A kind of composite conducting ink film and preparation method thereof
Technical field
The present invention relates to printing technical field of ink more particularly to a kind of composite conducting ink film and preparation method thereof.
Background technique
Ink is important materials used for printing packaging materials, it is being held pattern, text and Informational Expression by printing
It prints on object.With the development of printing technology, the kind of ink is continuously increased, and is usually divided into letterpress oil according to mode of printing
Ink, planographic ink, gravure printing ink, stencil printing ink, special printing inks.Wherein, special printing inks can divide
For conductive ink, foam ink, magnetic ink and fluorescent ink etc..In recent ten years, with the rapid development of electronic technology
With reach its maturity, the development of conductive ink is paid more and more attention, especially with the fast of radio frequency identification (RFID) technical application
Speed is popularized and market development, has more pushed the exploitation dynamics in industry to electrically conductive ink.
Electrically conductive ink is to be dispersed in manufactured paste-like ink in link stuff with conductive material, usually by conductive material, organic
Polymer support, modified additive and solvent composition, thus there is a degree of conduction property, it is opened in printed circuit, film
The application for closing the fields such as panel, plating bottom, keyboard contact, compliant conductive winding displacement, electronic shield, radio frequency identification (RFID) is wide
It is general.
Conductive material in electrically conductive ink is usually metal powder, common are silver, copper, nickel, aluminium, iron etc., wherein bronze system
Electrically conductive ink, silver powder system electrically conductive ink, copper powder system electrically conductive ink have had reached practical requirement, but in addition to silver powder, bronze
It is expensive and other metal powders are easy to oxidize and reduce electric conductivity.Therefore, low resistance conductive ink all largely uses at present
Silver powder system electrically conductive ink.
Prior art discloses a variety of electrically conductive inks, as patent 201010296831.X disclose a kind of electrically conductive ink and its
Preparation method, based on mass fraction, comprising: 40~55% flake silver powder, 5~10% silver-coated copper powder, 30~45% have
Airborne body A, 3~5% organic carrier B and 0.1~0.2% coupling agent.
Patent 201010293058.1 discloses a kind of Halogen-free low-temperature electrically conductive ink and preparation method thereof, the electrically conductive ink by
The raw material of following mass percentage content is prepared: 50~60% flake silver powder;2~5% spherical silver powder;10~20%
Organic carrier A;15~25% organic carrier B, 0.2~0.5% dispersing agent and 0.1~0.2% coupling agent.
But both the above electrically conductive ink silver powder content is higher, and silver powder belongs to noble metal, which results in electrically conductive inks
High expensive.In addition, silver paste printing ink is easy to appear silver ion migration phenomenon in use, in wet environment, in electricity
Silver is electrolysed under field action, and positively charged metallic silver cation shifts to cathode, short trouble finally occurs.These are all limited
The application of silver paste printing ink.
CN 103436099A discloses a kind of composite conducting ink, include: according to parts by weight 5~30 parts of film-forming resin,
20~40 parts of the mixture or flake silver powder of flake silver powder and nano-silver powder, the mixture or graphite of graphene and nano graphite flakes
0.1~5 part of alkene, 1.5~11 parts of additive, surplus is organic solvent.It also has good with lower silver content
Conductive effect.But silver content is still relatively high, and the electric conductivity and inoxidizability of its manufactured composite conducting ink film
Need to be further increased.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of composite conducting ink film and
Preparation method, composite conducting ink film provided by the invention has the silver content lower than the prior art, at low cost, together
When, electric conductivity and inoxidizability are very good, and the sheet resistance of composite conducting ink film of the invention is below 75m Ω.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of composite conducting ink films, which is characterized in that include according to parts by weight with
Lower raw material components:
Preferably, in the mixture of the graphene and graphene oxide, the mass ratio of graphene and graphene oxide is
1:(1.5~3), it may be, for example, 1:1,1:1.3,1:1.5,1:2,1:2.5 or 1:3 etc..
It preferably, further include 1.5~11 parts of additive in the raw material components of the conductive oil ink film, the additive includes
The organic solvent of 0.5~5 part of adhesion promoter and surplus, the adhesion promoter are silane coupling agent class or chlorinated polyolefin
Hydro carbons.
Preferably, the lamella size of the graphene and graphene oxide independently is 2 μm~10 μm.
Preferably, the flake silver powder thickness < 100nm;The D50 of the flake silver powder is 3 μm~7 μm;The nano silver
The partial size < 100nm of powder;In the mixture of the flake silver powder and nano-silver powder, the mass ratio of flake silver powder and nano-silver powder is
(8~10): 1.
Preferably, the film-forming resin is epoxy resin, polyester resin, acrylic resin, polyamide, modification
One of phenolic resin or cellulosic resin are a variety of.
Preferably, which is characterized in that the organic solvent is one of alcohols, ethers, ketone and esters solvent or more
Kind.
Preferably, further include in the additive dispersing agent, levelling agent, defoaming agent, anti-settling agent, thixotropic agent, white carbon black or
One of talcum powder is a variety of.
Second aspect, the present invention provide the preparation method of conductive oil ink film as described in relation to the first aspect, the method includes
Following steps:
(1) the hot evaporation copper metal layer in substrate;
(2) resin solution of film-forming resin is prepared, mixture or the sheet silver of flake silver powder and nano-silver powder is then added
The mixture and additive of powder, graphene and graphene oxide carry out pre-dispersed processing with stirring, then grind and carry out at dispersion
Reason, obtains electrically conductive ink slurry;
(3) the electrically conductive ink slurry that step (2) obtains is coated on the substrate for being vapor-deposited with copper metal layer that step (1) obtains
On, solidification obtains conductive oil ink film.
Preferably, the time stirred in the step (2) is 10~40min, may be, for example, 10min, 15min, 20min,
30min, 35min or 40min etc..
Preferably, the number ground in the step (2) is 2~6 times.
Preferably, cured temperature is 70~100 DEG C in the step (3), may be, for example, 70 DEG C, 80 DEG C, 85 DEG C, 90 DEG C
Or 100 DEG C etc..
Preferably, in the step (3) the cured time be 10~15min, may be, for example, 10min, 12min, 13min or
15min etc..
Adhesion promoter of the present invention is preferably silane coupling agent class or chlorinated polyolefin hydro carbons, and more preferably silane is even
Join agent, most preferably DOW CORNING Z-6040;There is no particular restriction to the adhesion promoter by the present invention, with those skilled in the art
The conventional adhesion promoter of electrically conductive ink is used for known to member, effect preferably to improve the attached of the films such as PET, PE and PP
Put forth effort.
Organic solvent of the present invention is preferably one of alcohols, ethers, ketone and esters solvent or a variety of, more preferably
For the one or two of butyl acetate, diethylene glycol dibenzoate and butyl;The present invention is to institute
Stating organic solvent, there is no particular restriction, with the conventional organic solvent well known to those skilled in the art for electrically conductive ink,
Those skilled in the art can select corresponding organic solvent according to specific needs.
The decentralized processing is not particularly limited in the present invention, preferably first using blender carry out sufficiently it is pre-dispersed after,
Decentralized processing is carried out with grinder again.Blender is not particularly limited in the present invention, with stirring well known to those skilled in the art
Equipment;The condition that the present invention stirs is not particularly limited, with stirring condition well known to those skilled in the art;This hair
It is bright that grinder is not particularly limited, decentralized processing is preferably carried out using three-roll grinder;The grinding time of grinder of the present invention
Number is not particularly limited, preferably 4 times grindings;The condition that the present invention is ground is not particularly limited, ripe with those skilled in the art
The grinding condition known.
Compared with the prior art, the invention has the following advantages:
The mixing that the present invention passes through addition copper, graphene and graphene oxide in the raw material components of composite conducting ink film
Object, and the matching relationship between both components and other components is adjusted, it can be greatly decreased in the prior art using noble silver
Content, and electric conductivity and inoxidizability are all significantly improved;It is deposited on copper metal layer to substrate, is further continued in the present invention
Electrically conductive ink slurry is coated on its surface, is conducive to improve associativity and electric conductivity, the table of obtained composite conducting ink film
Surface resistance is below 75m Ω.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
10g butyl acetate and 25g diethylene glycol dibenzoate are mixed to get mixed solution first, obtained
To resin solution.Then by the mixture of 1.3g dispersing agent DOW CORNING DC-3,0.5g graphene and graphene oxide (graphene with
Graphene oxide mass ratio is 1:1.5), 10g flake silver powder, 2g nanometers of spherical silver powder and 1.5g silane coupling agent DOW CORNING
Z-6040 and 70g ethylene glycol is added in resin solution, finally obtains mixture.Said mixture is filled using blender
It after point pre-dispersed, reuse three-roll grinder and carries out decentralized processing, three-roll grinder carries out 4 grindings, obtains electrically conductive ink slurry
Material.
Using PET plastic film as substrate, in substrate surface evaporation metal copper, the substrate for being vapor-deposited with copper metal layer is obtained.
Then above-mentioned electrically conductive ink slurry is coated on and is vapor-deposited in the substrate of copper metal layer, using the halftone of 200 mesh, into
Row silk-screen printing, then dry solidification 15 minutes under conditions of temperature is 70 DEG C, finally obtain composite conducting ink film.
Above-mentioned solidified oil ink film is detected, sheet resistance is 74m Ω;Using Chinese pencil, hardness is carried out to it
Test, hardness 4H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, doubling 10 times, measure table back and forth
Surface resistance is 80m Ω.
Embodiment 2
6g propylene glycol butyl ether acetate and 2g butyl are mixed to get mixed solution first, then are added thereto
2g epoxy resin 860, obtains resin solution.Then by 1.5g dispersing agent DOW CORNING DC-3,1.5g graphene and graphene oxide
Mixture (graphene and graphene oxide mass ratio be 1:3), it is molten that 5g flake silver powder and 50g ethylene glycol are added to resin
In liquid, mixture is finally obtained.By said mixture using blender carry out sufficiently it is pre-dispersed after, reuse three-roll grinder into
Row decentralized processing obtains electrically conductive ink slurry after three-roll grinder carries out 2 grindings.
Using silicon wafer as substrate, in substrate surface evaporation metal copper, the substrate for being vapor-deposited with copper metal layer is obtained.
Then above-mentioned electrically conductive ink slurry is coated on and is vapor-deposited in the substrate of copper metal layer, using the halftone of 200 mesh, into
Row silk-screen printing, then dry solidification 10 minutes under conditions of temperature is 100 DEG C, finally obtain composite conducting ink film film.
Above-mentioned solidified oil ink film is detected, sheet resistance is 70m Ω;Using Chinese pencil, hardness is carried out to it
Test, hardness 5H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, doubling 10 times, measure table back and forth
Surface resistance is 85m Ω.
Embodiment 3
10g propylene glycol butyl ether acetate and 10g butyl are mixed to get mixed solution first, then added thereto
The polyester resin 8060 for entering 5g, obtains resin solution.Then by mixture (graphene and the oxygen of 1g graphene and graphene oxide
Graphite alkene mass ratio is 1:2), 1.7g white carbon black, 8g flake silver powder and 55g ethylene glycol are added in resin solution, most
After obtain mixture.By said mixture using blender carry out sufficiently it is pre-dispersed after, reuse three-roll grinder and dispersed
Processing obtains composite conducting ink slurry after three-roll grinder carries out 6 grindings.
Using PET plastic film as substrate, in substrate surface evaporation metal copper, the substrate for being vapor-deposited with copper metal layer is obtained.
Then above-mentioned electrically conductive ink slurry is coated on and is vapor-deposited in the substrate of copper metal layer, using the halftone of 200 mesh, into
Row silk-screen printing, then dry solidification 12 minutes under conditions of temperature is 900 DEG C, finally obtain composite conducting ink film.
Above-mentioned solidified oil ink film is detected, sheet resistance is 68m Ω;Using Chinese pencil, hardness is carried out to it
Test, hardness 5H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, doubling 10 times, measure table back and forth
Surface resistance is 83m Ω.
Comparative example 1
In addition to not cupric, the type and content of other each components are same as Example 1.
The ink film obtained to this comparative example 1 detects, and sheet resistance is 180m Ω;Using Chinese pencil, to it
Carry out hardness test, hardness 3H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, back and forth doubling 10
Secondary, measuring sheet resistance is 152m Ω.
Comparative example 2
In addition to the mixture of graphene and graphene oxide is replaced with graphene, the type and content of other each components with
Embodiment 1 is identical.
The ink film obtained to this comparative example 1 detects, and sheet resistance is 120m Ω;Using Chinese pencil, to it
Carry out hardness test, hardness 4H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, back and forth doubling 10
Secondary, measuring sheet resistance is 152m Ω.
Comparative example 3
In addition to the mixture of graphene and graphene oxide is replaced with graphene oxide, the type of other each components and contain
It measures same as Example 1.
The ink film obtained to this comparative example 1 detects, and sheet resistance is 130m Ω;Using Chinese pencil, to it
Carry out hardness test, hardness 2H.After above-mentioned solidified oil ink film doubling, pressure is applied using 2kg counterweight, back and forth doubling 10
Secondary, measuring sheet resistance is 168m Ω.
The applicant's statement, method detailed of the invention that the present invention is explained by the above embodiments, but the present invention is not
Be confined to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of each raw material of product of the present invention
Addition, the selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.