CN110970173B - Method for manufacturing nano silver wire transparent conductive film with customizable patterns - Google Patents
Method for manufacturing nano silver wire transparent conductive film with customizable patterns Download PDFInfo
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- CN110970173B CN110970173B CN201911149426.2A CN201911149426A CN110970173B CN 110970173 B CN110970173 B CN 110970173B CN 201911149426 A CN201911149426 A CN 201911149426A CN 110970173 B CN110970173 B CN 110970173B
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- silver wire
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a method for manufacturing a pattern-customizable nano silver wire transparent conductive film, which is characterized in that the patterning of the nano silver wire transparent conductive film is realized by utilizing the change of the peeling force between a coating liquid with a UV irradiation anti-sticking function and a base film before and after UV irradiation and combining a bonding adhesive and a flexible transparent optical adhesive which are suitable for the nano silver wire transparent conductive film, and the patterned nano silver wire transparent conductive film taking the flexible transparent optical adhesive as a substrate is obtained. The invention has simple process and higher product yield, and the obtained conductive film has better optical performance and flexibility.
Description
Technical Field
The invention belongs to the field of display, and particularly relates to a method for manufacturing a nano silver wire transparent conductive film with customizable patterns.
Background
With the development of electronic displays to large size and flexibility, the requirement for flexibility of the conductive film is higher and higher. The ITO transparent conductive film with the largest market consumption at present has the problems of high sheet resistance and poor flexibility, and is not suitable for large-size display and flexible display. The nano silver wire in the new material becomes the optimal alternative material of ITO due to the excellent comprehensive properties of good optical property and flexibility, low sheet resistance and the like.
The sheet resistance of the nano silver wire transparent conductive film can be very low, and the nano silver wire transparent conductive film is completely suitable for large-size display. However, the silver nanowire transparent conductive films currently used in the market are formed by forming a silver nanowire conductive layer and a protective layer on a film substrate. Therefore, the existing transparent conductive film of nano silver wire has a film substrate. With the increasing requirements of flexible display and foldable display, higher requirements are put on the flexibility of the nano silver wire conductive film. The method for improving the flexibility of the rubber mainly comprises two parts: (1) replacing conventional film substrates such as PET (polyethylene terephthalate) with more flexible film substrates such as CPI (transparent polyimide); (2) the flexibility of the conductive layer is improved by modifying the conductive layer. The flexibility of the conductive layer can completely meet any situation through modification because the nano silver wire has good flexibility, but the flexibility of the film substrate limits the flexibility of the conductive film of the nano silver wire.
In addition, the currently marketed silver nanowire transparent conductive films are all complete unpatterned coil materials, and the processes of cutting, aging, patterning and the like are required when the silver nanowire transparent conductive films are used, so that the process is complex, and the product yield is reduced to a certain extent.
Aiming at the problems that the flexibility of the existing transparent conductive film of the nano silver wire is limited, the treatment process is complex during use, the yield is influenced and the like, the development of the flexible transparent conductive film of the nano silver wire which is not limited by the flexibility of the base film, can be applied to any flexible display field, and is convenient to use and high in yield is urgently needed.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention aims to provide the method for manufacturing the nano silver wire transparent conductive film with customizable patterns, so that the flexible nano silver wire transparent conductive film which can be applied to any flexible display field, is convenient to use and has high yield can be obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for manufacturing a nano silver wire transparent conductive film with customizable patterns is characterized by comprising the following steps:
step 1, arranging a nano silver wire transparent conductive film taking a base film as a substrate
11. Coating a coating liquid with a UV irradiation viscosity-reducing function on the surface of the base film, drying and curing to form a base coating, wherein a certain stripping force is formed between the base coating and the base film;
preferably, the base film can be any one of the film substrates commonly used for the current transparent conductive film of the nano silver wire, such as PET, COP or CPI;
preferably, the drying and curing is drying at 120 ℃ for 2-5 min;
preferably, the thickness of the bottom coating and the protective coating is controlled to be 50-200 nm;
12. coating nano silver wire conductive ink on the surface of the bottom coating and drying to form a nano silver wire conductive layer;
preferably, the drying is performed at 100-120 ℃ for 30-60 s;
13. coating the coating liquid with the UV irradiation viscosity reduction function on the surface of the nano silver wire conductive layer again, drying and curing, wherein the coating liquid uniformly permeates into the conductive layer in the drying and curing process and reaches the interface between the conductive layer and the bottom coating to form a protective layer, so that the nano silver wire transparent conductive film taking the base film as the substrate is obtained;
preferably, the drying and curing is drying at 120 ℃ for 2-5 min;
preferably, the thickness of the protective layer is controlled to be 50-200 nm;
step 2, patterning the nano silver wire transparent conductive film taking the base film as the substrate
21. Setting a mask (which can be a film or a chromium plate), wherein the mask comprises a light-transmitting area (namely an explosion area) and a shielding area (namely a non-explosion area) to form a required pattern, the light-transmitting area corresponds to the non-pattern area of the required conductive film pattern, and the shielding area corresponds to the pattern area;
attaching the mask plate to the surface of the protective layer, and then carrying out UV exposure to reduce the stripping force between the exposure area of the conductive film and the base film;
preferably, the UV exposure is at 400-1000mJ/cm2UV irradiation is carried out for 5-20s under energy, and after irradiation, the peeling force between the conductive film and the base film in the light exposure area is reduced to be less than 2N/2.5 cm;
22. arranging a concave-convex roller, wherein the convex surface of the concave-convex roller corresponds to an exposure area of the conductive film, the concave surface of the concave-convex roller corresponds to a non-exposure area, and bonding glue is uniformly coated on the convex surface of the concave-convex roller; sticking and removing the conductive film in the exposed area on the base film through the concave-convex roller, namely forming the conductive film with the required pattern on the base film;
step 3, transferring the patterned conductive film on the base film
31. Carrying out UV irradiation on the patterned conductive film on the base film to reduce the stripping force between the patterned conductive film and the base film, and simultaneously enabling the protective layer and the bottom coating layer of the conductive film to react and be connected into a whole at the interface of the bottom coating layer and the conductive layer;
preferably, the UV irradiation is at 400-2UV irradiation is carried out for 5-20s under energy, and after irradiation, the peeling force between the patterned conductive film and the base film is reduced to be less than 2N/2.5 cm;
32. the surface of the conductive film is adhered with flexible transparent optical cement, then the base film is torn off, namely the conductive film is transferred to the surface of the flexible transparent optical cement, so that the patterned nano silver wire transparent conductive film taking the flexible transparent optical cement as the substrate is prepared, and the structure of the patterned nano silver wire transparent conductive film sequentially comprises a flexible transparent optical cement protective layer, a nano silver wire conductive layer and a bottom coating from bottom to top, namely the bottom coating becomes the protective layer of the conductive film with the structure.
In practical application, for example, when the flexible transparent optical adhesive is used for a display screen, two layers of conductive films with matching patterns are often required to be arranged, and at this time, according to the required patterns, two patterned nano silver wire transparent conductive films with the base film as the substrate are firstly obtained according to the methods of the steps 1 and 2, and then according to the method of the step 3, the conductive films are respectively transferred to two sides of the flexible transparent optical adhesive.
Further, the coating liquid with the UV irradiation viscosity reduction function comprises the following components in percentage by mass:
preferably: the hydroxyl acrylate is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and caprolactone acrylate; the cross-linking agent is one of aliphatic diisocyanate; the molar ratio of hydroxyl in the hydroxyl acrylate to isocyanate in the cross-linking agent is 1: 1.1-1.3;
the UV resin is a mixture of any two of polyurethane acrylate WDS-4500 (Wuxi Victoria electronic materials Co., Ltd.), WDS-9500 (Wuxi Victoria electronic materials Co., Ltd.), WDS-9568 (Wuxi Victoria electronic materials Co., Ltd.), WDS-9700 (Wuxi Victoria electronic materials Co., Ltd.), DSM230A2 (Tesmann), DSM2421 (Tesmann), U400-1 (Handong trade), CN9013NS (Sadorma), CN9010 (Sadorma), DM87A (double bond chemical industry) and DM588 (double bond chemical industry) in a mass ratio of 1: 1;
preferably: the UV monomer is one of trimethylolpropane triacrylate, ditrimethyloltetraacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; the photoinitiator is one or a mixture of two of a cracking type free radical photoinitiator 1173, a photoinitiator 184, a photoinitiator 2959, a photoinitiator TPO and a photoinitiator 819 which are mixed according to any ratio; the solvent is a mixture of a solvent A, a solvent B and a solvent C according to a mass ratio of 1:1:1, wherein: the solvent A is acetone, butanone, ethyl acetate or methyl acetate, the solvent B is n-propanol, isopropanol, butanol, isobutanol or butyl acetate, and the solvent C is cyclohexanone, cyclohexanol, ethylene glycol, 1, 3-propanediol or 1, 3-butanediol.
The preparation method of the coating liquid with the UV irradiation viscosity-reducing function comprises the following steps: under dustless and yellow light environment, adding the solvent, the UV resin, the UV monomer and the acrylic hydroxy ester into a dispersion cylinder in sequence, and mechanically stirring for 30min at the speed of 500-2000 r/min; then sequentially adding the photoinitiator and the cross-linking agent, and continuously stirring for 10min to obtain the coating liquid with the UV irradiation viscosity-reducing function.
In steps 21 and 31, the peeling force of the conductive film and the base film before UV irradiation is more than 10N/2.5 cm. The coating liquid with the UV irradiation viscosity reduction function has certain shrinkage rate during UV curing, so that the stripping force is 1000mJ/cm after passing through 400-2After UV irradiation at energy for 5-20s, the temperature is reduced to less than 2N/2.5 cm.
The optical cement in the current market is mainly made of an ITO conductive film as a matched material, and has the problems of poor flexibility and poor matching property with a nano silver wire. Therefore, the invention also discloses an adhesive and a special flexible transparent optical adhesive for the nano silver wire transparent conductive film, which are disclosed in the patent already filed by the applicant (the application number is 2019111361542, and the name of the invention is 'special flexible transparent optical adhesive for the nano silver wire transparent conductive film and a preparation method thereof').
Further, in step 22, the adhesive glue comprises the following components in percentage by mass:
further, in step 32, the components of the flexible transparent optical adhesive in percentage by mass are:
the adhesive glue is used for adhering the conductive film in the non-pattern area from the base film, and the flexible transparent optical glue is used for not only transferring the patterned conductive film on the base film, but also serving as a new substrate of the transferred conductive film and protecting the same. In the formula system of the adhesive and the flexible transparent optical adhesive:
preferably, the synthesis of the polyurethane acrylic prepolymer comprises the following steps:
(a) dehydrating raw materials:
carrying out high-temperature vacuum-pumping dehydration treatment on raw materials of polyol, isocyanate and hydroxyl acrylate, wherein the treatment conditions are as follows: the temperature is 80-120 ℃, the vacuum degree is 0.05-0.1MPa, and the time is 2-4 h;
the polyhydric alcohol is one of PEG400, PEG-1000, PPG-400, PPG-1000 and PPG-2000 and polyoxypropylene triol-600 according to the hydroxyl molar ratio of 3-5: 1 mixing the components; the isocyanate is one of 1, 6-hexamethylene diisocyanate and trimethyl-1, 6-hexamethylene diisocyanate; the hydroxy acrylic ester is one of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
(b) polyol and isocyanate reaction:
in N2Under the environment protection, adding the isocyanate subjected to dehydration treatment into a flask, mechanically stirring at the speed of 200-500r/min, simultaneously heating to 60-70 ℃, and then dropwise adding the polyol subjected to dehydration treatment into the flask at a constant speed for 2 hours; after the dropwise addition is finished, continuously preserving heat, stirring and reacting until the-NCO content reaches a theoretical value and keeps unchanged, and stopping the reaction to obtain a first-step product;
wherein the molar ratio of-NCO in the isocyanate subjected to dehydration treatment to-OH in the polyol subjected to dehydration treatment is 1.1:1 so as to ensure that the-OH can be reacted completely;
(c) double bond reaction:
keeping the original mechanical stirring speed of the product of the first step, heating to 80 ℃, adding p-hydroxyanisole, dropwise adding the dehydrated hydroxyl acrylate into a flask at a constant speed for 1 h; after the dropwise addition is finished, continuously preserving heat, stirring and reacting until the-NCO content is 0, cooling to room temperature after the reaction is finished, and discharging to obtain a polyurethane acrylic prepolymer;
wherein: the mol ratio of-NCO in the first step product to-OH in the hydroxyl acrylic ester is 1:1.1, so as to ensure that-NCO can completely react; the addition amount of the p-hydroxyanisole accounts for 0.2% of the total mass of the isocyanate subjected to dehydration treatment in the step (b) and the polyol subjected to dehydration treatment.
Preferably: the active diluent is one of BDDA and HDDA and TMP (EO)6DA、TMP(EO)9DA and TMP (EO)15A mixture formed by mixing one of DA according to the mass ratio of 5-10: 1; the photoinitiator is one of a photoinitiator 173, a photoinitiator 184 and a photoinitiator 754; the tackifying resin is Piccotac 1095-N; the light stabilizer is one of light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer 944; the antioxidant is one of antioxidant 168, antioxidant 245, antioxidant 1010, antioxidant 1024, antioxidant 1076, antioxidant 1098 and antioxidant 1135; the ultraviolet absorbent is a mixture formed by mixing UV-531 and one of UV-P, UV-234, UV-320, UV-326, UV-327 and UV-320 in a mass ratio of 1: 1; the infrared absorbent is IRA HSYP 03.
The preparation method of the adhesive glue comprises the following steps: under yellow light and dustless environment, sequentially adding the reactive diluent, the polyurethane acrylic prepolymer and the tackifying resin into a dispersion cylinder, mechanically stirring and uniformly dispersing; then adding the photoinitiator, and continuously stirring and uniformly mixing to obtain the adhesive. When the adhesive is used, the adhesive is poured into the liquid tank, and then the concave-convex roller with the required concave-convex pattern is immersed into the liquid tank and rotates, so that the convex surface of the concave-convex roller is completely covered by the adhesive; and carrying out UV curing on the concave-convex roller covered with the bonding glue to form the required glue-carrying patterned concave-convex roller. The stripping force of the adhesive glue on the concave-convex roller and the conductive film is more than 20N/2.5 cm.
The preparation method of the flexible transparent optical cement comprises the following steps: (1) under yellow light and dustless environment, sequentially adding the reactive diluent, the polyurethane acrylic prepolymer and the tackifying resin into a dispersion cylinder, mechanically stirring and uniformly dispersing; then adding a light stabilizer, an antioxidant, an ultraviolet absorbent, an infrared absorbent and a photoinitiator in sequence, and continuously stirring uniformly to obtain a glue solution; (2) and coating the obtained glue solution to form a film, carrying out UV curing, attaching a release film, and finally rolling to obtain the flexible transparent optical glue. Preferably, the thickness of the glue solution coated film is 5-500 μm. The light transmittance of the flexible transparent optical adhesive is more than or equal to 99.5 percent, and the haze is less than or equal to 0.2 percent. And through reasonable configuration of the contents of the polyurethane acrylic prepolymer and the tackifying resin, the prepared optical adhesive has good adhesion with the nano silver wire conductive film, the stripping force is more than or equal to 20N/2.5cm, and the adhesion with other pure organic coatings is relatively low (the stripping force is between 5 and 10N/2.5 cm).
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the change of the peeling force between the coating liquid with the UV irradiation viscosity-reducing function and the base film before and after UV irradiation is combined with the adhesive and the flexible transparent optical adhesive which are suitable for the nano silver wire conductive film, so that the patterning of the nano silver wire transparent conductive film is realized, the patterned nano silver wire transparent conductive film taking the flexible transparent optical adhesive as the substrate is obtained, the process is simple, and the product yield is higher.
2. The patterned nano silver wire transparent conductive film taking the flexible transparent optical adhesive as the substrate is convenient to use, and patterns can be arranged as required.
3. Compared with the traditional film substrate, the optical adhesive is used as the substrate, and the optical adhesive has good optical performance (the light transmittance is higher than 95%) and good flexibility. In addition, when the existing silver nanowire transparent conductive film is used, for example, in a TP for a flexible display structure, the two conductive films need to be bonded by optical glue, and then bonded with the rest parts such as a cover plate by the optical glue. The invention directly uses the optical cement as the substrate, thereby saving the film substrate and being more convenient for the manufacture of the devices at the later stage.
4. The flexible transparent optical adhesive is suitable for the nano silver wire transparent conductive film and has the following advantages:
(1) good flexibility, matching with the nano silver wire and having a certain protection effect on the nano silver wire. The optical adhesive and the nano silver wire conducting layer have adjustable viscosity and large stripping force, and the nano silver wire conducting layer formed on the substrate can be directly stripped off and adhered to the surface of the optical adhesive through the adhesion of the optical adhesive, so that the prepared conducting film does not need to use the substrate, and better flexible display is realized.
(2) The main component of the polyurethane acrylic prepolymer of the flexible transparent optical adhesive of the invention uses polyether diol and aliphatic diisocyanate. The polyether structure has weak interaction force among molecular chains, the crystallinity of a reaction product is low, the optical property of the prepared optical cement is good, and meanwhile, the polyether structure has good aging resistance and flexibility; the aliphatic diisocyanate is resistant to light aging, excellent in weather resistance and free from yellowing. Therefore, the prepared transparent optical adhesive has good optical performance, excellent aging resistance and good flexibility, and is more suitable for flexible display.
(3) In the formula of the optical adhesive, the viscosity of the optical adhesive can be controlled and the stripping force can be adjusted by adjusting the content of the tackifying resin.
(4) The optical adhesive is added with the light stabilizer, the ultraviolet absorbent and the infrared absorbent, so that the damage of ultraviolet light and infrared light to nano silver wires can be effectively isolated; meanwhile, the antioxidant added into the optical cement can effectively reduce the oxidation damage speed of the nano silver wire. Therefore, the prepared transparent optical adhesive has a good protection effect on the nano silver wire, and the service life of the conductive film is effectively prolonged.
Drawings
FIG. 1 is a schematic view of a process for manufacturing a customizable pattern of a silver nanowire transparent conductive film according to the present invention;
FIG. 2 is a schematic structural diagram of the present invention when the performance of the obtained transparent conductive film of the nano silver wire is tested.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The following examples and comparative examples used the following formulation of silver nanowire conductive ink:
the preparation method comprises the following steps:
a. adding graphene oxide XF004L (with the thickness of 0.8-1.2nm and the sheet diameter of 0.5-5 mu m, and the thickness of the first-order Feng nanometer) into water, performing ultrasonic dispersion uniformly to obtain a graphene oxide aqueous solution with the concentration of 10mg/mL, pouring the graphene oxide aqueous solution into a closed flask, treating the graphene oxide aqueous solution for 15 hours at 210 ℃ by using an oven, then cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the thickness of less than or equal to 1nm and the sheet diameter of less than or equal to 10 nm.
b. Sequentially adding deionized water, graphene quantum dots and nano silver wires WJAG1 (wire diameter is 20nm, length-diameter ratio is 1000-minus-one 2000, fertilizer-combining microcrystalline material science and technology limited) into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to ensure that the surfaces of the nano silver wires and the graphene quantum dots are fully combined through coordination;
c. and adding hydroxyethyl cellulose into the solution, and stirring at the speed of 500r/min for 30min to obtain the nano silver wire conductive ink.
Example 1 preparation of adhesive and Flexible clear optical Adhesives
The preparation method of the polyurethane acrylic prepolymer used for the adhesive and the flexible transparent optical adhesive of the embodiment is as follows:
(a) dehydrating raw materials: performing high-temperature vacuum-pumping dehydration treatment on PEG-1000, polyether triol polyoxypropylene triol-600, 1, 6-hexamethylene diisocyanate and hydroxyethyl acrylate under the following treatment conditions: the temperature is 100 ℃, the vacuum degree is 0.1MPa, and the time is 2 h.
(b) Polyol and isocyanate reaction: in N2Under the protection environment, 5.5mol of dehydrated 1, 6-hexamethylene diisocyanate is added into a flask, the mixture is mechanically stirred at the speed of 500r/min and is slowly heated to 60 ℃,then dropwise adding the dehydrated mixed solution of 3.64mol of PEG-1000 and 0.91mol of polyether triol polyoxypropylene triol-600 into a flask at a constant speed for 2 h; after the dropwise addition is finished, continuously preserving heat, stirring and reacting, titrating the-NCO value once every 0.5h until the-NCO content reaches a theoretical value and keeps unchanged, and stopping the reaction to obtain a first-step product;
(c) double bond reaction: keeping the original mechanical stirring speed of the product in the first step, raising the reaction temperature to 80 ℃, adding 10g of p-hydroxyanisole, dropwise adding 1.1mol of dehydrated hydroxyethyl acrylate into a flask at a constant speed, and dropwise adding for 1 h; and after the dropwise addition is finished, continuously keeping the temperature and stirring for reaction, then titrating the-NCO value once every 0.5h until the-NCO content is 0, finishing the reaction, cooling to room temperature and discharging to obtain the polyurethane acrylic prepolymer.
The preparation method of the adhesive glue of the embodiment comprises the following steps: yellow light, dust free Environment, 90g HDDA, 10g TMP (EO)6DA. Adding 750g of polyurethane acrylic prepolymer and 110g of Piccotac1095-N into a dispersion cylinder in sequence, mechanically stirring and uniformly dispersing; then 40g of photoinitiator 173 is added, and the mixture is continuously stirred and uniformly mixed to obtain the adhesive. When the adhesive is used, the adhesive is poured into the liquid tank, and then the concave-convex roller with the required concave-convex pattern is immersed into the liquid tank and rotates, so that the convex surface of the concave-convex roller is completely covered by the adhesive; then UV curing (2000 mJ/cm) is carried out on the concave-convex roller covered with the bonding glue210s), the desired patterned concavo-convex roller with glue is formed. The stripping force of the adhesive glue on the concave-convex roller and the conductive film is more than 20N/2.5 cm.
The configuration method of the flexible transparent optical cement of the embodiment comprises the following steps:
(1) yellow light, dust free Environment, 90g HDDA, 10g TMP (EO)9DA. Adding 750g of polyurethane acrylic prepolymer and 90g of Piccotac1095-N into a dispersion cylinder in sequence, mechanically stirring and uniformly dispersing; then, sequentially adding 5g of light stabilizer 292, 5g of antioxidant 1024, 2.5g of UV-328, 2.5g of UV-531, 5g of IRA HSYP 03 and 40g of photoinitiator 754, and continuously stirring uniformly to obtain a glue solution;
(2) the resulting dope was coated to form a film and UV-cured (2000 mJ/cm)210s), attaching a release film, and finallyAnd (5) rolling to obtain the flexible transparent optical cement, wherein the thickness of the optical cement is 125 microns.
The flexible transparent optical adhesive prepared by the embodiment has no defects such as obvious dirt, impurities, gel, bubbles or damage and the like, the light transmittance is 99.6%, the haze is 0.2%, and the stripping force between the flexible transparent optical adhesive and a nano silver wire conducting layer is more than 20N/2.5 cm; after reliability tests such as xenon lamp aging, UV aging, high temperature and high humidity and the like are carried out, the performance of the material is not obviously reduced.
Example 2
The coating liquid with the UV irradiation viscosity reduction function used in this example was prepared by the following method: in a dustless and yellow environment, 972g of a solvent (a mixture of ethyl acetate, butanol and cyclohexanone in a mass ratio of 1:1: 1), 20g of a UV resin (a mixture of WDS-9500 and DSM2421 in a mass ratio of 1: 1), 4g of a UV monomer (trimethylolpropane triacrylate) and 2g of hydroxyethyl acrylate are sequentially added into a dispersion tank, and mechanically stirred at 1000r/min for 30 min; then, 1g of photoinitiator (photoinitiator 184) and 1g of cross-linking agent (1, 6-hexamethylene diisocyanate) are sequentially added, and stirring is continued for 10min, so that the coating liquid with the UV irradiation viscosity reduction function is prepared.
As shown in fig. 1, the present embodiment produces a transparent conductive film with a desired pattern of silver nanowires by the following steps:
step 1, arranging a nano silver wire transparent conductive film taking a PET base film as a substrate
11. Coating a coating liquid with a UV irradiation viscosity-reducing function on the surface of a PET base film, drying and curing at 120 ℃ for 2min to form a primer layer with the thickness of 100 +/-10 nm, wherein the stripping force between the primer layer and the base film is about 12N/2.5 cm;
12. coating nano silver wire conductive ink on the surface of the bottom coating, and drying for 30s at 110 ℃ to form a nano silver wire conductive layer with the thickness of about 100 nm;
13. coating the surface of the nano silver wire conducting layer with coating liquid with the UV irradiation viscosity reduction function again, drying and curing for 2min at 120 ℃, wherein the coating liquid uniformly permeates into the conducting layer in the drying and curing process and directly reaches the interface between the conducting layer and the bottom coating to form a protective layer with the thickness of 100 +/-10 nm, so that the nano silver wire transparent conducting film taking the base film as the substrate is obtained;
step 2, patterning the nano silver wire transparent conductive film taking the base film as the substrate
21. Setting a mask (chrome plate), wherein the mask comprises a light-transmitting area and a shielding area to form a required pattern, the light-transmitting area corresponds to a non-pattern area of the required conductive film pattern, and the shielding area corresponds to a pattern area;
attaching the mask plate to the surface of the protective layer, and then carrying out UV exposure (500 mJ/cm)2UV irradiation under energy for 10s) to reduce the peeling force between the exposed area of the conductive film and the base film to less than 2N/2.5 cm;
22. arranging a concave-convex roller, wherein the convex surface of the concave-convex roller corresponds to the exposed area of the conductive film, and the concave surface of the concave-convex roller corresponds to the non-exposed area, and the convex surface of the concave-convex roller is uniformly coated with bonding glue by the method in the embodiment 1; sticking and removing the conductive film in the exposed area on the base film through the concave-convex roller, namely forming the conductive film with the required pattern on the base film;
step 3, transferring the patterned conductive film on the base film
31. UV irradiation (1000 mJ/cm) is performed on the patterned conductive film on the base film2UV irradiation at energy for 10s) to reduce the peeling force between the patterned conductive film and the base film to less than 2N/2.5cm while the protective layer and the undercoat layer of the conductive film are reacted and integrated at the interface of the undercoat layer and the conductive layer;
32. the flexible transparent optical adhesive in the embodiment 1 is attached to the surface of the conductive film, and then the base film is torn off, that is, the conductive film is transferred to the surface of the flexible transparent optical adhesive, so that the patterned nano silver wire transparent conductive film taking the flexible transparent optical adhesive as the substrate is prepared.
Example 3
This example was carried out in the same manner as in example 2 except that the coating liquid having UV irradiation anti-sticking function was prepared by the following method: under a dustless and yellow light environment, 972g of a solvent (a mixture of ethyl acetate, butanol and cyclohexanone in a mass ratio of 1:1: 1), 20g of a UV resin (a mixture of CN9013NS and CN9010 in a mass ratio of 1: 1), 4g of a UV monomer (trimethylolpropane triacrylate) and 2g of hydroxyethyl acrylate are sequentially added into a dispersion tank, and mechanical stirring is carried out at the speed of 1000r/min for 30 min; then, 1g of photoinitiator (photoinitiator 184) and 1g of cross-linking agent (1, 6-hexamethylene diisocyanate) are sequentially added, and stirring is continued for 10min, so that the coating liquid with the UV irradiation viscosity reduction function is prepared.
Example 4
This example was carried out in the same manner as in example 2 except that the coating liquid having UV irradiation anti-sticking function was prepared by the following method: under the environment of no dust and yellow light, 972g of a solvent (a mixture of ethyl acetate, butanol and cyclohexanone in a mass ratio of 1:1: 1), 20g of UV resin (a mixture of CN9013NS and CN9010 in a mass ratio of 1: 1), 4g of a UV monomer (pentaerythritol tetraacrylate) and 2g of hydroxyethyl acrylate are sequentially added into a dispersion cylinder, and mechanical stirring is carried out at the speed of 1000r/min for 30 min; then, 1g of photoinitiator (photoinitiator 184) and 1g of cross-linking agent (1, 6-hexamethylene diisocyanate) are sequentially added, and stirring is continued for 10min, so that the coating liquid with the UV irradiation viscosity reduction function is prepared.
Example 5
This example was carried out in the same manner as in example 2 except that the coating liquid having UV irradiation anti-sticking function was prepared by the following method: under the environment of no dust and yellow light, 972g of a solvent (a mixture of ethyl acetate, butanol and cyclohexanone in a mass ratio of 1:1: 1), 20g of UV resin (a mixture of CN9013NS and CN9010 in a mass ratio of 1: 1), 4g of a UV monomer (pentaerythritol tetraacrylate) and 2g of hydroxyethyl acrylate are sequentially added into a dispersion cylinder, and mechanical stirring is carried out at the speed of 1000r/min for 30 min; then, 1g of photoinitiator (photoinitiator 819) and 1g of cross-linking agent (1, 6-hexamethylene diisocyanate) are sequentially added, and stirring is continued for 10min, so that the coating liquid with the UV irradiation viscosity-reducing function is prepared.
Comparative example 1
In this embodiment, a transparent conductive film with a desired pattern of silver nanowires is prepared by the same method as in embodiment 2, except that the flexible transparent optical adhesive used in step 32 is optical adhesive 3M 8146-5.
As shown in fig. 2, a layer of corresponding optical adhesive is further bonded on the top layer of the patterned flexible nano silver wire transparent conductive film with the flexible transparent optical adhesive as the substrate obtained in examples 2 to 5 and comparative example 1, and then performance tests are performed, wherein the performance ratio is shown in table 1.
Table 1: examples 2-example 5 Performance comparison with comparative example 1
From the comparison results of examples 2 to 5 and comparative example 1, it can be seen that the patterned nano silver wire conductive films manufactured by using the flexible transparent optical adhesive of example 1 and different base coatings have better matching performance and excellent aging resistance, and the flexible transparent optical adhesive of example 1 has better flexibility compared with 3M8146-5 with larger market amount.
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for manufacturing a nano silver wire transparent conductive film with customizable patterns is characterized by comprising the following steps:
step 1, arranging a nano silver wire transparent conductive film taking a base film as a substrate
11. Coating a coating liquid with a UV irradiation viscosity reduction function on the surface of the base film, drying and curing to form a bottom coating;
12. coating nano silver wire conductive ink on the surface of the bottom coating and drying to form a nano silver wire conductive layer;
13. coating the coating liquid with the UV irradiation viscosity reduction function on the surface of the nano silver wire conductive layer again, drying and curing, wherein the coating liquid uniformly permeates into the conductive layer in the drying and curing process and reaches the interface between the conductive layer and the bottom coating to form a protective layer, so that the nano silver wire transparent conductive film taking the base film as the substrate is obtained;
step 2, patterning the nano silver wire transparent conductive film taking the base film as the substrate
21. Setting a mask plate, wherein the mask plate comprises a light-transmitting area and a shielding area to form a required pattern, the light-transmitting area corresponds to a non-pattern area of the required conductive film pattern, and the shielding area corresponds to a pattern area;
attaching the mask plate to the surface of the protective layer, and then carrying out UV exposure to reduce the stripping force between the exposure area of the conductive film and the base film;
22. arranging a concave-convex roller, wherein the convex surface of the concave-convex roller corresponds to an exposure area of the conductive film, the concave surface of the concave-convex roller corresponds to a non-exposure area, and bonding glue is uniformly coated on the convex surface of the concave-convex roller;
sticking and removing the conductive film in the exposed area on the base film through the concave-convex roller, namely forming the conductive film with the required pattern on the base film;
step 3, transferring the patterned conductive film on the base film
31. Carrying out UV irradiation on the patterned conductive film on the base film to reduce the stripping force between the patterned conductive film and the base film, and simultaneously enabling the protective layer and the bottom coating layer of the conductive film to react and be connected into a whole at the interface of the bottom coating layer and the conductive layer;
32. and (3) attaching flexible transparent optical adhesive to the surface of the conductive film, and tearing off the base film, namely transferring the conductive film to the surface of the flexible transparent optical adhesive to obtain the patterned nano silver wire transparent conductive film taking the flexible transparent optical adhesive as the substrate.
2. The production method according to claim 1, wherein the coating liquid having a UV irradiation viscosity reduction function comprises, in mass percent:
3. the method of manufacturing according to claim 2, wherein: the hydroxyl acrylate is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and caprolactone acrylate; the cross-linking agent is one of aliphatic diisocyanate; the molar ratio of hydroxyl in the hydroxyl acrylate to isocyanate in the cross-linking agent is 1: 1.1-1.3;
the UV resin is a mixture of any two of polyurethane acrylate WDS-4500, WDS-9500, WDS-9568, WDS-9700, DSM230A2, DSM2421, U400-1, CN9013NS, CN9010, DM87A and DM588 in a mass ratio of 1: 1;
the UV monomer is one of trimethylolpropane triacrylate, ditrimethyloltetraacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate;
the photoinitiator is one or a mixture of two of a photoinitiator 1173, a photoinitiator 184, a photoinitiator 2959, a photoinitiator TPO and a photoinitiator 819 which are mixed according to any ratio;
the solvent is a mixture of a solvent A, a solvent B and a solvent C according to a mass ratio of 1:1:1, wherein: the solvent A is acetone, butanone, ethyl acetate or methyl acetate, the solvent B is n-propanol, isopropanol, butanol, isobutanol or butyl acetate, and the solvent C is cyclohexanone, cyclohexanol, ethylene glycol, 1, 3-propanediol or 1, 3-butanediol.
4. The method for manufacturing the adhesive tape according to claim 1, wherein the adhesive tape in the step 22 comprises the following components in percentage by mass:
5. the manufacturing method of claim 1, wherein the flexible transparent optical adhesive in step 32 comprises the following components in percentage by mass:
6. the manufacturing method according to claim 4 or 5, characterized in that: the synthesis of the polyurethane acrylic prepolymer comprises the following steps:
(a) dehydrating raw materials:
carrying out high-temperature vacuum-pumping dehydration treatment on raw materials of polyol, isocyanate and hydroxyl acrylate, wherein the treatment conditions are as follows: the temperature is 80-120 ℃, the vacuum degree is 0.05-0.1MPa, and the time is 2-4 h;
the polyhydric alcohol is one of PEG400, PEG-1000, PPG-400, PPG-1000 and PPG-2000 and polyoxypropylene triol-600 according to the hydroxyl molar ratio of 3-5: 1 mixing the components; the isocyanate is one of 1, 6-hexamethylene diisocyanate and trimethyl-1, 6-hexamethylene diisocyanate; the hydroxy acrylic ester is one of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
(b) polyol and isocyanate reaction:
in N2Under the environment protection, adding the isocyanate subjected to dehydration treatment into a flask, mechanically stirring at the speed of 200-500r/min, simultaneously heating to 60-70 ℃, and then dropwise adding the polyol subjected to dehydration treatment into the flask at a constant speed for 2 hours; after the dropwise addition is finished, continuously preserving heat, stirring and reacting until the-NCO content reaches a theoretical value and keeps unchanged, and stopping the reaction to obtain a first-step product;
wherein the molar ratio of-NCO in the isocyanate subjected to dehydration treatment to-OH in the polyol subjected to dehydration treatment is 1.1:1 so as to ensure that the-OH can be reacted completely;
(c) double bond reaction:
keeping the original mechanical stirring speed of the product of the first step, heating to 80 ℃, adding p-hydroxyanisole, dropwise adding the dehydrated hydroxyl acrylate into a flask at a constant speed for 1 h; after the dropwise addition is finished, continuously preserving heat, stirring and reacting until the-NCO content is 0, cooling to room temperature after the reaction is finished, and discharging to obtain a polyurethane acrylic prepolymer;
wherein: the mol ratio of-NCO in the first step product to-OH in the hydroxyl acrylic ester is 1:1.1, so as to ensure that-NCO can completely react; the addition amount of the p-hydroxyanisole accounts for 0.2% of the total mass of the isocyanate subjected to dehydration treatment in the step (b) and the polyol subjected to dehydration treatment.
7. The manufacturing method according to claim 4 or 5, characterized in that: the active diluent is one of BDDA and HDDA and TMP (EO)6DA、TMP(EO)9DA and TMP (EO)15A mixture formed by mixing one of DA according to the mass ratio of 5-10: 1;
the photoinitiator is one of a photoinitiator 173, a photoinitiator 184 and a photoinitiator 754;
the tackifying resin is Piccotac 1095-N.
8. The method of manufacturing according to claim 5, wherein: the light stabilizer is one of light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer 944;
the antioxidant is one of antioxidant 168, antioxidant 245, antioxidant 1010, antioxidant 1024, antioxidant 1076, antioxidant 1098 and antioxidant 1135;
the ultraviolet absorbent is a mixture formed by mixing UV-531 and one of UV-P, UV-234, UV-320, UV-326, UV-327 and UV-320 in a mass ratio of 1: 1;
the infrared absorbent is IRA HSYP 03.
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