A kind of composite conducting ink film and preparation method thereof
Technical field
The present invention relates to printing-ink technical field, particularly relate to a kind of composite conducting ink film and preparation method thereof.
Background technology
Ink is the important materials for packaging material printing, and it is by printing by pattern, word and Informational Expression on the substrate.Along with the development of printing technology, the kind of ink is continuously increased, and is generally divided into letterpress inks, planographic ink, gravure printing ink, stencil printing ink, special printing inks according to mode of printing.Wherein, special printing inks can be divided into conductive ink, foam ink, magnetic ink and fluorescent ink etc..In recent ten years, developing rapidly and reaching its maturity along with electronic technology, the development of conductive ink is increasingly subject to pay attention to, and especially with the quickly universal of RF identification (RFID) technology application and market development, has more promoted the exploitation dynamics to electrically conductive ink in industry.
Electrically conductive ink conductive material is dispersed in the paste-like ink made in link stuff, generally it is made up of conductive material, organic polymer carrier, property-modifying additive and solvent, thus there is a degree of conduction property, being widely used of the fields such as printed circuit, membrane switch panel, plating bottom, keyboard contact, compliant conductive winding displacement, electronic shield, RF identification (RFID).
Conductive material in electrically conductive ink is generally metal powder, common are silver, copper, nickel, aluminum, ferrum etc., wherein bronze system electrically conductive ink, argentum powder system electrically conductive ink, copper powder system electrically conductive ink have reached practical requirement, but outside desilver powder, bronze is expensive and other metal powders easily aoxidize and reduce electric conductivity.Therefore, current low resistance conductive ink uses argentum powder system electrically conductive ink all in a large number.
Prior art discloses multiple electrically conductive ink, as patent 201010296831.X discloses a kind of electrically conductive ink and preparation method thereof, in mass fraction, including: the flake silver powder of 40~55%, the silver-coated copper powder of 5~10%, 30~45% organic carrier A, 3~5% the coupling agent of organic carrier B and 0.1~0.2%.
Patent 201010293058.1 discloses a kind of Halogen-free low-temperature electrically conductive ink and preparation method thereof, and this electrically conductive ink is prepared from by the raw material of following mass percentage content: the flake silver powder of 50~60%;The spherical argentum powder of 2~5%;The organic carrier A of 10~20%;The organic carrier B of 15~25%, the dispersant of 0.2~0.5% and 0.1~0.2% coupling agent.
But, both the above electrically conductive ink argentum powder content is higher, and argentum powder belongs to noble metal, which results in the high expensive of electrically conductive ink.It addition, silver ion migration phenomenon in use easily occurs in silver paste printing ink, in wet environment, under electric field action, silver is by electrolysis, and positively charged argent cation shifts to negative electrode, short trouble finally occurs.These all limit the application of silver paste printing ink.
CN103436099A discloses a kind of composite conducting ink, meter includes by weight: the mixture of film-forming resin 5~30 parts, flake silver powder and nanometer silver powder or flake silver powder 20~40 parts, the mixture of Graphene and nano graphite flakes or Graphene 0.1~5 part, additive 1.5~11 parts, surplus is organic solvent.It has relatively low silver content, also has good conductive effect simultaneously.But, its silver content is still of a relatively high, and the electric conductivity of its composite conducting ink film made and non-oxidizability need to be improved further.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of composite conducting ink film and preparation method thereof, composite conducting ink film provided by the invention has the silver content lower than prior art, cost is low, simultaneously, its electric conductivity and non-oxidizability are very good, and the sheet resistance of the composite conducting ink film of the present invention is at below 75m Ω.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
First aspect, the invention provides a kind of composite conducting ink film, it is characterised in that meter includes following raw material components by weight:
Preferably, described Graphene is with the mixture of graphene oxide, and the mass ratio of Graphene and graphene oxide is 1:(1.5~3), for instance can be 1:1,1:1.3,1:1.5,1:2,1:2.5 or 1:3 etc..
Preferably, also including additive 1.5~11 parts in the raw material components of described conductive oil ink film, described additive includes the organic solvent of adhesion promoter 0.5~5 part and surplus, and described adhesion promoter is silane coupler class or chlorinated polyolefin hydro carbons.
Preferably, the lamella size of described Graphene and graphene oxide independently be 2 μm~10 μm.
Preferably, described flake silver powder thickness < 100nm;The D50 of described flake silver powder is 3 μm~7 μm;The particle diameter < 100nm of described nanometer silver powder;Described flake silver powder is with the mixture of nanometer silver powder, and the mass ratio of flake silver powder and nanometer silver powder is (8~10): 1.
Preferably, described film-forming resin is one or more in epoxy resin, polyester resin, acrylic resin, polyamide, phenol-formaldehyde resin modified or cellulosic resin.
Preferably, it is characterised in that described organic solvent is one or more in alcohols, ethers, ketone and esters solvent.
Preferably, described additive also includes in dispersant, levelling agent, defoamer, anti-settling agent, thixotropic agent, white carbon or Pulvis Talci one or more.
Second aspect, the preparation method that the present invention provides conductive oil ink film as described in relation to the first aspect, said method comprising the steps of:
(1) hot copper steam-plating metal level in substrate;
(2) resin solution of film resin it is configured to, it is subsequently adding mixture or the flake silver powder of flake silver powder and nanometer silver powder, the mixture of Graphene and graphene oxide and additive, carries out pre-dispersed process with stirring, grind again and carry out dispersion process, obtain electrically conductive ink slurry;
(3) the electrically conductive ink slurry that step (2) obtains is coated on the evaporation that step (1) obtains and has in the substrate of copper metal layer, solidify, obtain conductive oil ink film.
Preferably, in described step (2), the time of stirring is 10~40min, for instance can be 10min, 15min, 20min, 30min, 35min or 40min etc..
Preferably, the number of times ground in described step (2) is 2~6 times.
Preferably, the temperature solidified in described step (3) is 70~100 DEG C, for instance can be 70 DEG C, 80 DEG C, 85 DEG C, 90 DEG C or 100 DEG C etc..
Preferably, the time solidified in described step (3) is 10~15min, for instance can be 10min, 12min, 13min or 15min etc..
Adhesion promoter of the present invention is preferably silane coupler class or chlorinated polyolefin hydro carbons, more preferably silane coupler, it is most preferred that for DOW CORNING Z-6040;There is no particular restriction to described adhesion promoter for the present invention, and with the conventional adhesion promoter for electrically conductive ink well known to those skilled in the art, its effect is preferably the adhesive force improving the films such as PET, PE and PP.
Organic solvent of the present invention is preferably one or more in alcohols, ethers, ketone and esters solvent, more preferably one or both of butyl acetate, diethylene glycol dibenzoate and butyl;There is no particular restriction to described organic solvent for the present invention, and with the conventional organic solvent for electrically conductive ink well known to those skilled in the art, those skilled in the art can select corresponding organic solvent according to specific needs.
Described dispersion is processed and is not particularly limited by the present invention, it is preferred to first adopt blender carry out fully pre-dispersed after, then carry out dispersion process with grinder.Blender is not particularly limited by the present invention, with mixing plant well known to those skilled in the art;The condition of present invention stirring is not particularly limited, with stirring condition well known to those skilled in the art;Grinder is not particularly limited by the present invention, it is preferred to adopt three-roll grinder to carry out dispersion process;The grinding number of times of grinder of the present invention is not particularly limited, it is preferred to grind for 4 times;The condition that the present invention grinds is not particularly limited, with grinding condition well known to those skilled in the art.
Compared with the prior art, the method have the advantages that
The present invention by adding the mixture of copper, Graphene and graphene oxide in the raw material components of composite conducting ink film, and regulate the matching relationship between both components and other components, the content that uses noble silver can be greatly decreased in prior art, and electric conductivity and non-oxidizability are all significantly improved;In the present invention, copper steam-plating metal level is to substrate, is further continued for, at its surface-coated electrically conductive ink slurry, being conducive to improving associativity and electric conductivity, and the sheet resistance of the composite conducting ink film obtained is at below 75m Ω.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
Embodiment 1
First 10g butyl acetate and 25g diethylene glycol dibenzoate are mixed to get mixed solution, obtain resin solution.Then by 1.3g dispersant DOW CORNING DC-3, the mixture (Graphene and graphene oxide mass ratio are 1:1.5) of 0.5g Graphene and graphene oxide, 10g flake silver powder, 2g nanometer of spherical argentum powder and 1.5g silane coupler DOW CORNING Z-6040 and 70g ethylene glycol join in resin solution, finally obtain mixture.Said mixture is adopted blender carry out fully pre-dispersed after, re-use three-roll grinder and carry out dispersion process, three-roll grinder carry out 4 times grind, obtain electrically conductive ink slurry.
With PET film for substrate, at substrate surface evaporation metal copper, obtain being deposited with the substrate of copper metal layer.
Then above-mentioned electrically conductive ink slurry is coated on evaporation and has in the substrate of copper metal layer, use the half tone of 200 orders, carry out silk screen printing, then when temperature is 70 DEG C dry solidification 15 minutes, finally give composite conducting ink film.
Above-mentioned solidified oil ink film is detected, and its sheet resistance is 74m Ω;Using China's pencil, it is carried out hardness test, hardness is 4H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 80m Ω.
Embodiment 2
First 6g propandiol butyl ether acetate and 2g butyl are mixed to get mixed solution, then are added thereto to 2g epoxy resin 860, obtain resin solution.Then the mixture (Graphene and graphene oxide mass ratio are 1:3) of 1.5g dispersant DOW CORNING DC-3,1.5g Graphene with graphene oxide, 5g flake silver powder, and 50g ethylene glycol are joined in resin solution, finally obtain mixture.Said mixture is adopted blender carry out fully pre-dispersed after, re-use three-roll grinder and carry out dispersion process, three-roll grinder carry out 2 times grind after, obtain electrically conductive ink slurry.
With silicon chip for substrate, at substrate surface evaporation metal copper, obtain being deposited with the substrate of copper metal layer.
Then above-mentioned electrically conductive ink slurry is coated on evaporation and has in the substrate of copper metal layer, use the half tone of 200 orders, carry out silk screen printing, then when temperature is 100 DEG C dry solidification 10 minutes, finally give composite conducting ink film film.
Above-mentioned solidified oil ink film is detected, and its sheet resistance is 70m Ω;Using China's pencil, it is carried out hardness test, hardness is 5H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 85m Ω.
Embodiment 3
First 10g propandiol butyl ether acetate and 10g butyl are mixed to get mixed solution, then are added thereto to the polyester resin 8060 of 5g, obtain resin solution.Then by the mixture (Graphene and graphene oxide mass ratio are 1:2) of 1g Graphene with graphene oxide, 1.7g white carbon, 8g flake silver powder and 55g ethylene glycol join in resin solution, finally obtain mixture.Said mixture is adopted blender carry out fully pre-dispersed after, re-use three-roll grinder and carry out dispersion process, three-roll grinder carry out 6 times grind after, obtain composite conducting ink slurry.
With PET film for substrate, at substrate surface evaporation metal copper, obtain being deposited with the substrate of copper metal layer.
Then above-mentioned electrically conductive ink slurry is coated on evaporation and has in the substrate of copper metal layer, use the half tone of 200 orders, carry out silk screen printing, then when temperature is 900 DEG C dry solidification 12 minutes, finally give composite conducting ink film.
Above-mentioned solidified oil ink film is detected, and its sheet resistance is 68m Ω;Using China's pencil, it is carried out hardness test, hardness is 5H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 83m Ω.
Comparative example 1
Except not cupric, the kind of other each components is identical with embodiment 1 with content.
The ink film that this comparative example 1 is obtained detects, and its sheet resistance is 180m Ω;Using China's pencil, it is carried out hardness test, hardness is 3H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 152m Ω.
Comparative example 2
Except the mixture of Graphene Yu graphene oxide is replaced with Graphene, the kind of other each components is identical with embodiment 1 with content.
The ink film that this comparative example 1 is obtained detects, and its sheet resistance is 120m Ω;Using China's pencil, it is carried out hardness test, hardness is 4H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 152m Ω.
Comparative example 3
Except the mixture of Graphene Yu graphene oxide is replaced with graphene oxide, the kind of other each components is identical with embodiment 1 with content.
The ink film that this comparative example 1 is obtained detects, and its sheet resistance is 130m Ω;Using China's pencil, it is carried out hardness test, hardness is 2H.After above-mentioned solidified oil ink film doubling, adopting 2kg counterweight to apply pressure, back and forth doubling 10 times, recording sheet resistance is 168m Ω.
The applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, does not namely mean that the present invention has to rely on above-mentioned method detailed and could implement.The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.