stirring to settle and wash for 3 times to obtain the thermally reversible DA reaction polyurethane prepolymer.
Coating the thermally reversible DA reaction polyurethane prepolymer on the surface of the transparent functional layer by adopting a spin coating process, wherein the spin coating speed is 8000rpm, and the thickness of the thermally reversible DA reaction polyurethane layer is 20 microns, and then drying the sample in a vacuum drying oven at 70 ℃ for 24 hours until the weight is constant; and tearing the sample from the surface of the EVOH film to obtain the heat-repairing flexible transparent conductive film.
The prepared heat-repairing flexible transparent conductive film has the light transmittance of 73% at 550nm and the square resistance of 90 omega- □-1。
Scratching a flaw with the length of 3 cm and the depth of 5 mm on the surface of the conductive film by using an art designer knife, and then placing the conductive film under an infrared lamp (250W, the wavelength is 0.76-5 mu m) for heat treatment for 3 minutes, wherein the flaw disappears; the transmittance of the conductive film at 550nm after repair was measured and measured to be 73%, and the sheet resistance was measured to be 87. omega. □-1(ii) a The above process was repeated for the second time at the repaired scar, and the transmittance at 550nm of the conductive film after repair was measured to be 73%, and the sheet resistance was measured to be 95 Ω · □-1(ii) a The above procedure was repeated for the third time at the repaired scar, and the transmittance at 550nm of the conductive film after repair was measured to be 71%, and the sheet resistance was 107. omega. □-1。
Example 3
Ink-jet printing of the silver nanowire conductive mesh: uniformly mixing 10mL of deionized water and 40mL of ethylene glycol, and then adding 0.15g of silver nanowires (with the length of 10-15 microns and the diameter of 20-30 nm) into the mixed solution to obtain silver nanowire conductive ink; the printing voltage was 21V, the number of orifices was 2, and the printing speed was 60 μm · s by using the Flexible Electronics Printer ink-jet printing-1Under the condition, 5 layers are printed on the surface of the EVOH film to obtain the silver nanowire conductive net, and then the silver nanowire conductive net is subjected to heat treatment at 80 ℃ for 5 hours to form a transparent conductive layer on the surface of the EVOH film.
Respectively adding 4g of polyester acrylate oligomer (model CN8004) and 1g of furan methyl acrylate into 80g of cyclopentanone, and stirring at 2000rpm until the polyester acrylate oligomer and the furan methyl acrylate are completely dissolved; the solution was spin coated on the surface of the transparent conductive layer at 7000 rpm. And (3) irradiating the coated sample for 1 minute under an ultraviolet lamp (the model is GGY, the power is 250W, and the wavelength is 350-450 nm) for curing to form a transparent functional layer with the thickness of 70 nm.
Preparing thermally reversible DA polyurethane: 30g of polytetrahydrofuran diol is subjected to ultrasonic treatment for 1 hour under the condition of 300W to be in a liquid state, and then the polytetrahydrofuran diol is added into a dry three-neck flask under the protection of nitrogen; 30.5746g N, N-dimethylformamide subjected to reduced pressure distillation is added into a beaker, then 15.0156g of 4,4' -diphenylmethane diisocyanate is added into the beaker, the mixture is stirred at 1500rpm until the mixture is completely dissolved, then the mixture is added into a three-neck flask under the nitrogen atmosphere, and first polymerization is carried out at 60 ℃ for 3 hours at 250rpm, so as to generate a prepolymer terminated by-NCO; reducing the reaction temperature to 0 ℃ by using an ice water bath, slowly dropwise adding 5.32g of furfuryl amine, supplementing 6.5022g N, N-dimethylformamide, after dropwise adding is finished, recovering the reaction temperature to room temperature, and carrying out a second polymerization reaction in a nitrogen atmosphere to obtain furan ring-terminated isocyanate; 10.9698g of bismaleimide is added into the prepolymer system of the furan ring-terminated isocyanate, 13.4075g of solvent N, N-dimethylformamide is supplemented to be constant, and chain extension reaction is carried out for 24 hours at the temperature of 60 ℃ and the rotating speed of 250 rpm; after the reaction, the reaction solution is cooled to room temperature, and anhydrous ether is slowly dripped into the reaction solution under magnetic stirring to settle and wash for 3 times to obtain the thermally reversible DA reaction polyurethane prepolymer.
Coating the thermally reversible DA reaction polyurethane prepolymer on the surface of the functional layer by adopting a spin coating process, wherein the spin coating speed is 5000rpm, and the thickness of the thermally reversible DA reaction polyurethane layer is 100 microns, and then drying a sample in a vacuum drying oven at 70 ℃ for 24 hours until the weight is constant; and tearing the sample from the surface of the EVOH film to obtain the heat-repairing flexible transparent conductive film.
The prepared heat-repairing flexible transparent conductive film has the light transmittance of 78% at 550nm and the sheet resistance of 130 omega- □-1。
Scratching a flaw with the length of 3 cm and the depth of 5 mm on the surface of the conductive film by using an art designer knife, and then placing the conductive film under an infrared lamp (250W, the wavelength is 0.76-5 mu m) for heat treatment for 3 minutes, wherein the flaw disappears; the transmittance of the conductive film at 550nm after repair was measured to be 78%, and the sheet resistance was 137. omega. □-1(ii) a The above process was repeated for the second time at the repaired scar, and the transmittance of the conductive film after repair at 550nm was measured to be 75%, and the sheet resistance was 141 Ω · □-1(ii) a The above procedure was repeated for the third time at the repaired scar, and the transmittance of the conductive film after repair at 550nm was measured to be 71%, and the sheet resistance was 148. omega. □-1。
The embodiment shows that the heat-repairing flexible transparent conductive film and the preparation method thereof are provided, and the conductive film has high transparency, good self-repairing performance, good light transmittance and conductivity after being repaired for many times, and high repairing efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The thermal-repair flexible transparent conductive film is characterized by comprising a transparent conductive layer, a transparent functional layer and a thermally reversible DA (polyurethane) substrate layer which are sequentially stacked; the transparent conducting layer is a silver nanowire conducting net; the transparent functional layer is obtained by polymerizing polyester acrylate oligomer and furan methyl acrylate.
2. The heat-repaired flexible transparent conductive film according to claim 1, wherein the mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is 3-4: 1.
3. A method of making a thermally repaired flexible transparent conductive film according to claim 1 or 2 comprising the steps of:
spraying and printing a silver nanowire transparent conductive network pattern on the surface of the base material by adopting an ink-jet printing method to form a transparent conductive layer on the surface of the base material;
coating a functional layer solution comprising polyester acrylate oligomer and furan methyl acrylate on the surface of the transparent conductive layer, carrying out polymerization reaction, and curing to form a transparent functional layer;
coating a thermally reversible DA (polyurethane) prepolymer on the surface of the transparent functional layer, and drying to form a thermally reversible DA polyurethane substrate layer;
and peeling the transparent conductive layer, the transparent functional layer and the thermally reversible DA reaction polyurethane base layer from the base material to obtain the thermally repaired flexible transparent conductive film.
4. The preparation method of claim 3, wherein the process of inkjet printing the silver nanowire transparent conductive network pattern on the surface of the substrate comprises the following steps: mixing silver nanowires, water and ethylene glycol to obtain transparent conductive ink; spraying and printing the transparent conductive ink on the surface of a substrate to form a silver nanowire transparent conductive network pattern; the mass concentration of the silver nanowires in the transparent conductive ink is 0.2-0.35%; the volume ratio of the water to the ethylene glycol is 1: 3-5.
5. The method of manufacturing according to claim 4, wherein the inkjet printing is performed using a flexible electronic printer; the voltage of the jet printing is 20-36V, the number of the jet holes is 1-8, and the jet printing speed is 40-80 mu m.s-1。
6. The preparation method according to claim 3, wherein the functional layer solution is obtained by mixing a polyester acrylate oligomer, furan methyl acrylate and cyclopentanone; the mass ratio of the polyester acrylate oligomer to the furan methyl acrylate is 3-4: 1.
7. The method according to claim 3, wherein the method for preparing the thermally reversible DA-reactive polyurethane prepolymer comprises the following steps:
mixing polytetrahydrofuran diol, anhydrous 4,4' -diphenylmethane diisocyanate and an organic solvent, and carrying out a first polymerization reaction on the obtained first mixture in a protective atmosphere to obtain an-NCO-terminated prepolymer;
adding furfuryl amine and a supplementary organic solvent into the-NCO-terminated prepolymer, and carrying out a second polymerization reaction on the obtained second mixture in a protective atmosphere to obtain furan ring-terminated isocyanate;
and adding diphenylmethane bismaleimide and a supplementary organic solvent into the furan ring-terminated isocyanate, and carrying out chain extension reaction on the obtained third mixture under a protective atmosphere to obtain the thermally reversible DA reaction polyurethane prepolymer.
8. The preparation method according to claim 7, wherein the first mixture contains 39.65 to 39.75% by mass of polytetrahydrofuran diol and 19.8 to 19.9% by mass of 4,4' -diphenylmethane diisocyanate; the temperature of the first polymerization reaction is 50-70 ℃, and the time is 2.5-3.5 h.
9. The preparation method according to claim 7, wherein the mass content of the furfuryl amine in the second mixed material is 6.0-6.1%, and the amount of the supplementary solvent is 7.4-7.5% of the mass of the second mixed material.
10. The preparation method according to claim 7, wherein in the third mixture, the mass content of the diphenylmethane bismaleimide is 9.8-9.9%, and the amount of the supplemented solvent is 11.1-11.4% of the mass of the third mixture; the temperature of the chain extension reaction is 50-70 ℃, and the time is 20-25 h.
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