CN107345096A - A kind of preparation method of nano-silver thread silver complex composite conducting ink and its nesa coating - Google Patents
A kind of preparation method of nano-silver thread silver complex composite conducting ink and its nesa coating Download PDFInfo
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- 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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- C08J2483/04—Polysiloxanes
Abstract
The invention discloses a kind of nano-silver thread silver complex composite conducting ink, including nano-silver thread ink and silver complex ink, nano-silver thread ink accounts for percentage by weight 80~95%, and silver complex ink accounts for percentage by weight 5~20%；Described nano-silver thread ink includes nano-silver thread and dispersant, and nano-silver thread accounts for percentage by weight 0.5~5%, and dispersant accounts for percentage by weight 95~99.5%；Described silver complex ink includes silver complex and stabilizer, and silver complex accounts for percentage by weight 5~10%, and stabilizer accounts for percentage by weight 90~95%.The present invention can extend the storage life of composite conducting ink, be easy to industrialization production, improve electric conductivity and homogeneity after its film forming, can effectively reduce the speed that nano-silver thread separates out in nano-silver thread ink, prevent nano-silver thread is reunited from settling；Meanwhile it can also increase the resistance homogeneity after nano-silver thread film forming.
Description
Technical field
It is more particularly to a kind of to be based on nano-silver thread conductive ink and its nesa coating the present invention relates to liquid crystal technology field
Preparation method.
Background technology
Nesa coating is a kind of fexible film for having in visible-range high transmission rate and conductive characteristic, can be applied
In various fields such as touch-control, display, photovoltaic, illumination, wearable electronic devices.ITO conducting films occupy nesa coating at present
90% market, but it has the problem of expensive, pliability is poor, high energy consumption and resistance are high, so being badly in need of being applicable to curved
Qu Yingyong and the new substitution technology of large scale application.
Nano-silver thread nesa coating is to intersect IPN formation network structure with nano-silver thread to realize conducting function, passes through net
Mesh in network structure carries out printing opacity.Nano-silver thread nesa coating because its have can be achieved large area volume to volume processing technology,
The advantages of rate of good quality rate, low cost, low resistance, high printing opacity, low haze, high flexibility etc., progressively turn into and be most hopeful to substitute ITO
Nesa coating.
The principal element for influenceing nano-silver thread nesa coating properties of product is the formula and film forming work of nano-silver thread ink
Skill.Nano-silver thread surface-active is high, disperses sedimentation of reuniting easily occurs in a solvent, on the one hand causes be configured to Nano Silver
Line stability of ink is poor, storage life is short, it is difficult to industrialization production；On the other hand the film for causing nano-silver thread ink to be formed, electricity
It is poor to hinder homogeneity, is unsatisfactory for application demand.In order to solve these problems, technical staff employs many methods to adjust Nano Silver
The formula of line ink, reunited sedimentation and the problem of into film resistance homogeneity difference with improving nano-silver thread.Such as in nano-silver thread ink
High polymer is added, high polymer is effectively coated nano-silver thread surface, reunites so as to avoid nano-silver thread from contacting with each other,
Although the stability of nano-silver thread ink can be improved, after the addition of high polymer can dramatically increase nano-silver thread ink film forming
Resistance；Surfactant such as also is added in nano-silver thread ink, although the electricity after nano-silver thread ink film forming can be improved
Homogeneity is hindered, but the stability of nano-silver thread ink can not be improved, while can also influence the resistance after nano-silver thread ink film forming.
The content of the invention
The technical problem to be solved in the present invention is：For the problems of above-mentioned existing nano-silver thread ink and deficiency,
A kind of nano-silver thread-silver complex composite conducting ink is provided.
Another technical problem that the present invention solves is to provide a kind of high stability, high conductivity, high resistance homogeneity and received
The preparation method of rice silver wire nesa coating.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of nano-silver thread-silver complex composite conducting ink, including nano-silver thread ink and silver complex ink, its
In, nano-silver thread ink accounts for percentage by weight 80~95%, and silver complex ink accounts for percentage by weight 5~20%；Described receives
Rice silver wire ink includes nano-silver thread and dispersant, wherein, nano-silver thread accounts for percentage by weight 0.5~5%, and dispersant accounts for weight
Percentage 95~99.5%；Described silver complex ink includes silver complex and stabilizer, wherein, silver complex accounts for weight hundred
Divide ratio 5~10%, stabilizer accounts for percentage by weight 90~95%.
Above-mentioned nano-silver thread-silver complex composite conducting ink, the silver complex may be selected from AgSCN, AgOCN,
AgOCNBr、AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl、Ag(NH3)2Any one in CN.
Above-mentioned nano-silver thread-silver complex composite conducting ink, a diameter of 10~150nm of nano-silver thread, length 2
~200 μm.
Above-mentioned nano-silver thread-silver complex composite conducting ink, the stabilizer are organic molten for 150~280 DEG C of boiling point
Agent, any one in terpinol, 2- phenoxetols, glycerine, pungent two mercaptan or ethylene glycol.
Above-mentioned nano-silver thread-silver complex composite conducting ink, the dispersant are the solvent of 35~120 DEG C of boiling point, are selected
From appointing in water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene, butanone, methanol, chloroform or dichloromethane
Anticipate a kind of or dissolve each other two kinds.
The preparation method of the nano-silver thread nesa coating of the present invention, comprises the following steps：
(1) flexible transparent substrate is subjected to corona or plasma treatment；
(2) nano-silver thread described in claim 1-silver complex composite conducting ink is applied to flexible transparent substrate table
Face, nano-silver thread-silver complex composite conductive layers are formed after heat cure；
(3) protective layer coating solution is applied to nano-silver thread-silver complex composite conducting layer surface, after thermosetting or photocuring
Protective layer is formed, obtains nano-silver thread nesa coating.
The preparation method of above-mentioned nesa coating, the flexible transparent substrate are PEN, poly- carbonic acid
In ester, polyacrylate, dimethyl silicone polymer, polymethyl methacrylate, polyimides, polyethylene terephthalate
Any one, the thickness of the flexible transparent substrate is 7.5~225 μm.
The preparation method of above-mentioned nesa coating, the thickness of the nano-silver thread-silver complex composite conductive layers for 15~
300nm。
The preparation method of above-mentioned nesa coating, the protective layer be polyvinyl alcohol, polyurethane, polyester, acrylic resin,
The film that any one or two kinds of mixtures of polythiophene, organic-silicon-modified resin are formed, the thickness of the protective layer for 20~
150nm。
The preparation method of above-mentioned nesa coating, the mode of the coating stitch coating, slope flow coat cloth, micro- intaglio plate coating for bar
Or scraper for coating.
Beneficial effect
Compared with prior art, the present invention forms Nano Silver by adding silver complex ink in nano-silver thread ink
Line-silver complex composite conducting ink, its advantage are shown：
(1) effectively prevented with the dispersiveness of organic complex group and the electric conductivity of inorganic silver using silver complex
The generation of nano-silver thread reunion sedimentation, significantly improves the stability of nano-silver thread conductive ink, extends its storage life, be easy to produce
Industry metaplasia is produced.Meanwhile nano-silver thread effectively can be connected into network structure by silver complex, improve the electric conductivity after its film forming and
One property.
(2) due in silver complex ink stabilizer be higher boiling (>150 DEG C) organic solvent, so can effectively it reduce
The speed that nano-silver thread separates out in nano-silver thread ink, prevent nano-silver thread is reunited from settling；Meanwhile it can also suppress nano-silver thread ink
Water in film forming procedure low boiling low boiling (<120 DEG C) the quick volatilization of solvent dispersant, increase the electricity after nano-silver thread film forming
Hinder homogeneity.
(3) nano-silver thread nesa coating of the invention, can use volume to volume preparation technology, be more suitable for large area serialization
Industrialized production, technique is simple, manufacturing cost is low.
Embodiment
In order that technical scheme is more clearly understood, embodiments of the present invention will be made further detailed
Illustrate, but these embodiments do not limit other embodiments of the present invention only to explain the present invention.
A kind of nano-silver thread-silver complex composite conducting ink, including nano-silver thread ink and silver complex ink, its
In, nano-silver thread ink accounts for percentage by weight 80~95%, and silver complex ink accounts for percentage by weight 5~20%；Described receives
Rice silver wire ink includes nano-silver thread and dispersant, wherein, nano-silver thread accounts for percentage by weight 0.5~5%, and dispersant accounts for weight
Percentage 95~99.5%；Described silver complex ink includes silver complex and stabilizer, wherein, silver complex accounts for weight hundred
Divide ratio 5~10%, stabilizer accounts for percentage by weight 90~95%.
It is suitable for nano-silver thread a diameter of 10~150nm, preferably 15~50nm contained in nano-silver thread ink of the present invention,
If if silver wire is meticulous, its surface-active is high, easily winding is reunited each other；If silver wire slightly, can reduce to be formed excessively
The optical property of conductive film.Nano-silver thread length be 2~200 μm, preferably 10~50 μm, if if silver wire is too short, silver wire phase
It can not overlapped between mutually, can not form conductive network；If if silver wire is long, silver wire easily winds, is broken each other.Nano-silver thread
Percentage by weight is 0.5~5%, and if content is less than 0.5%, it is too high to form electrically conducting transparent film resistance；Content is higher than 5%
Words, nano-silver thread are easily reunited because its surface-active is high.It is suitable for dispersant contained in nano-silver thread ink of the present invention as boiling
The solvent of 35~120 DEG C of point, preferably water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene, butanone, methanol, trichlorine
Any one in methane or dichloromethane or dissolve each other two kinds.Dispersant weight percentage is 95~99.5%, for adjusting
The concentration and viscosity of nano-silver thread.
The silver complex being suitable in silver complex ink of the present invention may be selected from AgSCN, AgOCN, AgOCNBr,
AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl、Ag(NH3)2Any one in CN.Silver complex weight percent
Than for 5~10%, if content is less than 5%, contained organic complex group can not coat nano-silver thread well, not have prevention
The reunion sedimentation of nano-silver thread；If content is higher than 10%, the resistance and optical property of formed nesa coating can be influenceed.It is suitable
Together in the organic solvent that the stabilizer in silver complex ink of the present invention is 150~280 DEG C of boiling point, preferably terpinol, 2- benzene oxygen
Any one in base ethanol, glycerine, pungent two mercaptan or ethylene glycol.Stabilizer percentage by weight is 90~95%, and content is low
If 90%, it is impossible to disperse silver complex well；If content is higher than 95%, because its boiling point is too high, it is not easy to volatilize,
The speed of film forming can be influenceed.
A kind of preparation method of nano-silver thread nesa coating, this method comprise the following steps：
(1) flexible transparent substrate is subjected to corona or plasma treatment；
(2) nano-silver thread described in claim 1-silver complex composite conducting ink is passed through into the coating of bar seam, slope flow coat
Cloth, micro- intaglio plate coating or scraper for coating method are applied to flexible transparent substrate surface, and nano-silver thread-silver complex is formed after heat cure
Composite conductive layers；
(3) protective layer coating solution is stitched into coating, slope flow coat cloth, micro- intaglio plate coating or scraper for coating method by bar to be applied to and receive
Rice silver wire-silver complex composite conducting layer surface, forms protective layer after thermosetting or photocuring, obtains nano-silver thread electrically conducting transparent
Film.
The flexible transparent substrate requirement for being suitable for the present invention has certain heat resistance, if because flexible transparent substrate
It is inconsistent with nano-silver thread-silver complex composite bed and protective layer thermal expansion change in size during post-production, it will cause
The cracking of the two and stripping.Therefore the flexible transparent substrate of the present invention is more preferably less than from the small resin film of linear expansion coefficient
40ppm/ DEG C, such as PEN (PEN), makrolon (PC), polyacrylate (PVA), polydimethylsiloxanes
Appointing in alkane (PDMS), polymethyl methacrylate (PMMA), polyimides (PI), polyethylene terephthalate (PET)
Meaning is a kind of, preferably cheap, function admirable polyethylene terephtalate.The thickness of flexible and transparent base substrate
Spend for 7.5~225 μm, preferably 12~188 μm, if if excessively thin, base material mechanical strength is too low, be unfavorable for nano-silver thread-silver-colored network
The making of compound composite bed and protective layer；If blocked up, transmitance is too low, flexible is also deteriorated.The full light of flexible and transparent base substrate
Light transmittance requirement more than 80%, preferably more than 85%, mist degree requirement less than 3%, preferably less than 1.5%, to obtain optical property
Excellent nano-silver thread nesa coating.Flexible transparent substrate, need to be to it before silver wire-silver complex composite conducting ink is coated with
Corona or plasma treatment are carried out, surface energy requires more than 32dyn/cm, preferably more than 34dyn/cm.
The coating method of nano-silver thread-silver complex composite conducting ink may be selected from the coating of bar seam, slope flow coat cloth, nick version
Coating or scraper for coating in any one, preferably bar seam coating or slope flow coat cloth because the two is Non-Contact Coating side
Formula, in nano-silver thread-silver complex composite conducting ink, nano-silver thread, which is not easy to reunite, separates out and produces strip flaw.Nanometer
After silver wire-silver complex composite conducting ink is applied to flexible transparent substrate, it is heating and curing by 30~150 DEG C, forms nanometer
Silver wire-silver complex composite conductive layers, thickness are 15~300nm, preferably 50~150nm, if if excessively thin, film conductivity
Difference；If if blocked up, Film Optics poor performance.
Protective layer is arranged on nano-silver thread-silver complex composite conducting layer surface.Nano-silver thread is due to its surface-active pole
Height, on the one hand it is easily oxidized by oxygen, causes nano-silver thread layer resistance to raise in air ambient；Another aspect steam penetrates into
It nano-silver thread layer, can be electrolysed to form hydrogen ion and hydroxide ion, silver migration occurs, significantly reduce the life-span of nano-silver thread layer.
So need in nano-silver thread-silver complex composite conducting layer surface coating layer protective layer to complete to nano-silver thread-silver-colored network
The protection of compound composite conductive layers, to improve the high temperature oxidation resisting of nano-silver thread nesa coating and resistance to moisture.Meanwhile
The optical property of nano-silver thread nesa coating can be improved.Protective layer material of the present invention may be selected from polyvinyl alcohol, polyurethane, gather
Any one in ester, acrylic resin, polythiophene or organic-silicon-modified resin or two kinds of mixtures.Coating method may be selected from bar
Stitch any one in coating, slope flow coat cloth, micro- intaglio plate coating or scraper for coating method, the preferably coating of bar seam or slope flow coat
Cloth,, will not be multiple to nano-silver thread-silver complex of lower floor when being coated with protection materials because the two is Non-Contact Coating mode
Close the defects of conductive layer causes to scratch, wears, scratches.The thickness of protective layer of the present invention is 20~150nm, preferably 30~100nm.
If protective layer is excessively thin, it is impossible to be completely covered by nano-silver thread-silver complex composite conductive layers, do not have increase thin-film barrier
Effect；If film layer is blocked up, nano-silver thread-silver complex composite conductive layers resistance rise, film light transmittance can be caused to reduce.
The present invention is described in detail in reference to embodiments.
Embodiment 1
The first step：Handle flexible transparent substrate
From 100 μ m thick PET, breadth 550mm, full light transmission rate is 91.3%, mist degree 0.34%, 0.8kV electricity
After piezoelectricity is dizzy, surface energy 36dyn/cm.
Second step：Prepare nano-silver thread-silver complex composite bed
Preparation of nano silver wire-silver complex composite conducting ink：1) it is 25nm by line footpath, the nano-silver thread that length is 15 μm
It is dispersed in alcohol solvent, is configured to the nano-silver thread ink 8L that concentration is 0.5wt%；2) silver complex AgSCN is dispersed in
In stabilizer terpinol, the silver complex ink 2L that concentration is 10wt% is configured to；3) and then by 8L nano-silver threads ink and 2L
Silver complex ink mixes, and stirring 0.5h forms nano-silver thread-silver complex conductive ink.
It is coated with nano-silver thread-silver complex conductive ink：Coating machine is stitched by the above-mentioned nano-silver thread-silver prepared using bar
Complex compound conductive ink, pet sheet face is applied to 5m/min speed, 80 DEG C of dryings formed nano-silver thread that thickness is 100nm-
Silver complex conductive layer.
3rd step：Prepare protective layer
Prepare protective layer coating solution：0.5g polyurethane resins are dispersed in ethyl acetate solvent, form solid content as 2%
Polyurethane coated liquid.
Coat protective layer coating fluid：In the above-mentioned PET/ nano-silver threads-compound layer surface of silver complex prepared, using bar
The mode volume to volume of seam coating is coated with a strata urethane coating fluid, and 85 DEG C of dryings form the protective layer that thickness is 80nm.
Embodiment 2
The first step：Handle flexible transparent substrate
From 125 μ m thick PC, breadth 560mm, full light transmission rate is 88.2%, mist degree 0.78%, 0.6kV voltages
After corona, surface energy 38dyn/cm.
Second step：Prepare nano-silver thread-silver complex composite bed
Preparation of nano silver wire-silver complex composite conducting ink：1) it is 50nm by line footpath, the nano-silver thread that length is 10 μm
It is dispersed in aqueous solvent, is configured to the nano-silver thread ink 8.5L that concentration is 1wt%；2) silver complex AgOCN is dispersed in surely
Determine in agent 2- phenoxetols, be configured to 8wt% silver complex ink 1.5L；3) and then by 8.5L nano-silver threads ink and
1.5L silver complexes ink mixes, and stirring 0.5h forms nano-silver thread-silver complex conductive ink.
It is coated with nano-silver thread-silver complex conductive ink：Using slope flow coat cloth machine by the above-mentioned nano-silver thread-silver prepared
Complex compound conductive ink, PC surfaces are applied to 6m/min speed, 105 DEG C of dryings formed nano-silver thread that thickness is 50nm-
Silver complex conductive layer.
3rd step：Prepare protective layer
Prepare protective layer coating solution：By the organic-silicon-modified resin dispersions of 0.5g in isopropanol solvent, forming solid content is
2.5% organic-silicon-modified resin coating fluid.
Coat protective layer coating fluid：In the above-mentioned PC/ nano-silver threads-compound layer surface of silver complex prepared, using slope
The mode volume to volume of flow coat cloth is coated with one layer of organic-silicon-modified resin coating fluid, and 65 DEG C of dryings form the protection that thickness is 100nm
Layer.
Embodiment 3
The first step：Handle flexible transparent substrate
From 12 μ m thick PI, breadth 540mm, full light transmission rate is 89.5%, mist degree 0.53%, 1kV plasmas
After processing, surface energy 34dyn/cm.
Second step：Prepare nano-silver thread-silver complex composite bed
Preparation of nano silver wire-silver complex composite conducting ink：1) it is 15nm by line footpath, the nano-silver thread that length is 30 μm
It is dispersed in isopropanol solvent, is configured to the nano-silver thread ink 9L that concentration is 2wt%；2) silver complex AgOCNBr is disperseed
In stabilizer glycerine, the silver complex ink 1L that concentration is 6.5wt% is configured to；3) and then by 9L nano-silver threads ink and
1L silver complexes ink mixes, and stirring 0.5h forms nano-silver thread-silver complex conductive ink.
It is coated with nano-silver thread-silver complex conductive ink：The nano-silver thread prepared using micro- gravure coater by above-mentioned-
Silver complex conductive ink, PI surfaces are applied to 4m/min speed, 85 DEG C of dryings form the Nano Silver that thickness is 150nm
Line-silver complex conductive layer.
3rd step：Prepare protective layer
Prepare protective layer coating solution：0.5g polyacrylic resins are dispersed in alcohol solvent, it is 3% to form solid content
Polyacrylic resin coating fluid.
Coat protective layer coating fluid：In the above-mentioned PI/ nano-silver threads-compound layer surface of silver complex prepared, using scraping
The mode volume to volume of knife is coated with a layer polypropylene acid resin coating fluid, and 55 DEG C of dryings form the protective layer that thickness is 60nm.
Embodiment 4
The first step：Handle flexible transparent substrate
From 188 μ m thick PEN, breadth 550mm, full light transmission rate is 90.8%, mist degree 0.67%, 1kV coronas
After processing, surface energy 42dyn/cm.
Second step：Prepare nano-silver thread-silver complex composite bed
Preparation of nano silver wire-silver complex composite conducting ink：1) it is 30nm by line footpath, the nano-silver thread that length is 50 μm
It is dispersed in acetone solvent, is configured to the nano-silver thread ink 9.5L that concentration is 4wt%；2) by silver complex AgSCSN3It is scattered
In pungent two mercaptan of stabilizer, the silver complex ink 0.5L that concentration is 5wt% is configured to；3) it is and then 9.5L nano-silver threads is black
Water and the mixing of 0.5L silver complexes ink, stirring 0.5h form nano-silver thread-silver complex ink.
It is coated with nano-silver thread-silver complex composite conducting ink：Using knife type coater by the above-mentioned Nano Silver prepared
Line-silver complex conductive ink, PEN surfaces are applied to 6m/min speed, 90 DEG C of dryings form the nanometer that thickness is 200nm
Silver wire-silver complex conductive layer.
3rd step：Prepare protective layer
Prepare protective layer coating solution：0.5g polyvinyl alcohol is dispersed in ethyl acetate solvent, forms solid content as 1.5%
PVA paint.
Coat protective layer coating fluid：In the above-mentioned PEN/ nano-silver threads-compound layer surface of silver complex prepared, using bar
The mode volume to volume coating layer of polyethylene alcohol coating fluid of seam coating, 85 DEG C of dryings form the protective layer that thickness is 30nm.
Embodiment 5
The first step：Handle flexible transparent substrate
From 75 μ m thick PDMS, breadth 560mm, full light transmission rate is 91.2%, mist degree 0.47%, 0.8kV electricity
After dizzy processing, surface energy 46dyn/cm.
Second step：Prepare nano-silver thread-silver complex composite bed
Preparation of nano silver wire-silver complex composite conducting ink：1) it is 80nm by line footpath, the Nano Silver that length is 100 μm
Line is dispersed in ethyl acetate solvent, is configured to the nano-silver thread ink 9.2L that concentration is 5wt%；2) by silver complex Ag4Fe
(CM)6It is dispersed in stabilizer ethylene glycol, is configured to the silver complex ink 0.8L that concentration is 5.5wt%；3) and then by 9.2L
Nano-silver thread ink and the mixing of 0.8L silver complexes ink, stirring 0.5h form coating nano-silver thread-silver complex composite conducting
Ink.
It is coated with nano-silver thread-silver complex composite conducting ink：Using micro- gravure coater by the above-mentioned coating prepared
Nano-silver thread-silver complex composite conducting ink, PDMS surfaces are applied to 4m/min speed, 65 DEG C of dryings form thickness and are
300nm nano-silver thread layer.
3rd step：Prepare protective layer
Prepare protective layer coating solution：0.5g polythiophenes are dispersed in water, add 0.1g surfactants, formation contains admittedly
Measure the polythiophene coating fluid for 2.5%.
Coat protective layer coating fluid：In the above-mentioned PDMS/ nano-silver threads-compound layer surface of silver complex prepared, use
The mode volume to volume of slope flow coat cloth is coated with a strata thiophene coating fluid, and 105 DEG C of dryings form the protective layer that thickness is 50nm.
Comparative example 1
The first step：Handle flexible transparent substrate
With embodiment 1.
Second step：Prepare nano-silver thread layer
Preparation of nano silver wire ink：The nano-silver thread that by line footpath be 25nm, length is 15 μm is dispersed in alcohol solvent, is matched somebody with somebody
The nano-silver thread ink 8L that concentration is 0.5wt% is made.
It is coated with nano-silver thread ink：Using bar seam coating machine by the above-mentioned nano-silver thread ink prepared, with 5m/min's
Speed is applied to pet sheet face, and 80 DEG C of dryings form the nano-silver thread layer that thickness is 100nm.
3rd step：Prepare protective layer
With embodiment 1.
The square resistance and its homogeneity, Quan Guangtou of nano-silver thread nesa coating prepared by embodiment 1-5 and comparative example 1
Light rate, mist degree, yellow value degree and high temperature resistant and wet and heat ageing resistant performance indications, are shown in Table 1.
(1) square resistance (R) is tested
Condition：Using ST-21 type FOUR-POINT PROBE METERs, 23 ± 5 DEG C of temperature, relative humidity：(50 ± 10) %RH.
(2) full light light transmittance (T) and mist degree (H) test
Condition：Using light transmittance/mist degree analyzer, reference standard GB/T 2041-2008 transparent plastics light transmittances and mist degree
Measure, 23 ± 5 DEG C of temperature, relative humidity：(50 ± 10) %RH.
(3) yellow value degree (b*) is tested
Condition：Using chromascope, reference standard GB/T 2409-1980 plastics yellow colour index test methods, temperature 23 ± 5
DEG C, relative humidity：(50 ± 10) %RH.
(4) high temperature resistant is tested
Condition：80 DEG C of temperature, time 240h, with reference to GB/T 2918-1998 plastic samples status adjustments and the standard of experiment
Environment.Resistance variations (Δ R)=(RAfter aging-RBefore aging)/RBefore aging；Light transmittance changes (Δ T)=(TAfter aging-TBefore aging)/TBefore aging；Mist degree becomes
Change (Δ H)=(HAfter aging-HBefore aging)/HBefore aging；Yellowing changes (Δ b*)=(b*After aging-b*Before aging)/b*Before aging。
(5) wet and heat ageing resistant is tested
Condition：Humidity 95%RH, temperature 60 C, time 240h, with reference to GB/T 2918-1998 plastic sample status adjustments
With the standard environment of experiment.Resistance variations (Δ R)=(RAfter aging-RBefore aging)/RBefore aging；Light transmittance changes (Δ T)=(TAfter aging-
TBefore aging)/TBefore aging；Haze change (Δ H)=(HAfter aging-HBefore aging)/HBefore aging；Yellowing changes (Δ b*)=(b*After aging-b*Before aging)/
b*Before aging。
The embodiment 1-5 of table 1 and the test data table of comparative example 1
Found out by the data of table 1, the nano-silver thread nesa coating of embodiment 1-5 inventions does not add silver-colored network relative to comparative example 1
The nano-silver thread nesa coating that compound ink is formed, resistance is lower, homogeneity is more preferable, high temperature resistant, wet-heat resisting, anti-yellowing property
It is obvious excellent.
Claims (10)
1. a kind of nano-silver thread-silver complex composite conducting ink, it is characterised in that including nano-silver thread ink and silver complex
Ink, wherein, nano-silver thread ink accounts for percentage by weight 80~95%, and silver complex ink accounts for percentage by weight 5~20%；
Described nano-silver thread ink includes nano-silver thread and dispersant, wherein, nano-silver thread accounts for percentage by weight 0.5~5%,
Dispersant accounts for percentage by weight 95~99.5%；Described silver complex ink includes silver complex and stabilizer, wherein, silver-colored network
Compound accounts for percentage by weight 5~10%, and stabilizer accounts for percentage by weight 90~95%.
2. nano-silver thread according to claim 1-silver complex composite conducting ink, it is characterised in that the silver complexing
Thing may be selected from AgSCN, AgOCN, AgOCNBr, AgSCSN3、Ag4Fe(CM)6、Ag3Fe(CN)6、Ag(NH3)2Cl or Ag (NH3)2CN
In any one.
3. nano-silver thread according to claim 2-silver complex composite conducting ink, it is characterised in that the Nano Silver
Linear diameter is 10~150nm, and length is 2~200 μm.
4. nano-silver thread according to claim 3-silver complex composite conducting ink, it is characterised in that the stabilizer
For 150~280 DEG C of organic solvent of boiling point, the stabilizer is selected from terpinol, 2- phenoxetols, glycerine, pungent two mercaptan
Or any one in ethylene glycol.
5. nano-silver thread according to claim 4-silver complex composite conducting ink, it is characterised in that the dispersant
For 35~120 DEG C of solvent of boiling point, the dispersant be selected from water, ethanol, isopropanol, n-butanol, acetone, ethyl acetate, toluene,
Any one in butanone, methanol, chloroform or dichloromethane or dissolve each other two kinds.
6. a kind of preparation method of nano-silver thread nesa coating, comprises the following steps：
(1) flexible transparent substrate is subjected to corona or plasma treatment；
(2) nano-silver thread described in claim 1-silver complex composite conducting ink is applied to flexible transparent substrate surface,
Nano-silver thread-silver complex composite conductive layers are formed after heat cure；
(3) protective layer coating solution is applied to nano-silver thread-silver complex composite conducting layer surface, formed after thermosetting or photocuring
Protective layer, obtain nano-silver thread nesa coating.
7. the preparation method of nano-silver thread nesa coating according to claim 6, it is characterised in that the flexible and transparent
Substrate be PEN, makrolon, polyacrylate, dimethyl silicone polymer, polymethyl methacrylate,
Any one in polyimides, polyethylene terephthalate, the thickness of the flexible transparent substrate is 7.5~225 μm.
8. the preparation method of nano-silver thread nesa coating according to claim 6, it is characterised in that the Nano Silver
The thickness of line-silver complex composite conductive layers is 15~300nm.
9. the preparation method of nano-silver thread nesa coating according to claim 6, it is characterised in that the protective layer is
Any one or two kinds of mixture shapes of polyvinyl alcohol, polyurethane, polyester, acrylic resin, polythiophene, organic-silicon-modified resin
Into film, the thickness of the protective layer is 20~150nm.
10. the preparation method of nano-silver thread nesa coating according to claim 6, it is characterised in that the coating
Mode is that bar stitches coating, slope flow coat cloth, micro- intaglio plate coating or scraper for coating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574453A (en) * | 2019-09-30 | 2021-03-30 | Sk新技术株式会社 | Antistatic polyimide base film and flexible display panel using the same |
| CN114171239A (en) * | 2021-11-30 | 2022-03-11 | 深圳市华科创智技术有限公司 | Composite conductive ink, transparent conductive film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157807A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Method for preparing silver nanowires |
| CN107093500A (en) * | 2017-03-30 | 2017-08-25 | 华南理工大学 | A kind of graphic method of nano silver wire flexible transparent conductive film |
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2017
- 2017-08-30 CN CN201710765439.7A patent/CN107345096B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157807A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Method for preparing silver nanowires |
| CN107093500A (en) * | 2017-03-30 | 2017-08-25 | 华南理工大学 | A kind of graphic method of nano silver wire flexible transparent conductive film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574453A (en) * | 2019-09-30 | 2021-03-30 | Sk新技术株式会社 | Antistatic polyimide base film and flexible display panel using the same |
| CN112574453B (en) * | 2019-09-30 | 2023-11-24 | Sk新技术株式会社 | Antistatic polyimide base film and flexible display panel using the same |
| CN114171239A (en) * | 2021-11-30 | 2022-03-11 | 深圳市华科创智技术有限公司 | Composite conductive ink, transparent conductive film and preparation method thereof |
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Effective date of registration: 20210924 Address after: 071054, 6 Kennan Avenue, Baoding, Hebei Patentee after: CHINA LUCKY Group Corp. Patentee after: Shanghai Lekai New Material Technology Co.,Ltd. Address before: 071054, 6 Kennan Avenue, Baoding, Hebei Patentee before: CHINA LUCKY Group Corp. |