CN107345096B - Nano silver wire-silver complex compound conductive ink and preparation method of transparent conductive film thereof - Google Patents
Nano silver wire-silver complex compound conductive ink and preparation method of transparent conductive film thereof Download PDFInfo
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Abstract
The invention discloses nano silver wire-silver complex compound conductive ink which comprises 80-95 wt% of nano silver wire ink and 5-20 wt% of silver complex compound ink; the nano silver wire ink comprises nano silver wires and a dispersing agent, wherein the nano silver wires account for 0.5-5% by weight, and the dispersing agent accounts for 95-99.5% by weight; the silver complex ink comprises 5-10 wt% of silver complex and 90-95 wt% of stabilizer. The invention can prolong the storage life of the composite conductive ink, is easy for industrialized production, improves the conductivity and the uniformity of the composite conductive ink after film forming, can effectively reduce the speed of separating out the nano silver wires in the nano silver wire ink, and prevents the nano silver wires from agglomerating and settling; meanwhile, the resistance uniformity of the nano silver wire after film formation can be improved.
Description
Technical Field
The invention relates to the technical field of liquid crystal, in particular to a conductive ink based on a nano silver wire and a preparation method of a transparent conductive film of the conductive ink.
Background
The transparent conductive film is a flexible film with high light transmittance and conductive property in a visible light range, and can be applied to various fields such as touch control, display, photovoltaics, illumination, wearable electronic devices and the like. Currently, the ITO conductive film occupies 90% of the market of the transparent conductive film, but it has problems of high price, poor flexibility, high energy consumption and high resistance, so that a new alternative technology applicable to bending applications and large-size applications is urgently needed.
The nano silver wire transparent conductive film realizes the conductive function by forming a network structure by the cross interpenetration of the nano silver wires, and transmits light through meshes in the network structure. The silver nanowire transparent conductive film has become a most promising transparent conductive film for replacing ITO (indium tin oxide) because of the advantages of large-area roll-to-roll processing technology, high yield, low cost, low resistance, high light transmittance, low haze, high flexibility and the like.
The main factors influencing the performance of the product of the nano silver wire transparent conductive film are the formula and the film forming process of the nano silver wire ink. The nano silver wire has high surface activity, and is easy to agglomerate and settle when dispersed in a solvent, so that on one hand, the prepared nano silver wire ink has poor stability and short storage life, and is difficult to realize industrial production; on the other hand, the film formed by the nano silver wire ink has poor resistance uniformity and can not meet the application requirements. In order to solve these problems, technicians have adopted many methods to adjust the formula of the silver nanowire ink to solve the problems of agglomeration and sedimentation of the silver nanowires and poor uniformity of film-forming resistance. If the high polymer is added into the nano silver wire ink, the high polymer can effectively coat the surface of the nano silver wire, so that the nano silver wire is prevented from being agglomerated due to mutual contact, the stability of the nano silver wire ink can be improved, but the resistance of the nano silver wire ink after film forming can be obviously increased due to the addition of the high polymer; for example, the addition of a surfactant to the silver nanowire ink can improve the resistance uniformity of the silver nanowire ink after film formation, but cannot improve the stability of the silver nanowire ink, and also can affect the resistance of the silver nanowire ink after film formation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the problems and the defects of the existing nano silver wire ink, the nano silver wire-silver complex compound conductive ink is provided.
The invention solves another technical problem of providing a preparation method of the nano silver wire transparent conductive film with high stability, high conductivity and high resistance uniformity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the nano silver wire-silver complex compound conductive ink comprises 80-95 wt% of nano silver wire ink and 5-20 wt% of silver complex compound ink; the nano silver wire ink comprises a nano silver wire and a dispersing agent, wherein the nano silver wire accounts for 0.5-5 wt%, and the dispersing agent accounts for 95-99.5 wt%; the silver complex ink comprises a silver complex and a stabilizer, wherein the silver complex accounts for 5-10 wt%, and the stabilizer accounts for 90-95 wt%.
The silver complex compound conductive ink can be selected from AgSCN, AgOCN, AgOCNBr and AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl、Ag(NH3)2Any one of CN.
The diameter of the nano silver wire is 10-150 nm, and the length of the nano silver wire is 2-200 mu m.
The stabilizer is an organic solvent with a boiling point of 150-280 ℃, and is selected from any one of terpineol, 2-phenoxyethanol, glycerol, octanedithiol or ethylene glycol.
In the nano silver wire-silver complex compound conductive ink, the dispersing agent is a solvent with a boiling point of 35-120 ℃, and is selected from any one or two of water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene, butanone, methanol, chloroform or dichloromethane.
The preparation method of the nano silver wire transparent conductive film comprises the following steps:
(1) carrying out corona or plasma treatment on the flexible transparent substrate;
(2) coating the nano silver wire-silver complex compound conductive ink of claim 1 on the surface of a flexible transparent substrate, and thermally curing to form a nano silver wire-silver complex compound conductive layer;
(3) and coating the protective layer coating liquid on the surface of the nano silver wire-silver complex compound conductive layer, and forming a protective layer after thermosetting or photocuring to obtain the nano silver wire transparent conductive film.
According to the preparation method of the transparent conductive film, the flexible transparent substrate is any one of polyethylene naphthalate, polycarbonate, polyacrylate, polydimethylsiloxane, polymethyl methacrylate, polyimide and polyethylene terephthalate, and the thickness of the flexible transparent substrate is 7.5-225 micrometers.
According to the preparation method of the transparent conductive film, the thickness of the nano silver wire-silver complex compound conductive layer is 15-300 nm.
According to the preparation method of the transparent conductive film, the protective layer is a film formed by any one or a mixture of two of polyvinyl alcohol, polyurethane, polyester, acrylic resin, polythiophene and organic silicon modified resin, and the thickness of the protective layer is 20-150 nm.
According to the preparation method of the transparent conductive film, the coating mode is slot coating, slide coating, micro-gravure coating or scraper coating.
Advantageous effects
Compared with the prior art, the silver complex compound ink is added into the nano silver wire ink to form the nano silver wire-silver complex compound conductive ink, and the beneficial effects are as follows:
(1) the silver complex has the dispersibility of organic complex groups and the conductivity of inorganic silver, effectively prevents the occurrence of agglomeration and sedimentation of the nano silver wires, obviously improves the stability of the nano silver wire conductive ink, prolongs the storage life of the nano silver wire conductive ink, and is easy for industrial production. Meanwhile, the silver complex can effectively connect the nano silver wires into a network structure, and the conductivity and the uniformity of the film formed by the silver complex are improved.
(2) Because the stabilizing agent in the silver complex ink is an organic solvent with a high boiling point (150 ℃), the speed of separating out the nano silver wires in the nano silver wire ink can be effectively reduced, and the nano silver wires are prevented from agglomerating and settling; meanwhile, the rapid volatilization of the low-boiling-point (<120 ℃) solvent dispersant in the film forming process of the nano silver line ink can be inhibited, and the resistance uniformity of the nano silver line after film forming is improved.
(3) The nano silver wire transparent conductive film can adopt a roll-to-roll preparation process, is more suitable for large-area continuous industrial production, and has simple process and low manufacturing cost.
Detailed Description
In order to make the technical solution of the present invention more clear, the embodiments of the present invention will be described in further detail, but these examples are only for explaining the present invention and do not limit other embodiments of the present invention.
The nano silver wire-silver complex compound conductive ink comprises 80-95 wt% of nano silver wire ink and 5-20 wt% of silver complex compound ink; the nano silver wire ink comprises a nano silver wire and a dispersing agent, wherein the nano silver wire accounts for 0.5-5 wt%, and the dispersing agent accounts for 95-99.5 wt%; the silver complex ink comprises a silver complex and a stabilizer, wherein the silver complex accounts for 5-10 wt%, and the stabilizer accounts for 90-95 wt%.
The diameter of the nano silver wire contained in the nano silver wire ink is 10-150 nm, preferably 15-50 nm, if the silver wire is too thin, the surface activity is extremely high, and the silver wire are easy to be wound and agglomerated; if the silver wire is too thick, the optical properties of the formed conductive film may be degraded. The length of the nano silver wires is 2-200 mu m, preferably 10-50 mu m, if the silver wires are too short, the silver wires cannot be lapped with each other, and a conductive network cannot be formed; if the silver wires are too long, the silver wires are easily twisted and broken. The weight percentage of the nano silver wire is 0.5-5%, and if the content is lower than 0.5%, the resistance of the formed transparent conductive film is too high; if the content is higher than 5%, the nano silver wire is easy to agglomerate due to high surface activity. The dispersing agent contained in the nano silver wire ink is a solvent with a boiling point of 35-120 ℃, and preferably one or two of water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene, butanone, methanol, chloroform and dichloromethane. The weight percentage of the dispersing agent is 95-99.5%, and the dispersing agent is used for adjusting the concentration and viscosity of the nano silver wires.
The silver complex suitable for the silver complex ink of the present invention may be selected from the group consisting of AgSCN, AgOCN, AgOCNBr, AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl、Ag(NH3)2Any one of CN. The silver complex accounts for 5-10 wt%, and if the content is lower than 5%, the contained organic complex group can not well coat the nano silver wire, so that the agglomeration and sedimentation of the nano silver wire can not be prevented; when the content is more than 10%, the resistance and optical properties of the formed transparent conductive film are affected. The stabilizer suitable for the silver complex ink of the present invention is an organic solvent having a boiling point of 150 to 280 ℃, and preferably any one of terpineol, 2-phenoxyethanol, glycerol, octanedithiol, and ethylene glycol. The weight percentage of the stabilizer is 90-95%, and if the content of the stabilizer is less than 90%, the silver complex cannot be well dispersed; if the content is more than 95%, the film is not easily volatilized due to its too high boiling point, and the film forming rate is affected.
A preparation method of a nano silver wire transparent conductive film comprises the following steps:
(1) carrying out corona or plasma treatment on the flexible transparent substrate;
(2) coating the nano silver wire-silver complex compound conductive ink of claim 1 on the surface of a flexible transparent substrate by a slot coating method, a slide coating method, a micro-gravure coating method or a blade coating method, and forming a nano silver wire-silver complex compound conductive layer after thermal curing;
(3) and coating the protective layer coating liquid on the surface of the nano silver wire-silver complex compound conductive layer by a slit coating method, a slide coating method, a micro-gravure coating method or a scraper coating method, and forming a protective layer after thermosetting or photocuring to obtain the nano silver wire transparent conductive film.
The flexible transparent substrate suitable for the present invention requires a certain heat resistance because if the flexible transparent substrate is not consistent with the thermal expansion dimensional changes of the silver nanowire-silver complex composite layer and the protective layer during the later processing, it will cause cracking and peeling of the two. Therefore, the flexible transparent substrate of the present invention is selected from a resin film with a small linear expansion coefficient, preferably less than 40 ppm/DEG C, such as any one of polyethylene naphthalate (PEN), Polycarbonate (PC), Polyacrylate (PVA), Polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), Polyimide (PI), and polyethylene terephthalate (PET), and preferably, the flexible transparent substrate is selected from polyethylene terephthalate PET with low price and excellent performance. The thickness of the flexible transparent base substrate is 7.5-225 microns, preferably 12-188 microns, and if the thickness is too thin, the mechanical strength of the base material is too low, so that the manufacturing of a nano silver wire-silver complex compound layer and a protective layer is not facilitated; if the thickness is too large, the transmittance is too low and the flexibility is deteriorated. The total light transmittance of the flexible transparent substrate is required to be more than 80%, preferably more than 85%, and the haze is required to be less than 3%, preferably less than 1.5%, so that the nano silver wire transparent conductive film with excellent optical performance is obtained. Before coating the silver wire-silver complex compound conductive ink, the flexible transparent substrate needs to be subjected to corona or plasma treatment, and the surface energy is required to be more than 32dyn/cm, preferably more than 34 dyn/cm.
The coating mode of the nano silver wire-silver complex compound conductive ink can be any one of slot coating, slide coating, micro-gravure coating or scraper coating, and slot coating or slide coating is preferred, because the slot coating or the slide coating is a non-contact coating mode, the nano silver wire is not easy to agglomerate and separate out and generate stripe defects when the nano silver wire-silver complex compound conductive ink is used. After the nano silver wire-silver complex compound conductive ink is coated on a flexible transparent substrate, heating and curing at 30-150 ℃ are carried out, so that a nano silver wire-silver complex compound conductive layer is formed, the thickness is 15-300 nm, preferably 50-150 nm, and if the thickness is too thin, the conductivity of the film is poor; if too thick, the film will have poor optical properties.
The protective layer is arranged on the surface of the nano silver wire-silver complex compound conductive layer. Because the surface activity of the nano silver wire is extremely high, on one hand, the nano silver wire is easily oxidized by oxygen in the air environment, so that the resistance of the nano silver wire layer is increased; on the other hand, water vapor permeates into the nano silver wire layer, and can be electrolyzed to form hydrogen ions and hydroxyl ions, so that silver migration occurs, and the service life of the nano silver wire layer is obviously shortened. Therefore, a protective layer is required to be coated on the surface of the nano silver wire-silver complex compound conductive layer to complete the protection of the nano silver wire-silver complex compound conductive layer, so as to improve the high temperature oxidation resistance and moisture resistance of the nano silver wire transparent conductive film. Meanwhile, the optical performance of the nano silver wire transparent conductive film can be improved. The protective layer material can be selected from one or two mixtures of polyvinyl alcohol, polyurethane, polyester, acrylic resin, polythiophene or organic silicon modified resin. The coating mode can be any one of slot coating, slide coating, micro-gravure coating or scraper coating, and the slot coating or slide coating is preferred, because the slot coating and the slide coating are non-contact coating modes, the defects of scratch, abrasion, scratch and the like on the lower nano silver wire-silver complex compound conductive layer can not be caused when the protective material is coated. The thickness of the protective layer is 20-150 nm, preferably 30-100 nm. If the protective layer is too thin, the nano silver wire-silver complex compound conductive layer cannot be completely covered, and the barrier property of the film cannot be increased; if the film layer is too thick, the resistance of the silver nanowire-silver complex compound conductive layer is increased, and the light transmittance of the film is reduced.
The present invention will be described in detail with reference to examples.
Example 1
The first step is as follows: processing flexible transparent substrates
PET with the thickness of 100 mu m is selected, the breadth is 550mm, the total light transmittance is 91.3 percent, the haze is 0.34 percent, and the surface energy is 36dyn/cm after 0.8kV voltage corona.
The second step is that: preparation of nano silver wire-silver complex compound layer
Preparing the nano silver wire-silver complex compound conductive ink: 1) dispersing the nano silver wires with the wire diameter of 25nm and the length of 15 mu m in an ethanol solvent to prepare 8L of nano silver wire ink with the concentration of 0.5 wt%; 2) dispersing silver complex AgSCN in terpineol as a stabilizer to prepare 2L of silver complex ink with the concentration of 10 wt%; 3) then 8L of nano silver wire ink and 2L of silver complex ink are mixed and stirred for 0.5h to form the nano silver wire-silver complex conductive ink.
Coating the nano silver wire-silver complex conductive ink: and (3) coating the prepared nano silver wire-silver complex conductive ink on the surface of PET (polyethylene terephthalate) by using a strip and seam coating machine at the speed of 5m/min, and drying at 80 ℃ to form a 100 nm-thick nano silver wire-silver complex conductive layer.
The third step: preparation of the protective layer
Preparing a protective layer coating liquid: 0.5g of a polyurethane resin was dispersed in an ethyl acetate solvent to form a polyurethane coating liquid having a solid content of 2%.
Coating a protective layer coating liquid: and coating a layer of polyurethane coating liquid on the surface of the prepared PET/nano silver wire-silver complex compound layer in a roll-to-roll manner in a strip-and-seam coating manner, and drying at 85 ℃ to form a protective layer with the thickness of 80 nm.
Example 2
The first step is as follows: processing flexible transparent substrates
PC with the thickness of 125 mu m, the breadth of 560mm, the total light transmittance of 88.2 percent, the haze of 0.78 percent and the surface energy of 38dyn/cm after 0.6kV voltage corona are selected.
The second step is that: preparation of nano silver wire-silver complex compound layer
Preparing the nano silver wire-silver complex compound conductive ink: 1) dispersing the nano silver wire with the wire diameter of 50nm and the length of 10 mu m in a water solvent to prepare 8.5L of nano silver wire ink with the concentration of 1 wt%; 2) dispersing silver complex AgOCN in stabilizer 2-phenoxyethanol to prepare 1.5L of silver complex ink with 8 wt%; 3) then 8.5L of nano silver wire ink and 1.5L of silver complex ink are mixed and stirred for 0.5h to form the nano silver wire-silver complex conductive ink.
Coating the nano silver wire-silver complex conductive ink: and (3) coating the prepared nano silver wire-silver complex conductive ink on the surface of the PC at the speed of 6m/min by using a slide coater, and drying at 105 ℃ to form a 50 nm-thick nano silver wire-silver complex conductive layer.
The third step: preparation of the protective layer
Preparing a protective layer coating liquid: 0.5g of the silicone-modified resin was dispersed in an isopropyl alcohol solvent to form a silicone-modified resin coating liquid having a solid content of 2.5%.
Coating a protective layer coating liquid: and coating a layer of organic silicon modified resin coating liquid on the surface of the prepared PC/nano silver wire-silver complex compound layer in a gradient flow coating mode in a roll-to-roll mode, and drying at 65 ℃ to form a protective layer with the thickness of 100 nm.
Example 3
The first step is as follows: processing flexible transparent substrates
The surface energy is 34dyn/cm after 1kV plasma treatment by selecting PI with the thickness of 12 mu m, the breadth is 540mm, the total light transmittance is 89.5 percent, the haze is 0.53 percent.
The second step is that: preparation of nano silver wire-silver complex compound layer
Preparing the nano silver wire-silver complex compound conductive ink: 1) dispersing the nano silver wires with the wire diameter of 15nm and the length of 30 mu m in isopropanol solvent to prepare 2 wt% of nano silver wire ink 9L; 2) dispersing silver complex AgOCNBr in stabilizer glycerol to prepare 1L of silver complex ink with the concentration of 6.5 wt%; 3) then 9L of nano silver wire ink and 1L of silver complex ink are mixed and stirred for 0.5h to form the nano silver wire-silver complex conductive ink.
Coating the nano silver wire-silver complex conductive ink: and (3) coating the prepared nano silver wire-silver complex conductive ink on the surface of the PI at the speed of 4m/min by adopting a micro-gravure coating machine, and drying at 85 ℃ to form a 150 nm-thick nano silver wire-silver complex conductive layer.
The third step: preparation of the protective layer
Preparing a protective layer coating liquid: 0.5g of polyacrylic resin was dispersed in an ethanol solvent to form a polyacrylic resin coating liquid having a solid content of 3%.
Coating a protective layer coating liquid: and coating a layer of polyacrylic resin coating liquid on the surface of the prepared PI/nano silver wire-silver complex compound layer in a roll-to-roll manner in a scraper mode, and drying at 55 ℃ to form a protective layer with the thickness of 60 nm.
Example 4
The first step is as follows: processing flexible transparent substrates
The surface energy of the product after 1kV corona treatment is 42dyn/cm by selecting PEN with the thickness of 188 microns, the width of 550mm, the total light transmittance of 90.8 percent and the haze of 0.67 percent.
The second step is that: preparation of nano silver wire-silver complex compound layer
Preparing the nano silver wire-silver complex compound conductive ink: 1) dispersing the nano silver wire with the wire diameter of 30nm and the length of 50 mu m in an acetone solvent to prepare 9.5L of nano silver wire ink with the concentration of 4 wt%; 2) silver complex AgSCSN3Dispersing in stabilizer octanedithiol to prepare 0.5L silver complex ink with the concentration of 5 wt%; 3) then 9.5L of nano silver wire ink and 0.5L of silver complex ink are mixed and stirred for 0.5h to form nano silver wire-silver complex ink.
Coating the nano silver wire-silver complex compound conductive ink: and (3) coating the prepared nano silver wire-silver complex conductive ink on the surface of PEN at the speed of 6m/min by adopting a scraper coater, and drying at 90 ℃ to form a nano silver wire-silver complex conductive layer with the thickness of 200 nm.
The third step: preparation of the protective layer
Preparing a protective layer coating liquid: 0.5g of polyvinyl alcohol was dispersed in an ethyl acetate solvent to form a polyvinyl alcohol coating liquid having a solid content of 1.5%.
Coating a protective layer coating liquid: and coating a layer of polyvinyl alcohol coating liquid on the surface of the prepared PEN/nano silver wire-silver complex compound layer in a roll-to-roll manner in a strip seam coating manner, and drying at 85 ℃ to form a protective layer with the thickness of 30 nm.
Example 5
The first step is as follows: processing flexible transparent substrates
PDMS with the thickness of 75 μm, the breadth of 560mm, the total light transmittance of 91.2 percent, the haze of 0.47 percent and the surface energy of 46dyn/cm after 0.8kV corona treatment are selected.
The second step is that: preparation of nano silver wire-silver complex compound layer
Preparing the nano silver wire-silver complex compound conductive ink: 1) dispersing the nano silver wires with the wire diameter of 80nm and the length of 100 mu m in ethyl acetate solvent to prepare 9.2L of nano silver wire ink with the concentration of 5 wt%; 2) silver complex Ag4Fe(CM)6Dispersing in ethylene glycol as stabilizer to obtain 0.8L silver complex ink with concentration of 5.5 wt%; 3) then, 9.2L of nano silver wire ink and 0.8L of silver complex ink are mixed and stirred for 0.5h to form the coating nano silver wire-silver complex compound conductive ink.
Coating the nano silver wire-silver complex compound conductive ink: and (3) coating the prepared coating nano silver wire-silver complex compound conductive ink on the surface of PDMS (polydimethylsiloxane) by adopting a micro-gravure coating machine at the speed of 4m/min, and drying at 65 ℃ to form a nano silver wire layer with the thickness of 300 nm.
The third step: preparation of the protective layer
Preparing a protective layer coating liquid: 0.5g of polythiophene was dispersed in water, and 0.1g of a surfactant was further added to form a polythiophene coating liquid having a solid content of 2.5%.
Coating a protective layer coating liquid: and coating a layer of polythiophene coating liquid on the surface of the prepared PDMS/nano silver wire-silver complex compound layer in a gradient flow coating mode in a roll-to-roll mode, and drying at 105 ℃ to form a protective layer with the thickness of 50 nm.
Comparative example 1
The first step is as follows: processing flexible transparent substrates
The same as in example 1.
The second step is that: preparing a layer of silver nanowires
Preparing nano silver wire ink: the nano silver wire with the wire diameter of 25nm and the length of 15 mu m is dispersed in an ethanol solvent to prepare 8L of nano silver wire ink with the concentration of 0.5 wt%.
Coating the nano silver wire ink: and (3) coating the prepared nano silver wire ink on the surface of PET (polyethylene terephthalate) by adopting a strip and seam coating machine at the speed of 5m/min, and drying at 80 ℃ to form a nano silver wire layer with the thickness of 100 nm.
The third step: preparation of the protective layer
The same as in example 1.
The square resistance, the uniformity, the total light transmittance, the haze, the yellowness value, and the high temperature resistance and the resistance to wet heat aging of the silver nanowire transparent conductive films prepared in examples 1 to 5 and comparative example 1 are shown in table 1.
(1) Square resistance (R) test
Conditions are as follows: using an ST-21 type square resistance tester, the temperature is 23 +/-5 ℃, and the relative humidity is as follows: (50. + -. 10)% RH.
(2) All light transmittance (T) and haze (H) measurements
Conditions are as follows: a light transmittance/haze determinator is adopted, and the light transmittance and haze of the transparent plastic are determined according to the standard GB/T2041-: (50. + -. 10)% RH.
(3) Yellowness index (b) test
Conditions are as follows: adopting a colorimeter, referring to a standard GB/T2409-1980 plastic yellow index test method, wherein the temperature is 23 +/-5 ℃, and the relative humidity is as follows: (50. + -. 10)% RH.
(4) High temperature resistance test
Conditions are as follows: the temperature is 80 ℃ and the time is 240h, and the standard environment for regulating and testing the state of the GB/T2918-. Resistance change (Δ R) ═ RAfter aging-RBefore aging)/RBefore aging(ii) a Change in light transmittance (Δ T) ═ TAfter aging-TBefore aging)/TBefore aging(ii) a Haze change (. DELTA.H) (. H)After aging-HBefore aging)/HBefore aging(ii) a Change in yellowness (. DELTA.b) (. b)After aging-b*Before aging)/b*Before aging。
(5) Resistance to wet heat aging test
Conditions are as follows: the humidity is 95% RH, the temperature is 60 ℃, and the time is 240h, referring to the standard environment of GB/T2918-. Resistance change (Δ R) ═ RAfter aging-RBefore aging)/RBefore aging(ii) a Change in light transmittance (Δ T) ═ TAfter aging-TBefore aging)/TBefore aging(ii) a Haze change (. DELTA.H) (. H)After aging-HBefore aging)/HBefore aging(ii) a Change in yellowness (. DELTA.b) (. b)After aging-b*Before aging)/b*Before aging。
TABLE 1 test data tables for examples 1-5 and comparative example 1
As can be seen from the data in table 1, the silver nanowire transparent conductive films of examples 1 to 5 have lower resistance, better uniformity, and significantly excellent high temperature resistance, wet heat resistance, and yellowing resistance, compared to the silver nanowire transparent conductive film formed without adding silver complex ink in comparative example 1.
Claims (7)
1. The utility model provides a nanometer silver line transparent conductive film, its interlaminar structure from top to bottom is in proper order: the protective film, the nano silver wire-silver complex compound conductive layer and the flexible transparent substrate are characterized in that the nano silver wire-silver complex compound conductive layer is formed by coating nano silver wire-silver complex compound conductive ink on the surface of the flexible transparent substrate and thermally curing the coated nano silver wire-silver complex compound conductive ink;
the composite conductive ink comprises 80-95 wt% of nano silver wire ink and 5-20 wt% of silver complex compound ink;
the nano silver wire ink comprises a nano silver wire and a dispersing agent, wherein the nano silver wire accounts for 0.5-5 wt%, and the dispersing agent accounts for 95-99.5 wt%;
the silver complex ink comprises a silver complex and a stabilizer, wherein the silver complex accounts for 5-10 wt%, and the stabilizer accounts for 90-95 wt%;
the silver complex is selected from AgSCN, AgOCN, AgOCNBr, AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl or Ag (NH)3)2Any one of CN;
the stabilizer is an organic solvent with a boiling point of 150-280 ℃, and is selected from any one of terpineol, 2-phenoxyethanol, glycerol, octanedithiol or ethylene glycol;
the protective film is a film formed by any one or a mixture of two of polyvinyl alcohol, polyurethane, polyester, acrylic resin, polythiophene and organic silicon modified resin, and the thickness of the protective film is 20-150 nm;
the flexible transparent substrate is selected from any one of polyethylene naphthalate, polycarbonate, polyacrylate, polydimethylsiloxane, polymethyl methacrylate, polyimide or polyethylene terephthalate, the linear expansion coefficient is less than 40 ppm/DEG C, the total light transmittance of the flexible transparent substrate is required to be more than 80%, and the haze is required to be less than 3%; before coating the nano silver wire-silver complex compound conductive ink on the flexible transparent substrate, the flexible transparent substrate needs to be subjected to corona or plasma treatment, and the surface energy is required to be more than 32 dyn/cm.
2. The transparent conductive film of claim 1, wherein the diameter of the silver nanowires is 10-150 nm and the length thereof is 2-200 μm.
3. The silver nanowire transparent conductive film according to claim 2, wherein the dispersant is a solvent with a boiling point of 35-120 ℃, and the dispersant is selected from one or two of water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene, butanone, methanol, chloroform and dichloromethane.
4. A method for preparing the silver nanowire transparent conductive film according to any one of claims 1-3, comprising the steps of:
(1) carrying out corona or plasma treatment on the flexible transparent substrate;
(2) coating the nano silver wire-silver complex compound conductive ink on the surface of a flexible transparent substrate, and thermally curing to form a nano silver wire-silver complex compound conductive layer;
(3) and coating the protective film coating liquid on the surface of the nano silver wire-silver complex compound conductive layer, and forming a protective film after thermosetting or photocuring to obtain the nano silver wire transparent conductive film.
5. The method for preparing the silver nanowire transparent conductive film according to claim 4, wherein the flexible transparent substrate is any one of polyethylene naphthalate, polycarbonate, polyacrylate, polydimethylsiloxane, polymethyl methacrylate, polyimide and polyethylene terephthalate, and the thickness of the flexible transparent substrate is 7.5-225 μm.
6. The method for preparing the silver nanowire transparent conductive film according to claim 5, wherein the thickness of the silver nanowire-silver complex composite conductive layer is 15 to 300 nm.
7. The method for preparing the silver nanowire transparent conductive film according to claim 6, wherein the coating manner is slot coating, slide coating, micro-gravure coating or blade coating.
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