CN104130629B - Conductive ink and preparation method thereof - Google Patents
Conductive ink and preparation method thereof Download PDFInfo
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- CN104130629B CN104130629B CN201410371310.4A CN201410371310A CN104130629B CN 104130629 B CN104130629 B CN 104130629B CN 201410371310 A CN201410371310 A CN 201410371310A CN 104130629 B CN104130629 B CN 104130629B
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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
The invention provides a kind of conductive ink, comprise metal nanoparticle, dispersion agent, Alpha-hydroxy polycarboxylic acid and solvent; Wherein, metal nanoparticle surface has the metal oxides coating layer of this metal nanoparticle; Dispersion agent is the polymkeric substance with polyether backbone skeleton and end active functional group.Adopt conductive ink of the present invention by using the polymkeric substance with polyether backbone skeleton and end active functional group, its end active functional group and metal nanoparticle surface is utilized to form firmly anchorage effect, polyether backbone produces space stability ultimate load effect, 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 part removes, avoid remaining the electroconductibility being beneficial to and improving and burn till conducting wire.Meanwhile, also composite use Alpha-hydroxy polycarboxylic acid, the electroconductibility of conducting wire is burnt till in common raising, has excellent dispersiveness and oxidation-resistance simultaneously.
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 (PrintFullElectronicTechnology) 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 wherein forming conducting wire and figure is conductive ink, is generally made up of metal nanoparticle, protective material, dispersion agent, solvent and other auxiliary agents.
The existing conductive ink in order to obtain metal nanoparticle dispersiveness and oxidation resistant, usually needs the dispersion agent using the more material such as lipid acid, chain alkyl amine, polyvinylpyrrolidone, polymine, polyvinyl alcohol as metal nanoparticle in system.In order to improve the adaptability of conductive ink to different substrate materials, people wish that conductive ink can realize low-temperature sintering (< 300 DEG C); But the dispersion agent being coated on metal nanoparticle surface in low temperature sintering technology is difficult to removing, remains in conducting wire and affects electroconductibility.Meanwhile, the addition of dispersion agent again can not be too small, and time 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 taken into account of the electroconductibility of the dispersiveness of metal nanoparticle, oxidation-resistance and conducting wire is very large.And metal nanoparticle is 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, the raising of conducting wire electroconductibility will inevitably be hindered.
Based on above-mentioned defect, publication number is a kind of method that the patent of invention of CN1792127A discloses fine copper particle and sinters in reductibility organic compound atmosphere, reductibility organic compound is that to have by oxidation transformation be the alcohol compound of the hydroxyl containing oxygen base or aldehyde radical, and the reduction simultaneously realizing nano-metal particle promotes electroconductibility.But these gaseous reduction materials have inflammable and explosive defect, in preparation process control accuracy and difficulty huge, in conductive ink, therefore do not have temporarily the dispersiveness of good metal nanoparticle, means that the electroconductibility of oxidation-resistance and conducting wire is taken into account.
Summary of the invention
The object of the embodiment of the present invention is the above-mentioned deficiency overcoming prior art, provide a kind of metal nanoparticle to have excellent 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 kind of conductive ink, comprises metal nanoparticle, dispersion agent, Alpha-hydroxy polycarboxylic acid and solvent; Wherein,
Described metal nanoparticle surface has the metal oxides coating layer of this metal nanoparticle;
Described dispersion agent is the polymkeric substance with polyether backbone skeleton and end active functional group.
Conductive ink of the present invention has the polymkeric substance of polyether backbone skeleton and end active functional group by using, its end active functional group and metal nanoparticle surface is utilized to form firmly anchorage effect, polyether backbone produces space stability ultimate load effect, 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 part removes, avoid remaining the electroconductibility being beneficial to and improving and burn till conducting wire.Simultaneously, also composite use Alpha-hydroxy polycarboxylic acid, because it has ion characteristic and reductibility, electrostatic stabilization effect can be provided and can the oxide compound of reducing metal nano grain surface in heat treatment process, and can thermal destruction be there is and remove within the scope of 150 ~ 300 DEG C, thus improve the electroconductibility of burning till conducting wire, there is excellent dispersiveness and oxidation-resistance simultaneously.
The present invention also proposes a kind of preparation method of above-mentioned conductive ink further, comprises the steps:
Obtain the metal nanoparticle that surface has oxide cladding layers;
Described metal nanoparticle dispersion agent is carried out in solvent coated preliminary dispersion liquid, the consumption of wherein said dispersion agent is that dispersion agent is to 50% ~ 120% of the saturated covering amount of metal nanoparticle;
In described preliminary dispersion liquid, add Alpha-hydroxy polycarboxylic acid, and dispersedly namely obtain conductive ink.
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, according to its character, specific substep dispersion is carried out to raw material, and according to measurement result feedback consumption in dispersion, make each performances such as the dispersiveness of the conductive ink of preparation, electroconductibility, oxidation-resistance realize optimum balance.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, 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, be 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 functional group.
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 improving except the oxidation-resistance of metal nanoparticle, also contribute to the anchoring group of raising dispersion agent to the adsorptive power on metal nanoparticle surface, thus improve the dispersion stabilization of metal nanoparticle.The content of the oxide passivation layer on metal nanoparticle surface can by carrying out thermogravimetric analysis in oxygen atmosphere and measure having; Consider for from reducing the effect of burning till the resistivity of conducting wire, the mass percent that preferred oxides passivation layer accounts for metal nanoparticle is less than 10%.Preferably, the particle size range of the metal nanoparticle of the present invention's use 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 energy required for sintering is also higher, not easily realizes low-temperature sintering; When the particle diameter of metal nanoparticle is less than 5nm, so the specific surface area of these particles becomes very large, and activity is higher, and the amount realizing the dispersion agent required for stable dispersion is also larger, organic impurity residual after sintering increases, thus reduces the electroconductibility of burning till conducting wire.
Further, above-mentioned dispersion agent adopts the polymkeric substance with polyether backbone skeleton and end active functional group, its polyether backbone skeleton is made up of oxyethyl group (EO) and/or propoxy-(PO) structural unit, and its end active functional group is amino and/or carboxyl.This has the active function groups of the polymkeric substance of polyether backbone skeleton and end active functional group, 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, and forms good sterically hindered effect, is beneficial to the reunion stoped between metal nanoparticle, thus improve the dispersiveness of metal nanoparticle; Again by regulating the ratio of oxyethyl group (EO) and propoxy-(PO) in polyether backbone, the consistency of polymkeric substance and solvent system can also be changed.
And reduction redox residual effect linear for structure in force, the polymkeric substance of polyether backbone skeleton and end active functional group preferably adopts the polyether backbone skeleton of following representation and the polymkeric substance of end active functional group:
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 the one in alkyl, alkoxyl group, hydroxyl and aldehyde radical; X and y represents 0 or positive integer, and x+y>=2; N represents the positive integer being greater than 1, 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, be that the thermostability of polymkeric substance of main chain is poorer with polyethers.If polyether backbone contains more propoxy-(PO), pending methyl group on propoxy-(PO) makes main chain is full of branch point, methyne hydrogen on branch point is more easily taken away, and pending methyl group also can weaken the bond energy of C-C key in polyether backbone and C-O key, thus makes the thermostability of polyether backbone be deteriorated further.The C-O key of polyether backbone just starts to occur by thermal destruction at higher than the temperature of 160 DEG C, and at higher temperatures, C-C key also can rupture.Under anaerobic, directly there is random homolysis chain-breaking reaction and degrade in the C-O key in polyether backbone and C-C key, the product after thermal destruction has low-molecular-weight polyethers, ethanol, acetaldehyde, propionic aldehyde, acetone, propylene and other end-group structures to be the thermal degradation products of ketone, aldehyde, alcohol and ether.Under aerobic conditions, except random homolysis chain-breaking reaction can occur for the C-O key in polyether backbone and C-C key, in polyether backbone, the existence of Sauerstoffatom increases the unstable of hydrogen on its α position carbon atom, makes polyether backbone more easily thermal oxidative reaction occur.Adopt the above-mentioned dispersion agent of polymkeric substance as conductive ink with polyether backbone skeleton, so during sintering, easy thermal destruction becomes volatile small molecules product, the residual quantity of burning till organic impurity in conducting wire can be reduced, thus be conducive to the electroconductibility improving conducting wire.
In the above-described embodiment, preferably the weight-average molecular weight with the polymkeric substance of polyether backbone skeleton and end active functional group of the present invention is 500 ~ 4000 further; When its weight-average molecular weight is lower than 500, sterically hindered effect reduces, and is unfavorable for the dispersiveness improving 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, thus 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 HUNTSMAN company of the U.S.
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 see 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 adopted in the present invention is in the molecular structure containing the hydroxyl of more than 1 or 1, and the carboxyl of more than 2 or 2, 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 functional group as the aforementioned, but it has ion characteristic, electric charge on metal nanoparticle surface band can be given, between metal nanoparticle, produce the stabilization of Coulomb repulsion, thus stop the reunion between metal nanoparticle; Therefore when with when there is the polymkeric substance of polyether backbone skeleton and end active functional group and Alpha-hydroxy polycarboxylic acid in composite use, can 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 DEG C, formed residual hardly, can not electroconductibility be had an impact; Therefore, use Alpha-hydroxy polycarboxylic acid as the dispersion agent of conductive ink, not only can the oxide skin of reducing metal nano grain surface, the residual quantity of burning till organic impurity in conducting wire can also be reduced, thus improve the electroconductibility of conducting wire.
More preferably, the total carbon atom number of the Alpha-hydroxy polycarboxylic acid adopted in the present invention is no more than 10, and micromolecular ion characteristic is relatively better, is easier to dispersion and thermal destruction.As the example of the Alpha-hydroxy polycarboxylic acid that the present invention uses, 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.
Last in conductive ink, as dispersion medium, ensure that each material overallly can form good dispersed system, also need to add solvent; This solvent in use carries out as dispersion medium, is not particularly limited.But for molecular structure and the contained molecular characterization of above-mentioned each component, 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 DEG C, finally can volatilizees or decompose in the process of sintering, reduce residual.The alcoholic solvents such as such as ethanol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, sec-octyl alcohol, hexalin, phenylcarbinol, Terpineol 350, ethylene glycol, glycol ether; 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, ethyleneglycol monopropylether, 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, diethylene glycol methyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diethylene glycol propyl ether acetic ester, glycol ether isopropyl ether acetic ester, diethylene glycol butyl ether acetic ester, 3-methoxypropionate, 3-ethoxyl ethyl propionate, 3-ethoxypropanoate; The amide solvents such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
Adopt conductive ink of the present invention by using the polymkeric substance with polyether backbone skeleton and end active functional group, its end active functional group and metal nanoparticle surface is utilized to form firmly anchorage effect, polyether backbone produces space stability ultimate load effect, 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 part removes, avoid remaining the electroconductibility being beneficial to and improving and burn till conducting wire.Simultaneously, also composite use Alpha-hydroxy polycarboxylic acid, because it has ion characteristic and reductibility, electrostatic stabilization effect can be provided and can the oxide compound of reducing metal nano grain surface in heat treatment process, and can thermal destruction be there is and remove within the scope of 150 ~ 300 DEG C, thus improve the electroconductibility of burning till conducting wire, there is excellent dispersiveness and oxidation-resistance simultaneously.
The present invention also proposes a kind of preparation method of above-mentioned conductive ink further, comprises the steps:
S10, mensuration has the polymkeric substance of polyether backbone skeleton and end active functional group to the saturated covering amount of metal nanoparticle;
S20, carries out coated preliminary dispersion liquid in a solvent by the metal nanoparticle polymkeric substance with polyether backbone skeleton and end active functional group; Wherein, the polymer loading with polyether backbone skeleton and end active functional group is 50% ~ 120% of saturated covering amount;
S30, after again being disperseed by preliminary dispersion liquid Alpha-hydroxy polycarboxylic acid, dissolves in solvent; Namely conductive ink of the present invention is obtained; Wherein the consumption of Alpha-hydroxy polycarboxylic acid is 1% ~ 10% of the weight of metal nanoparticle.
State on the invention in preparation method, due to the different polymerization single polymerization monomers with the polymer raw material of polyether backbone skeleton and end active functional group, active group different amts; When carrying out the preparation of conductive ink in the present invention, in order to make the consumption of dispersion agent just in time correspondence can meet homodisperse consumption, can not cross again multiresidue increases residual possibility simultaneously; Therefore need in step slo first to measure the saturated covering amount of the polymkeric substance with polyether backbone skeleton and end active functional group, because the polymer ends active function groups having polyether backbone skeleton and an end active functional group above-mentioned and metal nanoparticle surface form firmly anchorage effect, thus are formed coated to nano-metal particle.Utilize this feature, specifically carrying out mensuration process is:
S11, uses the excessive polymkeric substance with polyether backbone skeleton and end active functional group to disperse in a solvent to make metal nanoparticle by fully coated, obtains dispersion liquid;
S12, removes the polymkeric substance with polyether backbone skeleton and end active functional group unnecessary in dispersion liquid by methods such as high speed centrifugation, ultrafiltration or centrifugal ultrafiltrations, isolates the metal nanoparticle be wrapped by;
S13, measures the content of metal nanoparticle surface organic matter by thermogravimetry, be there is polyether backbone skeleton and end active functional group polymkeric substance to the saturated covering amount of metal nanoparticle.
Then in step S20, adopt the polymkeric substance with polyether backbone skeleton and end active functional group being equivalent to saturated covering amount 50 ~ 120% to disperse in a solvent nm gold particles; Just usage quantity can reach balance, both ensure that the abundant of coated dispersion, and controlled residual amount.
Again disperse after finally adopting the Alpha-hydroxy polycarboxylic acid of the weight 1% ~ 10% of metal nanoparticle to add in step s 30; The consumption controlling Alpha-hydroxy polycarboxylic acid in this step its object is to, and 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 be reduced sufficiently; When the consumption of Alpha-hydroxy polycarboxylic acid is higher than 10% of metal nanoparticle weight, more Alpha-hydroxy polycarboxylic acid degrades gasification phenomenon comparatively acutely in sintering process, 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, according to its character, specific substep dispersion is carried out to raw material, and according to measurement result feedback consumption in dispersion, make each performances such as the dispersiveness of the conductive ink of preparation, electroconductibility, oxidation-resistance realize optimum balance.
In order to make the above-mentioned preparation method of the present invention clearly easy to understand and effect embodiment, be illustrated below by way of multiple embodiment:
Embodiment 1
S11, by the polyetheramine of 0.75g
l-207 (EO/PO=33/10, weight-average molecular weight is 2000, HUNTSMAN company of the U.S. 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 about 5 quality %) and ultrasonic disperse 20 minutes, make copper nano particles fully quilt
l-207 institute is coated;
S12 adds 200g Virahol, and use centrifugal ultrafiltration method elimination partial solvent, the concentration being concentrated into copper nano particles is about 50 quality %; Repeat additional Virahol and centrifugal ultrafiltration operates 3 times, unnecessary
l-207 removes with filtrate, obtains the dispersion liquid that copper nano particles content is about 50 quality %, re-uses film filter and isolates copper nano particles in dispersion liquid;
S13, gets the 80 DEG C of dryings 2 hours in a vacuum of a part of isolated copper nano particles, then 600 DEG C of process 30 minutes in nitrogen atmosphere, and calculated weight, analyzes and find that weight reduces 4.2%; Can think thermal weight loss be by
the thermal destruction of L-207 causes.As can be seen here,
the saturated covering amount of L-207 to copper nano particles is 4.2 quality %.80 DEG C of dryings are after 2 hours in a vacuum from the copper nano particles gone out to get a part again, and in nitrogen atmosphere, 250 DEG C process 30 minutes, find that weight reduces 2.0% through gravimetric analysis.Infer thus, copper nano particles is surface coated
l-207 is about 48% in the thermal destruction rate of nitrogen atmosphere 250 DEG C process after 30 minutes;
S20, presses 3:6:1 and prepares 77.83g mixed solvent, add 0.67g by Virahol, 2-Butoxyethyl acetate and glycol ether
l-207 (being equivalent to 80% of saturated covering amount) and 20g copper nano particles, ultrasonic disperse 20 minutes, forms preliminary dispersion liquid;
S30, supplements 1.5g citric acid, stirs 30 minutes in preliminary dispersion liquid, and obtained copper nano particles content is the conductive ink of 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), equally according in the identical mode of embodiment 1, prepare the conductive ink that copper nano particles content is 20 quality %, and measuring 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 measuring resistivity, outcome record is in table 1.
Embodiment 4
By the polyetheramine in embodiment 1
l-207 and citric acid are replaced by methoxy poly (ethylene glycol) propionic acid respectively, and (molecular weight is 2000, Jiaxing Bo Mei Bioisystech Co., Ltd manufactures) and oxysuccinic acid, equally according to the preparation method that embodiment 1 is identical, prepare the conductive ink that copper nano particles content is 20 quality %, and measuring resistivity, outcome record is in table 1.
Comparative example 1
Virahol and Terpineol 350 are pressed 3:1 weight ratio preparation 79g mixed solvent, add 1g polyvinylpyrrolidone (PVPK30, molecular-weight average is 58000, Chemical Reagent Co., Ltd., Sinopharm Group) and dissolve, add 20g copper nano particles (median size is 45nm, and maximum particle diameter is less than 100nm, and surface copper oxide content is about 5 quality %), ultrasonic disperse 20 minutes, obtained copper nano particles content is the conductive ink of 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 (PVPK30, molecular-weight average is 58000, Chemical Reagent Co., Ltd., Sinopharm Group), in the mode that embodiment 1 is identical, 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 resistivity by the following method:
OSP-8 spreading rod (Japanese Ao Si skill company manufactures) is used to coat on Kapton by conductive ink, in air dry oven at 100 DEG C of temperature dry 20 minutes, again in nitrogen atmosphere 250 DEG C process 30 minutes, make metal nanoparticle sinter conducting film into; Use roughmeter SJ-301 (rich company of Japan three manufactures) to measure the thickness D of conducting film, measure the sheet resistance R of conducting film according to four probe method, calculated the resistivity of conducting film by calculating formula ρ=R × D.Its result is as following table 1:
From in the data of upper table, conductive ink of the present invention, can realize sintering below 300 DEG C, 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 uses the polyvinylpyrrolidone being 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 uses 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 about 2 times of the present invention.Therefore Comparatively speaking, the electroconductibility final effect of conductive ink of the present invention can obtain goodish lifting.And in above-mentioned preparation process, its all preparation process is more controlled, comparing existing needs adopts the preparation method such as reducing atmosphere, and its step process and security etc. each side of producing 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 amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within 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 metal oxides coating layer of this metal nanoparticle;
Described dispersion agent is the polymkeric substance with polyether backbone skeleton and end active functional group.
2. conductive ink as claimed in claim 1, it 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, it 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 polyether backbone skeleton and end active functional group polymkeric substance be the polymkeric substance of 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 the one in alkyl, alkoxyl group, hydroxyl or aldehyde radical; X and y represents 0 or positive integer, and x+y>=2; N represents the positive integer being greater than 1, 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 functional group weight-average molecular weight be 500 ~ 4000.
6. conductive ink as claimed in claim 1 or 2, it 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 is 1% ~ 10% of the weight of described metal nanoparticle.
7. conductive ink as claimed in claim 1 or 2, it is characterized in that, described solvent is the polar solvent of atmospheric boiling point within the scope of 60 ~ 300 DEG C.
8. the preparation method of the conductive ink as described in any one of claim 1 to 7, is characterized in that, comprises the steps:
Obtain the metal nanoparticle that surface has oxide cladding layers;
Described metal nanoparticle dispersion agent is carried out in described solvent coated preliminary dispersion liquid, the consumption of wherein said dispersion agent is that dispersion agent is to 50% ~ 120% of the saturated covering amount of metal nanoparticle;
In described preliminary dispersion liquid, add Alpha-hydroxy polycarboxylic acid, and dispersedly namely obtain conductive ink.
9. the preparation method of conductive ink as claimed in claim 8, it is characterized in that, the addition of described Alpha-hydroxy polycarboxylic acid is 1% ~ 10% of the weight of described metal nanoparticle.
10. the preparation method of conductive ink as claimed in claim 8 or 9, is characterized in that, before preliminary for described preparation dispersion liquid step, also comprises and measures described dispersion agent to the saturated covering amount step of metal nanoparticle:
Fully coated to metal nanoparticle at described solvent with excessive described dispersion agent;
Remove unnecessary dispersion agent, and isolate the metal nanoparticle be wrapped by;
Detect the content of the surface coated dispersion agent of metal nanoparticle, be the saturated covering amount of described dispersion agent to metal nanoparticle.
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| KR100754326B1 (en) * | 2006-02-15 | 2007-09-03 | 삼성전기주식회사 | Manufacturing Method of Metal Nanoparticle |
| KR100830871B1 (en) * | 2006-10-11 | 2008-05-21 | 삼성전기주식회사 | Method for surface modification of nondispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method |
| JP4867905B2 (en) * | 2007-12-11 | 2012-02-01 | セイコーエプソン株式会社 | Conductor pattern forming ink, conductor pattern, and wiring board |
| CN101519552B (en) * | 2008-02-29 | 2011-08-24 | 中国科学院化学研究所 | Method for preparing inkjet water-soluble ink containing noble metal nano particles |
| DE102009015470A1 (en) * | 2008-12-12 | 2010-06-17 | Byk-Chemie Gmbh | Process for the preparation of metal nanoparticles and metal nanoparticles obtained in this way and their use |
| CN101805538B (en) * | 2010-04-08 | 2014-05-07 | 中国科学院宁波材料技术与工程研究所 | Lower-temperature sintered conductive ink |
| 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 |
-
2014
- 2014-07-30 CN CN201410371310.4A patent/CN104130629B/en active Active
- 2014-10-13 WO PCT/CN2014/088470 patent/WO2016015382A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| CN104130629A (en) | 2014-11-05 |
| WO2016015382A1 (en) | 2016-02-04 |
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