CN107365528A - Electrically conducting transparent ink composite and transparent conductive film based on nano-silver thread - Google Patents
Electrically conducting transparent ink composite and transparent conductive film based on nano-silver thread Download PDFInfo
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- CN107365528A CN107365528A CN201710543413.8A CN201710543413A CN107365528A CN 107365528 A CN107365528 A CN 107365528A CN 201710543413 A CN201710543413 A CN 201710543413A CN 107365528 A CN107365528 A CN 107365528A
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- Prior art keywords
- electrically conducting
- ink composite
- conducting transparent
- nano
- transparent ink
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
Disclose electrically conducting transparent ink composite and transparent conductive film based on nano-silver thread.Epoxy resin and polyacrylonitrile-based carbon fibre are added in the electrically conducting transparent ink composite of the present invention, and the addition of polyacrylonitrile-based carbon fibre is less than the addition of epoxy resin, on the one hand, it can prevent the nano-silver thread of the ratio of height to diameter caused by nano-silver thread content is higher from coalescing sedimentation, improve the service life and stability of electrically conducting transparent ink composite；On the other hand, the light transmittance of the conductive ink composition caused by largely addition binding agent or thickener etc. can be avoided low；In addition, polyacrylonitrile-based carbon fibre has excellent electric conductivity, the addition of polyacrylonitrile-based carbon fibre will not reduce the electrical conductivity of electrically conducting transparent ink composite, and the density of electrically conducting transparent ink composite is small, light weight, disclosure satisfy that the portability demand of electronic installation now.
Description
Technical field
The present invention relates to ink class field of material technology, more particularly to the electrically conducting transparent ink composite based on nano-silver thread
And transparent conductive film.
Background technology
The background of related of the present invention is illustrated below, but these explanations might not form the existing of the present invention
Technology.
The properties such as the optics of the metal material of nano-scale, magnetic, heat pass, diffusion and machinery with micron-scale
Metal material differs widely, therefore also has more many application potentials.In general, one-dimensional nano structure material refers to
There is the size of nanometer on two dimension directions, and its length is not necessarily limited to nano-scale, such as nanotube, nanometer
Rod, nanofiber and nano metal line etc..
Electrically conducting transparent ink has highly important status in display and solar energy industry.At present, it is more using oxidation
Indium tin (Indium Tin Oxide, ITO) prepares transparent conductive film, but the amount of storage of indium and tin is limited, ITO materials into
This height, ITO materials on large scale processing procedure have using limitation so that nano metal line transparent conductive film application with opening
Hair becomes more and more important.
The development for the transparent conductive film that nano metal line makes still is limited by the stability of nano metal line ink.
In the case of the solid content of metal wire is high, the metal wire of high length-diameter ratio is easily coalesced and settled, and this causes nano metal line oily
Ink can not preserve for a long time.Therefore, application it is upper solid content of the nano metal line in ink must be often down to it is very low, and
A large amount of thickeners or binding agent are added to prevent nano metal line from settling.Because the solid content of nano metal line is not high, and separately have
The addition of dielectric thickener or binding agent so that by the electrical conductivity of the transparent conductive film of nano metal line printing ink to manufacture
All the time be less than as the electrical conductivity of the transparent conductive film made by ITO, and add in electrically conductive ink substantial amounts of thickener or
Binding agent can cause the light transmittance of manufactured transparent conductive film to reduce, while also improve mist degree.And in order to make electrical conductivity height
Transparent conductive film, the coating thickness of nano metal line ink must also improve, so as to meet electronic installation now
The demand of thickness more and more thinner.
The content of the invention
It is an object of the invention to overcome one or more problems present in prior art, propose that one kind is based on Nano Silver
The electrically conducting transparent ink composite and transparent conductive film of line, electrical conductivity and light transmittance are high, rheological characteristic and the cohesive force to base material
Good, cost is low.
Electrically conducting transparent ink composite of the invention based on nano-silver thread, include the component of following mass fraction：
Nano-silver thread, 0.5%-15%；
Epoxy resin, 20%-30%；
Polyacrylonitrile-based carbon fibre, 9%-18%；
Organic solvent, 50%-60%；The organic solvent includes the one or more in alcohols, ethers and esters.
Present invention also offers using transparent conductive film made from above-mentioned electrically conducting transparent ink composite.
Epoxy resin and polyacrylonitrile-based carbon are added in electrically conducting transparent ink composite of the invention based on nano-silver thread
Fiber, and the addition of polyacrylonitrile-based carbon fibre is less than the addition of epoxy resin, on the one hand, polyacrylonitrile-based carbon fibre
Each fento form the network structure of stretching, extension, the nanometer of the ratio of height to diameter caused by nano-silver thread content is higher can be prevented
Silver wire coalescence sedimentation, improve the service life and stability of electrically conducting transparent ink composite；On the other hand, due to drop need not be passed through
Low nano-silver thread content, a large amount of addition mode such as binding agent or thickener prevent nano-silver thread from settling, thus can avoid due to
The light transmittance of conductive ink composition is low caused by a large amount of addition binding agents or thickener etc.；In addition, polyacrylonitrile-based carbon is fine
Dimension has excellent electric conductivity, and the addition of polyacrylonitrile-based carbon fibre will not reduce the electrical conductivity of electrically conducting transparent ink composite,
The density of electrically conducting transparent ink composite is small, light weight, disclosure satisfy that the portability demand of electronic installation now.
Embodiment
The illustrative embodiments of the present invention are described in detail below.Description to illustrative embodiments is only
For illustration purposes, it is definitely not to the present invention and its application or the limitation of usage.
Electrically conducting transparent ink composite of the invention based on nano-silver thread, include the component of following mass fraction：
Nano-silver thread, 0.5%-15%；
Epoxy resin, 20%-30%；
Polyacrylonitrile-based carbon fibre, 9%-18%；
Organic solvent, 50%-60%.
In the present invention, the mass fraction of nano-silver thread is 0.5%-15%, such as 0.5%, 5%, 10%, 15%.If receive
The addition of rice silver wire is too small, then the electrical conductivity of gained electrically conducting transparent ink composite is low, and poorly conductive is poor.Nano-silver thread adds
Dosage is excessive, can not only increase the possibility of nano-silver thread sedimentation, can also greatly increase the production cost of ink composite.This
Outside, if the addition of nano-silver thread is excessive, nano-silver thread can not be well-bonded and be retracted to the degree to contact with each other, is produced more
Metal voids so that the resistivity of electrically conducting transparent ink composite and thus obtained transparent conductive film is higher.Existing skill
Art is when preparing electrically conducting transparent ink composite, the addition some up to 20% of nano-silver thread, some as little as 0.05%, but
The present inventor has found in chronic study procedure, in the components system of the present invention, if the mass fraction of nano-silver thread
Less than 0.5%, such as when 0.05%, the electrical conductivity of gained electrically conducting transparent ink composite is very low, or even can not form stabilization
Electric current.If the mass fraction of nano-silver thread is more than 15%, such as 20%, 25% or 30%, gained electrically conducting transparent ink combination
The mobility of thing is excessively poor, it is difficult to is coated uniformly on substrate surface, causes coating layer thickness to differ；Further, thickness is less
Region nano-silver thread and base material strong bonded, the larger region nano-silver thread of thickness are layered in substrate surface intersecting, generation,
Nano-silver thread coated in base material upper strata uniform, firm can not be attached to substrate surface, low with the adhesion strength of base material, easy
Drop, under high temperature or external mechanical force effect, the figure layer of thickness thicker region is easily deformed, even if to electrically conducting transparent
Binding agent or other known diluent are added in the component of ink composite, can not also avoid the generation of the above situation.
In certain embodiments, of length no more than 35 μm of nano-silver thread, draw ratio are 150-300 μm.Consolidate in draw ratio
In the case of fixed, the length of nano-silver thread is longer, easier intersecting or produces reunion during coated on base material, on the one hand,
What the degree difference that nano-silver thread intersecting or generation at substrate surface diverse location are reunited, intersecting or generation were reunited
Nano-silver thread is more, and the coating layer thickness of substrate surface corresponding position is bigger, causes on base material intersecting at diverse location
Silver wire it is in uneven thickness, influence the using effect and aesthetic feeling of the design of product；On the other hand, it is conductive after electrically conducting transparent ink setting
Distance between silver particles diminishes, and free electron moves to form electric current along extra electric field direction, has good electric conductivity, nanometer
The degree that silver wire intersecting or generation are reunited is bigger, and the mobile route of free electron is longer, and the resistivity of electrically conductive composition is got over
It is high.In the case where the length of nano-silver thread is fixed, the draw ratio of nano-silver thread is bigger, and the relative length of nano-silver thread is longer,
Easier intersecting during coated on base material, cause on base material the in uneven thickness of the silver wire of intersecting at diverse location,
Influence the electric conductivity of the conductive film of coating；The draw ratio of nano-silver thread is smaller, and the conductance of obtained circuit board is lower, in addition,
When the circuit board using conductive ink composition printing is bent or deformed, too small draw ratio causes nano-silver thread to form
Circuit it is easily breaking because crack occurs in circuit board.
Epoxy resin after solidification has excellent adhesive strength to the surface of metal and nonmetallic materials, can avoid by
The current stability difference or current interruptions of the printed circuit board caused by nano-silver thread comes off from base material, gained electrically conducting transparent
The dielectric properties of film are good, and shrinkage factor is small, and product size stability is good.The hardness of epoxy resin is high, it is possible to increase transparent to lead
The wear resistance of electric ink composite.In the present invention, the addition of epoxy resin is 20%-30%, for example, 20%, 25% or
30%.If addition is excessive, the poor fluidity of gained electrically conducting transparent ink composite, if addition is too small, gained electrically conducting transparent
Ink composite is easily deformed, come off from base material, and not wear-resisting.In addition, epoxy resin has excellent electric conductivity, asphalt mixtures modified by epoxy resin
The addition of fat does not interfere with the electric conductivity of obtained electrically conducting transparent ink composite.
In some preferred embodiments, electrically conducting transparent ink composite further comprises：Aromatic amine and/or diaminourea two
Phenylsulfone.In the curing process, epoxy resin can react with aromatic amine and/or diamino diphenyl sulfone, and increase is transparent
The intensity of conductive ink composition and the caking property to base material.Preferably, the quality of aromatic amine and/or diamino diphenyl sulfone point
Number is no more than 5%.The addition of aromatic amine and/or diamino diphenyl sulfone is excessive, although can increase electrically conducting transparent ink group
The intensity of compound and the caking property to base material, but its mobility can be reduced so that electrically conducting transparent ink composite is difficult to uniformly
Coated in the electric conductivity on base material, influenceing thus obtained circuit board.
In order to solve the problems, such as that metal wire easily settles in existing ink composite, the present invention adds into ink composite
Polyacrylonitrile-based carbon fibre.The present inventor studies for a long period of time discovery, when in composition system simultaneously comprising epoxy resin and
During polyacrylonitrile-based carbon fibre, if the addition of polyacrylonitrile-based carbon fibre is more than the addition of epoxy resin, excessive is poly-
Acrylonitrile base carbon fiber is easily settled after the other components in adsorption combined objects system.Therefore, polypropylene in the present invention
The addition of itrile group carbon fiber is less than the addition of epoxy resin, it is preferable that when epoxy resin and polyacrylonitrile-based carbon fibre
Mass ratio is：1.5-2.0:When 1, the stability of gained electrically conducting transparent ink composite is best, electrical conductivity is higher.On the one hand, gather
Each fento of acrylonitrile base carbon fiber forms the network structure of stretching, extension, can prevent from causing because nano-silver thread content is higher
Ratio of height to diameter nano-silver thread coalescence sedimentation, improve electrically conducting transparent ink composite service life and stability；On the other hand,
Due to that need not prevent nano-silver thread from settling by reducing nano-silver thread content, largely adding the mode such as binding agent or thickener, because
This can be avoided the light transmittance of the conductive ink composition caused by largely addition binding agent or thickener etc. low；In addition,
Polyacrylonitrile-based carbon fibre has excellent electric conductivity, and the addition of polyacrylonitrile-based carbon fibre will not reduce electrically conducting transparent ink group
The electrical conductivity of compound, the density of electrically conducting transparent ink composite is small, light weight, disclosure satisfy that the portability of electronic installation now and needs
Ask.
The component of following mass fraction is may further include in the electrically conducting transparent ink composite of the present invention：0.5%-
2% organobentonite.Addition organobentonite can increase dispersing uniformity of the nano-silver thread in composition system, improve
The electrical conductivity of electrically conducting transparent ink composite；Suspension stability of the nano-silver thread in composition system is improved, prevents Nano Silver
Line settles；Improve the rheological characteristic of composition system, good film-forming property.Bentonite addition is too low, can not play above-mentioned effect
Fruit.Organobentonite is met water and easily expanded, and can form gel in organic solvent, when its adding too much, can influence group
The rheological stability of compound system.
During using electrically conducting transparent ink printed circuit board, it is desirable to which electrically conducting transparent ink has preferable mobility, otherwise difficult
So that electrically conducting transparent ink is uniformly coated on base material.The present invention is using the one kind or more included in alcohols, ethers and esters
The organic solvent of kind, the viscosity of electrically conducting transparent ink system can be reduced, improve the mobility of electrically conducting transparent ink composite, from
And it is easy to electrically conducting transparent ink composite being uniformly printed on base material.By weight percentage, the addition of organic solvent can
To be 50%-60%, such as 50%, 55% or 60%；If the addition of organic solvent is too low, conductive ink composition glues
Degree is big, poor fluidity, is unfavorable for electrically conducting transparent ink composite being uniformly printed on base material, when the addition of organic solvent is low
To a certain degree when, or even can not be fully in dissolved constituent system other solids fractions；If the adding too much of organic solvent,
The viscosity of electrically conducting transparent ink composite is too low, mobility is excessive, easily flows everywhere during coated on base material, influences circuit board
Printing.In addition, too high organic solvent addition can also reduce cohesive force of the electrically conducting transparent ink composite to base material, make solid
Electrically conducting transparent ink composite after change easily comes off from base material.Preferably, made using the mixture of ethyl acetate and chloroform
For organic solvent, the rheological characteristic of electrically conducting transparent ink composite can be significantly improved.
Influenced each other in electrically conducting transparent ink composite of the present invention between the addition of each component, in certain embodiments,
Conductive ink composition includes the component of following mass fraction：Nano-silver thread 8%；Epoxy resin, 21.3%；Polyacrylonitrile-based carbon
Fiber, 14.2%；Organic solvent, 55%；1.5% organobentonite.Using the electrically conducting transparent ink group of this constituent mass
Compound, the mobility on base material is more preferable, and adhesion is stronger, and electrical conductivity is good；Solidification temperature is low, hardening time is short.
Present invention also offers using transparent conductive film made from above-mentioned electrically conducting transparent ink composite.
It is illustrative to technical scheme with reference to specific embodiment.
Embodiment 1
Conductive ink composition includes the component of following mass fraction：Nano-silver thread 8%；Epoxy resin, 25%；Polypropylene
Itrile group carbon fiber, 10.5%；Organic solvent, 55%.
Embodiment 2-8
In addition to the component proportion listed by table 1 below, other conditions are same as Example 1.
The assay method of conductive ink composition specific insulation is：Conductive ink composition is printed onto transparent base
On, film-forming is then carried out, solidification temperature is 150 DEG C, hardening time 10min.After sample is cooled to room temperature, using low electricity
Hinder the specific insulation of tester measurement transparent conductive film.
To the adhesion strength of base material using maximum load power as index, its measuring method is conductive ink composition：Will test
Copper base material of covering carry out scouring with ethyl acetate and deoil, then conductive ink composition is applied on transparent base, two panels is saturating
Bright base material closes up, and is put in curing oven and solidifies after being fixed using metal racks, and solidification temperature is 150 DEG C, hardening time
20min.After sample is cooled to room temperature, two transparent bases are pulled round about respectively using tensile testing machine, tested
Maximum load power between two transparent bases.Maximum load power is bigger, shows adhesion of the conductive ink composition to base material
Bigger, bonding is more firm.
Each embodiment component proportion of table 1 and test result
Note：Embodiment in upper table, organic solvent is used as using the mixture of ethyl acetate and chloroform；Added in embodiment 6*
1.5% bentonite；The aromatic amine of addition 2% in embodiment 7*；The aromatic amine of addition 8% in embodiment 8*.
From embodiment 5 as can be seen that when the addition of polyacrylonitrile-based carbon fibre is more than epoxy resin, gained is transparent to lead
The specific insulation of conductive film is 2.3E-5 Ω cm, light transmittance 83%.When the addition of polyacrylonitrile-based carbon fibre is less than
During epoxy resin, the specific insulation of gained transparent conductive film is remarkably decreased, and light transmittance significantly improves；Referring to embodiment 1-4,
When the mass ratio of epoxy resin and polyacrylonitrile-based carbon fibre is respectively 3:1、2:1、1.5:1 and 1.2:When 1, gained electrically conducting transparent
The specific insulation of film gradually reduces, and light transmittance gradually steps up.
In embodiment 3 and embodiment 6*, epoxy resin is identical with the mass ratio of polyacrylonitrile-based carbon fibre.Inventor is surveying
Found during examination, after adding organobentonite, the dispersing uniformity of electrically conducting transparent ink composite is more preferable, is applied on base material
Evenly, as can be seen from the table, addition organobentonite can improve electrically conducting transparent ink to the transparent conductive film covered
The electrical conductivity and light transmittance of composition.
In embodiment 3 and embodiment 7*, epoxy resin is identical with the mass ratio of polyacrylonitrile-based carbon fibre.The data from table
As can be seen that after addition aromatic amine, electrically conducting transparent ink composite is more preferable to the caking property of base material.Added in embodiment 8*
8% aromatic amine, thus obtained electrically conducting transparent ink composite bonding is agglomerating, and mobility is poor, can not be coated uniformly on
On bright base material, therefore the correlation test data of the embodiment are not obtained.
Although with reference to illustrative embodiments, invention has been described, but it is to be understood that the present invention does not limit to
The embodiment that Yu Wenzhong is described in detail and shown, in the case of without departing from claims limited range, this
Art personnel can make various changes to the illustrative embodiments.
Claims (9)
1. the electrically conducting transparent ink composite based on nano-silver thread, it is characterised in that include the component of following mass fraction：
Nano-silver thread, 0.5%-15%；
Epoxy resin, 20%-30%；
Polyacrylonitrile-based carbon fibre, 9%-18%；
Organic solvent, 50%-60%；The organic solvent includes the one or more in alcohols, ethers and esters.
2. electrically conducting transparent ink composite as claimed in claim 1, it is characterised in that further comprise following mass fraction
Component：0.5%-2% organobentonite.
3. electrically conducting transparent ink composite as claimed in claim 2, it is characterised in that include the component of following mass fraction：
Nano-silver thread 8%；Epoxy resin, 21.3%；Polyacrylonitrile-based carbon fibre, 14.2%；Organic solvent, 55%；1.5% it is organic
Bentonite.
4. electrically conducting transparent ink composite as claimed in claim 1, it is characterised in that further comprise：Aromatic amine and/or two
Aminodiphenyl base sulfone.
5. electrically conducting transparent ink composite as claimed in claim 4, it is characterised in that the aromatic amine and/or diaminourea two
The mass fraction of phenylsulfone is no more than 5%.
6. electrically conducting transparent ink composite as claimed in claim 1, it is characterised in that the nano-silver thread it is of length no more than
35 μm, draw ratio is 150-300 μm.
7. electrically conducting transparent ink composite as claimed in claim 1, it is characterised in that the epoxy resin and the polypropylene
The mass ratio of itrile group carbon fiber is：1.5-2.0:1.
8. electrically conducting transparent ink composite as claimed in claim 1, it is characterised in that the organic solvent is：Ethyl acetate
And chloroform.
9. using transparent conductive film made from the electrically conducting transparent ink composite as described in claim 1-9 is any.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710543413.8A CN107365528A (en) | 2017-07-05 | 2017-07-05 | Electrically conducting transparent ink composite and transparent conductive film based on nano-silver thread |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710543413.8A CN107365528A (en) | 2017-07-05 | 2017-07-05 | Electrically conducting transparent ink composite and transparent conductive film based on nano-silver thread |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912844A (en) * | 2018-06-27 | 2018-11-30 | 苏州向心力纳米科技有限公司 | A kind of silver ink and preparation method thereof |
| CN109280423A (en) * | 2018-08-31 | 2019-01-29 | 谭亚 | A kind of preparation method of electrically conductive ink |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650652A (en) * | 2013-11-22 | 2015-05-27 | 苏州冷石纳米材料科技有限公司 | Nano-silver conductive ink and preparation method thereof |
| CN105001708A (en) * | 2015-03-31 | 2015-10-28 | 安徽省嘉信包装印务有限公司 | Transparent electric-conduction ink |
-
2017
- 2017-07-05 CN CN201710543413.8A patent/CN107365528A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650652A (en) * | 2013-11-22 | 2015-05-27 | 苏州冷石纳米材料科技有限公司 | Nano-silver conductive ink and preparation method thereof |
| CN105001708A (en) * | 2015-03-31 | 2015-10-28 | 安徽省嘉信包装印务有限公司 | Transparent electric-conduction ink |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912844A (en) * | 2018-06-27 | 2018-11-30 | 苏州向心力纳米科技有限公司 | A kind of silver ink and preparation method thereof |
| CN109280423A (en) * | 2018-08-31 | 2019-01-29 | 谭亚 | A kind of preparation method of electrically conductive ink |
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