CN104130629A - Electric-conduction ink and preparation method thereof - Google Patents
Electric-conduction ink and preparation method thereof Download PDFInfo
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- CN104130629A CN104130629A CN201410371310.4A CN201410371310A CN104130629A CN 104130629 A CN104130629 A CN 104130629A CN 201410371310 A CN201410371310 A CN 201410371310A CN 104130629 A CN104130629 A CN 104130629A
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- 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
Abstract
Provided electric-conduction ink comprises a metal nanometer particle, a dispersing agent, alpha-hydroxy polycarboxylic acid and a solvent; the surface of the metal nanometer particle is provided with a metal element oxide cladding layer of the metal nanometer particle; and the dispersing agent is a polymer with a polyether main-chain skeleton and a terminal active functional group. According to the electric-conduction ink, by using the polymer with the polyether main-chain skeleton and the terminal active functional group and utilizing the terminal active functional group to form firm anchoring effect with the metal nanometer particle surface, the polyether main chain generates steric hindrance stabilizing effect, agglomeration among metal nanometer particles is resisted, and also the polyether main chain is easy to crack and degrade under a heat treatment condition and are partially eliminated by forming a micromolecule product, so that residue is avoided and the electric conductivity of a sintered conducting circuit is facilitated. Also, by compounding and using alpha-hydroxy polycarboxylic acid, the electric conductivity of the sintered conducting circuit is synergistically improved, and also the electric-conduction ink possesses excellent dispersity and anti-oxidation property.
Description
Technical field
The invention belongs to printed electronic technical field of ink, be specifically related to a kind of conductive ink and preparation method thereof.
Background technology
Full printed electronics technology (Print Full Electronic Technology) refer to employing fast, efficiently and flexibly printing technology directly on substrate, form conducting wire and figure, or the process of other electron devices and system.The key that wherein forms conducting wire and figure is conductive ink, generally metal nanoparticle, protective material, dispersion agent, solvent and other auxiliary agents, consists of.
Existing in order to obtain metal nanoparticle dispersiveness and the good conductive ink of oxidation-resistance, in system, usually need to use the materials such as more lipid acid, chain alkyl amine, polyvinylpyrrolidone, polymine, polyvinyl alcohol as the dispersion agent of metal nanoparticle.In order to improve the adaptability of conductive ink to different substrate materials, people wish that conductive ink can realize low-temperature sintering (300 ℃ of <); But the dispersion agent that is coated on metal nanoparticle surface in low temperature sintering technology is difficult to remove, remains in and in conducting wire, affect electroconductibility.Meanwhile, the addition of dispersion agent again can not be too small, and when too small, dispersion agent is excessively thin at metal nanoparticle surface formation coating layer, not only can not keep the dispersiveness of metal nanoparticle, also can reduce the oxidation-resistance of metal nanoparticle.Therefore the difficulty that, the electroconductibility of the dispersiveness of metal nanoparticle, oxidation-resistance and conducting wire is taken into account is very large.And metal nanoparticle, in manufacture, storage or dispersion process, inevitably forms oxide skin more or less on its surface, if these oxide compounds are not reduced in sintering process, will inevitably hinder the raising of conducting wire electroconductibility.
Based on above-mentioned defect, publication number is the method that the patent of invention of CN1792127A discloses a kind of fine copper particle sintering in reductibility organic compound atmosphere, reductibility organic compound is that to have to be the alcohol compound containing the hydroxyl of oxygen base or aldehyde radical by oxidation transformation, and the reduction that simultaneously realizes nano-metal particle promotes electroconductibility.Yet these gaseous reduction materials have inflammable and explosive defect, in preparation process, control accuracy and difficulty are huge, the means that therefore do not have temporarily the electroconductibility of dispersiveness, oxidation-resistance and the conducting wire of good metal nanoparticle to take into account in conductive ink.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, provide a kind of metal nanoparticle to have good dispersiveness and oxidation-resistance, and organic substance residues is few after low-temperature sintering simultaneously, the high conductive conductive ink in conducting wire.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A conductive ink, comprises metal nanoparticle, dispersion agent, Alpha-hydroxy polycarboxylic acid and solvent; Wherein,
Described metal nanoparticle surface has the metallic element oxide compound coating layer of this metal nanoparticle;
Described dispersion agent is the polymkeric substance with polyether backbone skeleton and end active function groups.
Conductive ink of the present invention has the polymkeric substance of polyether backbone skeleton and end active function groups by use, utilize its end active function groups and metal nanoparticle surface to form firmly anchorage effect, polyether backbone produces sterically hindered stabilization, stop the reunion between metal nanoparticle, and easily there is fracture degraded in its polyether backbone under heat-treat condition, form small molecules product and partly remove, avoiding remaining being beneficial to and improve the electroconductibility of burning till conducting wire.Simultaneously, composite use Alpha-hydroxy polycarboxylic acid also, because it has ion characteristic and reductibility, electrostatic stabilization effect can be provided and can reducing metal in heat treatment process the oxide compound of nano grain surface, and within the scope of 150～300 ℃, can there is thermal destruction and remove, thereby improve the electroconductibility of burning till conducting wire, there is good dispersiveness and oxidation-resistance simultaneously.
The present invention further also proposes a kind of preparation method of above-mentioned conductive ink, comprises the steps:
Obtain the metal nanoparticle that surface has oxide compound coating layer;
Described metal nanoparticle is coated in solvent with dispersion agent and obtains preliminary dispersion liquid, the consumption of wherein said dispersion agent be dispersion agent to the saturated covering amount of metal nanoparticle 50%～120%;
In described preliminary dispersion liquid, add Alpha-hydroxy polycarboxylic acid, and the dispersed conductive ink that obtains.
Adopt the above-mentioned preparation method of the present invention, according to the raw material of institute's conductive ink of the present invention, in preparation, raw material is carried out to specific substep dispersion according to its character, and in dispersion according to measurement result feedback consumption, make each performances such as dispersiveness, electroconductibility, oxidation-resistance of the conductive ink of preparation realize optimum balance.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of conductive ink, comprises metal nanoparticle, dispersion agent, Alpha-hydroxy polycarboxylic acid and solvent; Wherein, described dispersion agent is the polymkeric substance with polyether backbone skeleton and end active function groups.
Wherein, metal nanoparticle of the present invention adopts at least one nano particle in copper, silver, gold, nickel, aluminium, platinum, palladium or its alloy; And metal nanoparticle surface has the oxide passivation layer of its metallic element.Oxide passivation layer is coated on metal nanoparticle surface, except contributing to improve the oxidation-resistance of metal nanoparticle, the adsorptive power of the anchoring group that also contributes to improve dispersion agent to metal nanoparticle surface, thus the dispersion stabilization of metal nanoparticle improved.The content of the oxide passivation layer on metal nanoparticle surface can be measured by carry out thermogravimetric analysis in having oxygen atmosphere; For considering from reducing the effect of the resistivity of burning till conducting wire, the mass percent that preferred oxides passivation layer accounts for metal nanoparticle is less than 10%.The particle size range of the metal nanoparticle that preferably, the present invention uses is 5～100nm; Because when metal nanoparticle particle diameter is greater than 100nm, the settling velocity of its dispersion liquid can be accelerated, and the needed energy of sintering is also higher, is difficult for realizing low-temperature sintering; When the particle diameter of metal nanoparticle is less than 5nm, the specific surface area of these particles becomes very large so, and activity is higher, and the amount that realizes the needed dispersion agent of stable dispersion is also larger, organic impurity residual after sintering increases, thereby reduces the electroconductibility of burning till conducting wire.
Further, above-mentioned dispersion agent adopts the polymkeric substance with polyether backbone skeleton and end active function groups, its polyether backbone skeleton is comprised of oxyethyl group (EO) and/or propoxy-(PO) structural unit, and its end active function groups is amino and/or carboxyl.This has the active function groups of the polymkeric substance of polyether backbone skeleton and end active function groups, as amino or carboxyl, can form organometallic compound or organometallic complex with the oxide passivation layer on metal nanoparticle surface and adsorb; And its polyether backbone has good snappiness and is easy to swing, forms good sterically hindered effect, is beneficial to the reunion stoping between metal nanoparticle, thereby improve the dispersiveness of metal nanoparticle; By the ratio of oxyethyl group (EO) and propoxy-(PO) in adjusting polyether backbone, can also change the consistency of polymkeric substance and solvent system again.
For structure linearity and reduction redox residual effect, the polymkeric substance of polyether backbone skeleton and end active function groups preferably adopts the polyether backbone skeleton of following representation and the polymkeric substance of end active function groups in force:
In formula, R represents amino or the carboxyl of active function groups, R
1represent H atom or methyl, R
2represent hydrogen atom or alkyl, R
3represent a kind of in alkyl, alkoxyl group, hydroxyl and aldehyde radical; X and y represent 0 or positive integer, and x+y>=2; N represents to be greater than 1 positive integer, and m represents positive integer.
When the polyether backbone of polymkeric substance contains more C-O key, C-O bond dissociation energy (351kJ/mol) is slightly lower than the C-C bond dissociation energy (360kJ/mol) on long-chain hydrocarbon polymkeric substance (as polyethylene, polypropylene and polyacrylic resin), therefore, take the thermostability of the polymkeric substance that polyethers is main chain poorer.If polyether backbone contains more propoxy-(PO), pending methyl group on propoxy-(PO) makes to be full of on main chain branch point, methyne hydrogen on branch point is more easily taken away, and pending methyl group also can weaken C-C key in polyether backbone and the bond energy of C-O key, thereby make the further variation of thermostability of polyether backbone.The C-O key of polyether backbone just starts to be subject to thermal destruction at the temperature higher than 160 ℃, and at higher temperature, C-C key also can rupture.Under oxygen free condition, directly there is random homolysis chain-breaking reaction and degrade in the C-O key in polyether backbone and C-C key, it is the thermal destruction product of ketone, aldehyde, alcohol and ether that the product after thermal destruction has low-molecular-weight polyethers, ethanol, acetaldehyde, propionic aldehyde, acetone, propylene and other end-group structures.Under aerobic conditions, the C-O key in polyether backbone and C-C key can occur random homolysis chain-breaking reaction, and in polyether backbone, the existence of Sauerstoffatom increases the unstable of hydrogen on its α position carbon atom, makes polyether backbone that thermal oxidative reaction more easily occur.Adopt and above-mentionedly there is the polymkeric substance of polyether backbone skeleton as the dispersion agent of conductive ink, easy thermal destruction becomes volatile small molecules product during sintering so, can reduce the residual quantity of burning till organic impurity in conducting wire, thereby be conducive to improve the electroconductibility of conducting wire.
In the above-described embodiment, further preferably the weight-average molecular weight with the polymkeric substance of polyether backbone skeleton and end active function groups of the present invention is 500～4000; When its weight-average molecular weight is lower than 500, sterically hindered effect reduces, and is unfavorable for improving the dispersiveness of metal nanoparticle; When its weight-average molecular weight is higher than 4000, intermolecular reactive force increases, and molecular chain is elongated, and intermolecular winding probability increases, thereby reduces thermal degradation, is unfavorable for improving the electroconductibility of burning till conducting wire.
In use,
the polymkeric substance of structure has the polyetheramine of U.S. HUNTSMAN company
b-60, B-200, L-100, L-200, L-207, L-300 etc.And it is another kind of
the polymkeric substance of structure, as methoxyl group polyglycol acetic acid, methoxyl group polyglycol propionic acid, methoxy poly (ethylene glycol) amine, α-aldehyde radical-ω-carboxy polyethylene glycol, α-aldehyde radical-omega-amino-polyoxyethylene glycol, α-carboxyl-ω-hydroxyl polyoxyethylene glycol, alpha-amino group-ω-hydroxyl polyoxyethylene glycol etc., concrete structure can be referring to as follows:
(methoxyl group polyglycol acetic acid),
(methoxyl group polyglycol propionic acid),
(methoxy poly (ethylene glycol) amine),
(alpha-amino group-ω-hydroxyl polyoxyethylene glycol).
Further, the Alpha-hydroxy polycarboxylic acid adopting in the present invention contains more than 1 or 1 hydroxyl in molecular structure, and 2 or 2 carboxyls above, and has at least on the α position carbon atom of 1 carboxyl and have hydroxyl.Wherein, carboxyl can form organometallic compound or organometallic complex with the oxide passivation layer on metal nanoparticle surface and adsorb, the sterically hindered effect of these micromolecular Alpha-hydroxy polycarboxylic acids does not have the polymkeric substance of polyether backbone skeleton and end active function groups as the aforementioned, but it has ion characteristic, can give electric charge on metal nanoparticle surface band, between metal nanoparticle, produce the stabilization of Coulomb repulsion, thereby stop the reunion between metal nanoparticle; Therefore with have the polymkeric substance of polyether backbone skeleton and end active function groups and Alpha-hydroxy polycarboxylic acid in composite use in the situation that, dispersed metal nano particle effectively.
Meanwhile, Alpha-hydroxy polycarboxylic acid has stronger reductibility, and under the condition of heating, the oxide compound of energy reducing metal nano grain surface forms high conductive metal simple-substance.And more importantly, Alpha-hydroxy polycarboxylic acid easily resolves into the products such as carbonic acid gas, carbon monoxide, water and micromolecular carbonyl compound and removes within the scope of 150～300 ℃, form hardly residually, can not exert an influence to electroconductibility; Therefore, use Alpha-hydroxy polycarboxylic acid as the dispersion agent of conductive ink, oxide skin that not only can reducing metal nano grain surface, can also reduce the residual quantity of burning till organic impurity in conducting wire, thereby improve the electroconductibility of conducting wire.
More preferably, the total carbon atom number of the Alpha-hydroxy polycarboxylic acid molecule adopting in the present invention is no more than 10, and micromolecular ion characteristic is relatively better, is easier to disperse and thermal destruction.The example of the Alpha-hydroxy polycarboxylic acid using as the present invention, such as oxysuccinic acid, tartrate, citric acid, 2-hydroxyl pentanedioic acid, 2,3 ,-dihydroxyl pentanedioic acid, 2,4-dihydroxyl pentanedioic acid, 3-methyl-2,4-dihydroxyl pentanedioic acid, 2,3,4-trihydroxy glutaric acid etc.
Finally, in conductive ink, as dispersion medium, guarantee that each material can wholely form good dispersed system, also needs to add solvent; This solvent in use carries out as dispersion medium, is not particularly limited.But for the molecular structure of above-mentioned each component and contained molecular characterization, in order to promote the effect of dispersed system, preferably adopt polar solvent; Can be selected from one or more the mixture in alcohols, ester class, ketone, alcohol ethers, ether-ether class and amides, and the boiling point under its normal pressure is within the scope of 60～300 ℃, finally in the process of sintering, can volatilize or decompose, and reduces residual.Such as alcoholic solvents such as ethanol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, secondary octanol, hexalin, phenylcarbinol, Terpineol 350, ethylene glycol, glycol ethers; The esters solvents such as ethyl acetate, butylacetate, butyl propionate, butyl butyrate, gamma-butyrolactone, dimethyl succinate, Methyl glutarate, adipic acid dimethyl ester, methyl benzoate; The ketones solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-butyl ketone, pimelinketone, isophorone; The alcohol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol list isopropyl ether, ethylene glycol monobutyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglyme, diethyl carbitol; The solvent of ether ester type such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic ester, glycol ether methyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, glycol ether propyl ether acetic ester, glycol ether isopropyl ether acetic ester, diethylene glycol butyl ether acetic ester, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters; The amide solvents such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
Adopt conductive ink of the present invention by use, to there is the polymkeric substance of polyether backbone skeleton and end active function groups, utilize its end active function groups and metal nanoparticle surface to form firmly anchorage effect, polyether backbone produces sterically hindered stabilization, stop the reunion between metal nanoparticle, and easily there is fracture degraded in its polyether backbone under heat-treat condition, form small molecules product and partly remove, avoiding remaining being beneficial to and improve the electroconductibility of burning till conducting wire.Simultaneously, composite use Alpha-hydroxy polycarboxylic acid also, because it has ion characteristic and reductibility, electrostatic stabilization effect can be provided and can reducing metal in heat treatment process the oxide compound of nano grain surface, and within the scope of 150～300 ℃, can there is thermal destruction and remove, thereby improve the electroconductibility of burning till conducting wire, there is good dispersiveness and oxidation-resistance simultaneously.
The present invention further also proposes a kind of preparation method of above-mentioned conductive ink, comprises the steps:
S10, measures and has the saturated covering amount of the polymkeric substance of polyether backbone skeleton and end active function groups to metal nanoparticle;
S20 is coated to obtain preliminary dispersion liquid by metal nanoparticle with the polymkeric substance with polyether backbone skeleton and end active function groups in solvent; Wherein, to have the polymer loading of polyether backbone skeleton and end active function groups be saturated covering amount 50%～120%;
S30, after preliminary dispersion liquid is disperseed again with Alpha-hydroxy polycarboxylic acid, dissolves in solvent; Obtain conductive ink of the present invention; 1%～10% of the weight that wherein consumption of Alpha-hydroxy polycarboxylic acid is metal nanoparticle.
In the above-mentioned preparation method of the present invention, due to polymerization single polymerization monomer, the active group different amts of the different polymer raw materials with polyether backbone skeleton and end active function groups; While carrying out the preparation of conductive ink in the present invention, for the consumption that makes dispersion agent just in time correspondence meet homodisperse consumption, can not cross again multiresidue simultaneously increases residual possibility; Therefore in step S10, need first to thering is the saturated covering amount of the polymkeric substance of polyether backbone skeleton and end active function groups, to measure, because form firmly anchorage effect on above-mentioned polymer ends active function groups and the metal nanoparticle surface with polyether backbone skeleton and end active function groups, thereby nano-metal particle formed coated.Utilize this feature, specifically carry out mensuration process and be:
S11, is used the excessive polymkeric substance with polyether backbone skeleton and end active function groups in solvent, to disperse metal nanoparticle is fully coated, and obtains dispersion liquid;
S12, removes the unnecessary polymkeric substance with polyether backbone skeleton and end active function groups in dispersion liquid by methods such as high speed centrifugation, ultrafiltration or centrifugal ultrafiltrations, isolates the metal nanoparticle being wrapped by;
S13, measures the content of metal nanoparticle surface organic matter by thermogravimetry, be and have the saturated covering amount of the polymkeric substance of polyether backbone skeleton and end active function groups to metal nanoparticle.
Then in step S20, adopt the polymkeric substance with polyether backbone skeleton and end active function groups that is equivalent to saturated covering amount 50～120% to disperse in solvent nm gold particles; Just can usage quantity can reach balance, both guarantee the abundant of coated dispersion, and controlled residual amount.
After adding, again disperses the last Alpha-hydroxy polycarboxylic acid that adopts the weight 1%～10% of metal nanoparticle in step S30; Its object of consumption of controlling Alpha-hydroxy polycarboxylic acid in this step is, when the consumption of Alpha-hydroxy polycarboxylic acid is less than 1% of metal nanoparticle weight, the oxide compound on metal nanoparticle surface can not fully be reduced; When the consumption of Alpha-hydroxy polycarboxylic acid is higher than 10% of metal nanoparticle weight, the more Alpha-hydroxy polycarboxylic acid gasification phenomenon of degrading in sintering process is comparatively violent, easily makes conducting film produce hole or crackle, reduces conducting film compactness.
Adopt the above-mentioned preparation method of the present invention, according to the raw material of institute's conductive ink of the present invention, in preparation, raw material is carried out to specific substep dispersion according to its character, and in dispersion according to measurement result feedback consumption, make each performances such as dispersiveness, electroconductibility, oxidation-resistance of the conductive ink of preparation realize optimum balance.
In order to make the above-mentioned preparation method of the present invention more know that easy to understand and effect embody, below by a plurality of embodiment, be illustrated:
Embodiment 1
S11, by the polyetheramine of 0.75g
l-207 (EO/PO=33/10, weight-average molecular weight is 2000, U.S. HUNTSMAN company manufactures) be dissolved in 20g Virahol, (median size is 45nm to add the copper nano particles of 5g, maximum particle diameter is less than 100nm, surface copper oxide content is 5 about quality %) and ultrasonic dispersion 20 minutes, make fully quilt of copper nano particles
l-207 is coated;
S12 appends 200g Virahol, uses centrifugal ultrafiltration method elimination partial solvent, and the concentration that is concentrated into copper nano particles is 50 quality % left and right; Repeat to append Virahol and centrifugal ultrafiltration operation 3 times, unnecessary
l-207 removes with filtrate, and obtaining copper nano particles content is the dispersion liquid of 50 quality % left and right, re-uses film filter and isolates the copper nano particles in dispersion liquid;
S13, get a part of isolated copper nano particles in a vacuum 80 ℃ dry 2 hours, then in nitrogen atmosphere 600 ℃ process 30 minutes, calculated weight, analyzes and finds that weight reduces 4.2%; Can think thermal weight loss be by
the thermal destruction of L-207 causes.As can be seen here,
l-207 is 4.2 quality % to the saturated covering amount of copper nano particles.Get again a part from 80 ℃ after dry 2 hours in a vacuum of the copper nano particles going out, in nitrogen atmosphere, process 30 minutes for 250 ℃, through gravimetric analysis, find that weight reduces 2.0%.Infer thus, copper nano particles is surface coated
l-207 is about 48% in 250 ℃ of thermal destruction rates of processing after 30 minutes of nitrogen atmosphere;
S20, presses 3:6:1 preparation 77.83g mixed solvent by Virahol, 2-Butoxyethyl acetate and glycol ether, adds 0.67g
l-207 (be equivalent to saturated covering amount 80%) and 20g copper nano particles, ultrasonic dispersion 20 minutes, forms preliminary dispersion liquid;
S30 supplements 1.5g citric acid in preliminary dispersion liquid, stirs 30 minutes, makes the conductive ink that copper nano particles content is 20 quality %.Measure resistivity, outcome record is in table 1.
Embodiment 2
By the polyetheramine in embodiment 1
l-207 is replaced by methoxy poly (ethylene glycol) propionic acid, and (molecular weight is 2000, Jiaxing Bo Mei Bioisystech Co., Ltd manufactures), same according in the identical mode of embodiment 1, prepare the conductive ink that copper nano particles content is 20 quality %, and measure resistivity, outcome record is in table 1.
Embodiment 3
By the polyetheramine in embodiment 1
l-207 is replaced by methoxy poly (ethylene glycol) amine, and (molecular weight is 2000, Jiaxing Bo Mei Bioisystech Co., Ltd manufactures), according to the mode identical with embodiment 1, prepare the conductive ink that copper nano particles content is 20 quality %, and measure resistivity, outcome record is in table 1.
Embodiment 4
By the polyetheramine in embodiment 1
l-207 and citric acid are replaced by respectively methoxy poly (ethylene glycol) propionic acid, and (molecular weight is 2000, Jiaxing Bo Mei Bioisystech Co., Ltd manufactures) and oxysuccinic acid, same according to the identical preparation method of embodiment 1, prepare the conductive ink that copper nano particles content is 20 quality %, and measure resistivity, outcome record is in table 1.
Comparative example 1
Virahol and Terpineol 350 are pressed to 3:1 weight ratio preparation 79g mixed solvent, add 1g polyvinylpyrrolidone (PVP K30, molecular-weight average is 58000, Chemical Reagent Co., Ltd., Sinopharm Group) also dissolve, add 20g copper nano particles (median size is 45nm, and maximum particle diameter is less than 100nm, and surface copper oxide content is 5 quality % left and right), ultrasonic dispersion 20 minutes, makes the conductive ink that copper nano particles content is 20 quality %.Measure resistivity, outcome record is in table 1.
Comparative example 2
By the polyetheramine in embodiment 1
l-207 is replaced by polyvinylpyrrolidone (PVP K30, molecular-weight average is 58000, Chemical Reagent Co., Ltd., Sinopharm Group), in the identical mode of embodiment 1, prepare the conductive ink that copper nano particles content is 20 quality %, and measure resistivity, outcome record is in table 1.
In the various embodiments described above, measure by the following method resistivity:
Use OSP-8 spreading rod (Japanese Ao Si skill company manufacture) that conductive ink is coated on Kapton, in air dry oven, at 100 ℃ of temperature, be dried 20 minutes, again in nitrogen atmosphere 250 ℃ process 30 minutes, make metal nanoparticle sinter conducting film into; Use roughmeter SJ-301 (Japanese San Feng company manufacture) to measure the thickness D of conducting film, according to four probe method, measure the sheet resistance R of conducting film, by calculating formula ρ=R * D, calculate the resistivity of conducting film.Its result is as following table 1:
From the data of upper table, conductive ink of the present invention, can realize sintering below at 300 ℃, and after sintering, organic substance residues is few, and the conducting wire resistivity of burning till is lower than 20 μ Ω cm.Comparative example 1 is used the polyvinylpyrrolidone that is difficult to thermal destruction to make dispersion agent, and the oxide compound on copper nano particles surface is not reduced, and the conducting wire resistivity of burning till is high.Although comparative example 2 is used citric acid by the Reduction of Oxide on copper nano particles surface, but still some is difficult to the polyvinylpyrrolidone of thermal destruction, the resistivity of the conducting wire of burning till is about 2 times of left and right of the present invention.Therefore Comparatively speaking, the electroconductibility final effect of conductive ink of the present invention can access goodish lifting.And in above-mentioned preparation process, its all preparation process is more controlled, compare and existingly need to adopt the preparation methods such as reducing atmosphere, the step process of its production and security etc. each side is all gentleer, and process regulation difficulty reduces greatly.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a conductive ink, is characterized in that, comprises metal nanoparticle, dispersion agent, Alpha-hydroxy polycarboxylic acid and solvent; Wherein,
Described metal nanoparticle surface has the metallic element oxide compound coating layer of this metal nanoparticle;
Described dispersion agent is the polymkeric substance with polyether backbone skeleton and end active function groups.
2. conductive ink as claimed in claim 1, is characterized in that, the particle size range of described metal nanoparticle is 5～100nm.
3. conductive ink as claimed in claim 1 or 2, is characterized in that, the mass percent that described metal nanoparticle surface oxide layer accounts for described metal nanoparticle is less than 10%.
4. conductive ink as claimed in claim 1 or 2, is characterized in that, described in there is the polymkeric substance that the polymkeric substance of polyether backbone skeleton and end active function groups is following structural formula:
In formula, R represents amino or the carboxyl of active function groups, R
1represent H atom or methyl, R
2represent hydrogen atom or alkyl, R
3represent a kind of in alkyl, alkoxyl group, hydroxyl or aldehyde radical; X and y represent 0 or positive integer, and x+y>=2; N represents to be greater than 1 positive integer, and m represents positive integer.
5. conductive ink as claimed in claim 1 or 2, is characterized in that, described in there is the polymkeric substance of polyether backbone skeleton and end active function groups weight-average molecular weight be 500～4000.
6. conductive ink as claimed in claim 1 or 2, is characterized in that, described Alpha-hydroxy polycarboxylic acid total carbon atom number is no more than 10;
And/or
The addition of described Alpha-hydroxy polycarboxylic acid be described metal nanoparticle weight 1%～10%.
7. conductive ink as claimed in claim 1 or 2, is characterized in that, described solvent is the polar solvent of atmospheric boiling point within the scope of 60～300 ℃.
8. the preparation method of the conductive ink as described in claim 1 to 7 any one, is characterized in that, comprises the steps:
Obtain the metal nanoparticle that surface has oxide compound coating layer;
Described metal nanoparticle is coated in described solvent with dispersion agent and obtains preliminary dispersion liquid, the consumption of wherein said dispersion agent be dispersion agent to the saturated covering amount of metal nanoparticle 50%～120%;
In described preliminary dispersion liquid, add Alpha-hydroxy polycarboxylic acid, and the dispersed conductive ink that obtains.
9. the preparation method of conductive ink as claimed in claim 8, is characterized in that, 1%～10% of the weight that the addition of described Alpha-hydroxy polycarboxylic acid is described metal nanoparticle.
10. the preparation method of conductive ink as claimed in claim 8 or 9, is characterized in that, before the preliminary dispersion liquid step of described preparation, also comprises and measures the saturated covering amount step of described dispersion agent to metal nanoparticle:
Fully coated to metal nanoparticle at described solvent with excessive described dispersion agent;
Remove unnecessary dispersion agent, and isolate the metal nanoparticle being wrapped by;
The content that detects the surface coated dispersion agent of metal nanoparticle, is the saturated covering amount of described dispersion agent to metal nanoparticle.
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| PCT/CN2014/088470 WO2016015382A1 (en) | 2014-07-30 | 2014-10-13 | Conductive ink and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017080307A1 (en) * | 2015-11-12 | 2017-05-18 | 广州华睿光电材料有限公司 | Composition for printing electronic devices and application thereof in electronic devices |
| CN108652753A (en) * | 2018-02-02 | 2018-10-16 | 浙江清华柔性电子技术研究院 | It is used to form the pattern material and labeling method of organism surface label |
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| ES2496440T3 (en) * | 2011-12-21 | 2014-09-19 | Agfa-Gevaert | Dispersion containing metal nanoparticles, metal oxide or metal precursor, a polymeric dispersant and a thermally cleavable agent |
| JP6277719B2 (en) * | 2013-01-09 | 2018-02-14 | 日油株式会社 | Non-aqueous dispersant and non-aqueous dispersion composition |
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| CN101519552A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院化学研究所 | Method for preparing inkjet water-soluble ink containing noble metal nano particles |
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| CN108291105A (en) * | 2015-11-12 | 2018-07-17 | 广州华睿光电材料有限公司 | Application for the composition of printed electronic device and its in electronic device |
| CN108652753A (en) * | 2018-02-02 | 2018-10-16 | 浙江清华柔性电子技术研究院 | It is used to form the pattern material and labeling method of organism surface label |
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| Publication number | Publication date |
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| WO2016015382A1 (en) | 2016-02-04 |
| CN104130629B (en) | 2016-01-20 |
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