KR20150118624A - Manufacture method of basic ink containing carbon-nonbonding metal nanoparticles & metal nanoparticles particle-dispersed ink - Google Patents

Abstract

The present invention relates to a method for manufacturing an ink base containing carbon-nonbonding metal nanoparticle and a metal nanoparticle-dispersed ink and to a technology for complexing nano-carbon materials in a manufacturing process to prevent condensation of matal nano-particles within the ink and to enhance dispersibility. The present invention provides the method for manufacturing the ink base containing carbon-nonbonding metal nanoparticle comprising the steps of: positioning the carbon-nonbonding metal within a non-oxidizing solvent; breaking the metal by applying energy to the metal; and obtaining a product formed together with the nano-carbon materials by breaking the surrounding solvent as the broken metal forms nanoparticles. Additionally, the present invention provides together the metal nanoparticle-dispersed ink having a characteristic of mixing an additive with the ink base containing the carbon non-bonding metal nanoparticles.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing an ink base material containing carbon-noncondensable metal nanoparticles and an ink containing metal nanoparticles dispersed therein,

The present invention relates to a method for producing an ink base containing carbon-non-noble metal nanoparticles and an ink in which metal nanoparticles are dispersed, and it is an object of the present invention to prevent aggregation of metal nano- To a technique for improving dispersibility.

Metal nanoparticles generally exhibit properties different from metal particles having a diameter in the micrometer range, which are commercially available as particles having a diameter of 100 nm or less. The metal nanoparticles have a very large specific surface area per unit volume or mass unit, and thus the activation energy at the surface is rapidly increased. This tendency becomes worse as the particle becomes smaller, and it has a thermodynamically very unstable state. Therefore, fine nanoparticles have a tendency to reduce surface energy through agglomeration and behave like large particles. Such agglomeration is a major obstacle to the production of conductive inks and requires a highly dispersive technique. Also, when the metal nanoparticles are exposed to oxygen or air, the surface is easily oxidized and the physical properties of the electroconductive ink are greatly degraded. Therefore, in order to produce conductive ink with metal nanoparticles, a fundamental problem-solving approach is needed.

In order to prepare a conductive coating, an ink containing metal nanoparticles must be prepared. For this purpose, there is a need for a technique for allowing metal nanoparticles to disperse evenly in the ink without aggregation.

Accordingly, it is an object of the present invention to provide an ink base manufacturing method capable of fundamentally interrupting the agglomeration of metal nanoparticles by enclosing metal nanoparticles with nano carbon species, and to provide an ink added with such an ink base agent.

In the present invention, metal located in a non-oxidizing solvent is burst by energy to form metal nanoparticles, and at the same time, a nano carbon stream is formed so that the nanocarbon stream surrounds metal nanoparticles, Synthetic metal nanoparticles are formed. In the ink base prepared as described above, the metal nanoparticles are uniformly dispersed without aggregation. An additive may be added to the metal nanoparticles to be used as a conductive ink, and the conductive ink may be coated on the substrate to obtain a conductive coating.

In the present invention, a metal that forms a matrix of the metal nanoparticles does not form a bond with carbon. The use of carbon-free metal to increase the electrical conductivity of the conductive ink.

In addition, at least one of phosphorus (P), sulfur (S), and boron (B) may be added to the nano-carbon species or metal nanoparticles during the production of the ink base.

In addition, the metal used in the present invention does not form a metal carbide compound in order to maximize the conductivity of the ink coating. Particularly, it is known that carbon nanotubes and onion carbon (onion carbon) capsules are simultaneously formed through a laser ablation method, a sputtering method, a plasma method and the like.

Therefore, the present invention is to produce metal nanoparticles by dissolving carbon-free metal in a non-oxidizing liquid solvent atmosphere, but the surrounding solvent is broken by the energy of metal explosion, and nano carbon flow is generated at the same time to form a complex with metal nanoparticles .

The ink base material containing the carbon-non-noble metal nanoparticles provided by the present invention is a conductive material having excellent electrical conductivity, which is excellent in dispersibility, surface oxidation resistance, coating property and the like due to its production method (conductive paste for conductive ink, For example.

1 is a flow chart of a method for producing an ink base containing carbon-non-crystalline metal nanoparticles and a method for producing an ink in which metal nanoparticles are dispersed.
[Fig. 2] is a photograph of a concentrated ink base.
[Figure 3] is an XRD pattern of copper nanoparticles complexed with nano-carbon species.
[Fig. 4] is an FE-TEM image of copper nanoparticles complexed with nano-carbon species.
[Fig. 5] is an FE-SEM photograph of silver nanoparticles complexed with nano-carbon species.

Ⅰ. Method for manufacturing an ink base containing carbon-non-crystalline metal nanoparticles

The present invention relates to a method for producing a non-oxidizing gas, comprising the steps of: (a) placing a carbon- (b) applying energy to the metal to pop the metal; And (c) breaking the surrounding solvent while the metal being formed forms nanoparticles to obtain a product in which the nanocarbon streams are formed together; ≪ / RTI > wherein the carbon noble metal nanoparticles comprise carbon noble metal nanoparticles.

Hereinafter, the present invention will be described in detail with reference to the embodiments. However, the following embodiments are provided to enable those skilled in the art to understand the present invention sufficiently, so that the scope of the present invention is not limited to the embodiments no.

In the present specification, the term "nano-carbon" refers to graphene, onion carbon, and CHO compounds. The carbon nanowires are generated simultaneously with the metal nanoparticles when the metal in the non-oxidation solvent is burst by energy.

When the ratio of the oxygen atoms contained in the non-oxidation solvent to -OH, -COOH, -O-, -COO-, -CHO, etc. is high, the metal nanoparticles generated by energy- . However, in the present invention, the peak amount of the metal oxide was 0 to 5% in the XRD measurement of the metal nanoparticles. A value of 5% is sufficient for sample handling.

The carbon-noncombustible metal generally excludes a metal having a carbon compound (Fe, Co, Ni, Mo, W and alloys thereof). In the present invention, any one of Al, Cu, Ag, Sn, Or an alloy containing at least 50% of any one of Al, Cu, Ag, Sn, Au and Pt. XRD measurement of the metal nanoparticles produced from the above-mentioned carbon-free metal shows that the amount of the metal oxide peak is less than 5%. Very small carbon atoms can be doped into the lattice gap of the metal atom structure (solid solution) and this state can be slightly overdone. In this case, a small amount (less than 5%) of the amount of metal oxide peak appears in the XRD measurement will be. In the case of Cu95Ni5 as an example of the alloy, the amount of carbide in the XRD phase is 5% or less.

Examples of a method of applying energy to the metal include a laser irradiation method, an arc discharge method, and an electric explosion method.

The laser irradiation may be performed by irradiating a laser through the window with a window through which the laser can pass through the laser in the reactor. In this case, it is possible to irradiate through the liquid / vapor interface considering the laser transmittance of each solvent.

As the arc discharge method, various methods of forming a plasma by arc discharge in a liquid can be applied.

The electric explosion method is a method in which two electrodes are positioned in a liquid solvent, and a wire-shaped carbon-free metal is interposed therebetween, and the metal is blown by an electric force applied to the electrode.

All of the above methods can be referred to as a plasma generation method in the near range, and other plasma generation methods can be selected and applied.

A concrete embodiment of the electric explosion method will be described as follows.

Example  1: electric explosion method Example

An embodiment of the electric explosion method applied in the step (b) of the present invention is as follows. A non-oxidizing solvent is placed in a sealed reactor, and two electrodes are placed in the reactor. A metal wire (carbon non-metal) having a diameter of 0.1 to 0.8 mm is continuously supplied between the two electrodes, Lt; / RTI > As a result, a metal located between the two electrodes is blown out, and a metal wire is successively fed, which is located between the two electrodes, and is then blown by electric energy applied to the electrode. This was repeated to produce a large amount of metal nanoparticles containing nanocarbon species.

The present invention is characterized in that the non-oxidizing solvent in step (a) is a non-aromatic solvent, and the product of step (c) comprises 5 to 30 wt% of nano- A method for producing an ink base material containing the "

Here, the content of the "nano carbon species in the drying step (c) step" means the content of the nano carbon species in the total amount of the metal nanoparticles and the nano carbon species produced when the metal is blown by the externally applied energy. That is, the amount of particles (metal nanoparticles and nanocarbon) excluding the solvent is a standard.

Most of the non-aromatic solvents are alkane, alkene, chain, cyclic solvents, and solvents having a small amount of oxygen, which contain functional groups in these solvents. These solvents were found in the present invention for the first time that the content of carbon is relatively low as compared with that of aromatic and the amount of nano carbon finally produced is 5 to 30 wt% in the product.

Examples of the non-aromatic solvent include acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, But are not limited to, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexanone, distilled water, pyridine, nitromethane, acrylonitrile, octadecylamine, dimethylsulfoxide, Ethyl acetate, chloroform, methyl ethyl ketone, formic acid, nitroethane, 2-ethoxy ethanol, and the like. 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, ethylene glycol, acetone, methyl alcohol, ethyl alcohol, iso Propyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, chloro, trimethylbenzene, pyridine, nitromethane, At least one of acrylonitrile, octadecylamine, dimethylsulfoxide, methylenechloro, alpha-terpinol, N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP).

Specific examples in which metal nanoparticles and nano-carbon streams are produced in a non-aromatic solvent are as follows.

Example  2: Non-oxidizing Non-aromatic  Solvent phase Ag  Nanoparticle generation

[Table 1] shows the analysis of the formation of Ag nanoparticles in a non-aromatic solvent for non-oxidation. It was found that the longer the carbon chain of the non-aromatic solvent and the higher the carbon content, the larger the carbon content of the product. The content of the nano-carbon species when the product was dried was 5 to 30 wt%. Content analysis was done by EDS. The Ag on the XRD showed a pure metal phase. Particularly, it can be seen that the carbon content is increased in the case of monosaccharides, disaccharides, monosaccharides, polysaccharides and polymeric solvents having high viscosity.

[Table 1]

Example  3: Non-oxidizing Non-aromatic Alcohol  Solvent phase Cu  Nanoparticle generation

[Table 2] shows the analysis of the formation of Cu nanoparticles in a solvent containing a non-aromatic alcohol group. Also in this example, it was found that the longer the carbon chain of the non-aromatic alcohol solvent and the higher the carbon content, the larger the content of the nano-carbon stream of the product.

[Table 2]

The present invention is characterized in that the non-oxidizing solvent in step (a) is an aromatic solvent, and the product of step (c) comprises 40 to 70 wt% of nano- A method for producing an ink base material containing the " When the aromatic compounds in the non-oxidizing solvent are contained in an amount of 50% or more, the carbon content in the solvent increases and the nano-carbon content in the final product becomes different from that in the non-aromatic solvent. .

The aromatic solvent may be any one or more of toluene, benzene, nitrobenzene, aniline, phenol, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, naphthalene, xylene, xylene and anthracene.

Specific examples in which metal nanoparticles and nano carbon streams are produced in an aromatic solvent are as follows.

Example  4 : Non-oxidizing  Aromatic solvent phase Cu  Nanoparticle generation

[Table 3] shows the analysis of the formation of Cu nanoparticles in non-oxidizing aromatic solvents. The greater the number of benzene rings in the aromatic solvent, the greater the amount of nano-carbon species produced, because of the higher benzene ring carbon content. Through the present invention, the content of the nano-carbon species of the product was 40 to 70 wt%. The reason for the high carbon content in comparison with the results in [Table 1] is interpreted to be that the aromatic solvent has a very high carbon content relative to the non-aromatic solvent.

[Table 3]

The present invention also provides a method for producing an ink base containing carbon-noncombustible metal nanoparticles, characterized in that the non-oxidizing solvent in step (a) is a mixture of a non-aromatic solvent and an aromatic solvent. That is, the carbon content in the solvent can be controlled by mixing the non-aromatic solvent and the aromatic solvent as needed, which means that the content ratio of the nano-carbon stream produced in the step (c) can be controlled.

Specific examples in which metal nanoparticles and nano-carbon species are produced in a solvent in which a non-aromatic solvent and an aromatic solvent are mixed are as follows.

Example  5: Non-aromatic  A solvent phase in which a solvent and an aromatic solvent are mixed Cu  Nanoparticle generation

[Table 4] shows the analysis of the formation of Cu nanoparticles in a solvent in which non-aromatic solvents and aromatic solvents are mixed. It can be seen that the more the aromatic solvent is added to the non-aromatic solvent, the higher the carbon content. Therefore, by properly mixing the non-aromatic solvent and the aromatic solvent, the nano-carbon content in the product can be controlled within the range of 5 to 70 wt%.

This is fundamentally different from the technique of artificially controlling carbon content through post-processing. That is, it is a new concept to control the content of nanocarbon in the final product by controlling the mixing ratio of the solvent and the non-aromatic and aromatic compounds.

[Table 4]

The present invention relates to a method of producing an ink base containing carbon-noncombustible metal nanoparticles, wherein a doping element is added to the solvent of the step (a), and a doping element is added to the product of the step (c) Together.

The doping element may be at least one of nitrogen, phosphorus, sulfur, and boron. The doping elements may form a direct bond with carbon in a high energy atmosphere, form a direct bond with the metal, or be formed in a solid solution form.

If the doping element is present in the solvent of step (a), a doping element may be added to the product of step (c) without any additional doping element addition.

Example  4: Nitrogen (N) doping experiment

In this embodiment, copper is added to various solvents and nitrogen (N) is added in the doping element. [Table 5] shows the results of measurement of nitrogen doping amount for nano carbon species and metal nanoparticles. These results show that various elements can be doped by adding a material that can break chemical bonds in a high energy atmosphere.

[Table 5]

The present invention relates to " (d) concentrating the product; The present invention provides a method for producing an ink base material containing carbon-noncombustible metal nanoparticles.

The method of concentrating the product at this time includes, for example, a method of removing the supernatant after natural precipitation, a method of removing supernatant after centrifugation, a method of concentrating under reduced pressure, a method of concentrating by heating, , And a method of removing the solvent using freeze-drying. This step (d) is a step required to control the viscosity of the ink base.

Specific examples of the concentration process are as follows.

Example  7: ink base (metal nanoparticles Slurry ) ≪ / RTI &

Cu nanoparticles complexed with nano-carbon species prepared in IPA solvent maintain spherical shape with primary particle size of 5-100 nm and are mixed in solution so that Cu nanoparticles can be obtained by centrifugation And made into a slurry form. The centrifugation process is carried out at a speed of 1,000 to 2,000 rpm for about 20 minutes to separate the supernatant from the supernatant, and recover the precipitate. The concentrated slurry obtained through this process has a solids content of 75 to 85 wt%. It is 7 ~ 17 times more concentrated than the solid content 5 ~ 9wt% before concentration. An appropriate viscosity can be exhibited when an ink is produced based on such a concentrated slurry (ink base). A photograph of the concentrated slurry is shown in Fig.

Ⅱ. Ink containing metal nanoparticles dispersed therein

The present invention also provides " an ink in which metal nanoparticles are dispersed, wherein an additive is mixed in an ink base prepared by the above-mentioned method ".

The additive may be a binder, a monomer, a polymer, a resin, a copolymer, a ceramic precursor, a polyimide precursor, a metal binder, a ceramic binder, a nanoparticle binder, a surfactant, a functional material, a solvent, One or more of a base, a salt, an ionic species, a labeling agent, a pressure-sensitive adhesive, a nanoparticle, a metal nanowire, a metal nanoflake, a carbon nanotube, an oxide, a ceramic, a magnetic substance, . Hereinafter, various materials that can be applied as additives will be described in detail.

1. Binder

(1) a thermosetting resin; (2) a photocurable resin; (3) a silane compound which causes a condensation reaction by hydrolysis; and (4) A thermoplastic resin, and (5) a conductive polymer.

(1) Thermosetting resin

The thermosetting resin may be at least one of urethane resin, epoxy resin, melamine resin and polyimide.

(2) Photocurable resin

The photocurable resin may be at least one selected from the group consisting of epoxy resin, polyethylene oxide, urethane resin, reactive oligomer, reactive monofunctional monomer, reactive bifunctional monomer, reactive trifunctional monomer, and photoinitiator.

① Reactive oligomer

The reactive oligomer may be at least one of an epoxy acrylate, a polyester acrylate, a urethane acrylate, a polyether acrylate, a thiolate, an organosilicon polymer, and an organosilicon copolymer.

② Reactive monofunctional monomer

The reactive monofunctional monomer may be selected from the group consisting of 2-ethylhexyl acrylate, orthyldecyl acrylate, isodecyl acrylate, didecyl methacrylate, 2-phenoxyethyl acrylate, nonylphenol ethoxy lake monoacrylate, Acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, or hydroxybutyl methacrylate is used as the initiator. Or more.

③ Reactive bifunctional monomer

The reactive bifunctional monomer may be selected from the group consisting of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, At least one of pentyl glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol methacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate and 1,6-hexanediol diacrylate is applied .

④ Reactive trifunctional monomer

The reactive trifunctional monomer may be any one or more of trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, glycidylpentatriacrylate and glycidylpentatriacrylate. have.

⑤ Photo initiator

The photoinitiator may be at least one selected from the group consisting of benzophenone, benzyldimethylketal, acetophenone, anthraquinone, and thioxanthone.

(3) Silane compound

The silane compound may be at least one of tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes.

① tetraalkoxysilanes

The tetraalkoxysilanes may be at least one of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane.

② Trialkoxysilanes

The trialkoxysilanes may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxy Silane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydride Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltri At least one of methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane can be applied.

③ Dialkoxysilanes

Examples of the dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- Butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di- Di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, At least one of diethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane can be applied.

(4) Thermoplastic resin

The thermoplastic resin may be at least one selected from the group consisting of polystyrene, polystyrene derivatives, polystyrene butadiene copolymers, polycarbonate, polyvinyl chloride, polysulfone, polyethersulfone, polyetherimide, polyacrylate, polyester, polyimide, polyamic acid, cellulose acetate, , Polyolefin, polymethyl methacrylate, polyether ketone, and polyoxyethylene can be applied.

(5) Conductive polymer

The conductive polymer may be at least one selected from the group consisting of a polythiophene-based homopolymer, a polythiophene-based copolymer, polyacetylene, polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene) and pentacene.

2. Metal Nanowire

The metal nanowires may be copper nanowires or silver nanowires. The addition of such metal nanowires can improve the electrical conductivity of the ink.

3. Dispersant

Examples of the dispersing agent include BYK, block copolymer, BTK-Chemie, Triton X-100, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyvinylpyrrole, polyvinyl alcohol, (Eg, sodium dodecylsulfonate, sodium dodecyl benzene sulfonate (NaDDBS), sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, SDS), 4-vinylbenzoic acid cetyltrimethylammounium 4-vinylbenzoate, pyrene derivatives, Gum Arabic, GA, and nafion.

4. Surfactants

Examples of the surfactant include LDS (lithium dodecyl sulfate), CTAC (Cetyltrimethyl ammonium chloride), DTAB (Dodecyl-trimethyl ammonium bromide), nonionic C12E5 (Pentaoxoethylenedocyl ether), Dextrin (polysaccharide) GA (Gum Arabic), and ethylene carbonate (EC).

Example  8 : Cu  Electrical conductivity of ink containing nanoparticles

The electrical conductivity of the thin film formed by coating the ink containing Cu nanoparticles prepared by the present invention on a glass substrate having a size of about 7 x 3 cm was measured. 0.5-1 ml of the ink prepared on the glass substrate was dropped and coated by the doctor blade method. In the ink manufacturing process, a small amount of polymer may be added as a coating uniformity of a thin film and a neck formation improving material of nanoparticles. [Table 6] shows the difference in electric conductivity according to the annealing temperature after the formation of the thin film when toluene and IPA were supplied for the formation of nano carbon stream. When the graphene and carbon source are IPA at 150 ° C, they show excellent electrical characteristics of about 3? / ?.

[Table 6]

Example  9: Analysis results

[Figure 3] shows XRD results of Cu nanoparticles containing nanocarbon generated on IPA. Carbon peaks are observed under the pure Cu XRD diffraction peak as in the diffraction peak.

It can be seen that various nano carbon species (Onion, graphene, organic matter, etc.) surrounding Cu nanoparticles are observed when these states are observed using an electron microscope FE-TEM (see FIG. 4). These nano carbon species prevent aggregation of metal nanoparticles as much as possible. In particular, it was also confirmed that grapins were independently formed in a plate shape and a spherical shape (see (c) and (d) of FIG. 4). FIG. 5 shows the results of FE-SEM analysis of Ag nanoparticles having nanocarbon compounds.

S01: (a) Step S02: Step (b)
S03: (c) Step S04: (d)
S05: Step of mixing ink with an additive to prepare an ink

Claims (23)

(a) positioning a carbon-noncombustible metal in a non-oxidizing solvent;
(b) applying energy to the metal to pop the metal; And
(c) breaking the surrounding solvent while the metal being formed forms nanoparticles to obtain a product in which nanocarbon streams are formed together; Wherein the metal nanoparticles are mixed with the carbon nanoparticles.
The method of claim 1,
The carbon-noncombustible metal in step (a) is an alloy containing at least 50% of any one of Cu, Al, Ag, Sn, Au and Pt or any one of Cu, Al, Ag, Sn, Wherein the carbon nanofibers are made of carbon noble metal nanoparticles.
The method of claim 1,
Wherein the step (b) is performed by any one of a laser irradiation method, an arc discharge method, and an electric explosion method.
The method of claim 1,
The non-oxidizing solvent in step (a) is a non-aromatic solvent,
Wherein the product of step (c) comprises 5 to 30 wt% of nano-carbon particles when dried.
5. The method of claim 4,
The non-aromatic solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, , Dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexanone, distilled water, pyridine, nitromethane, acrylonitrile, octadecylamine, dimethylsulfoxide, methylene chloride, diethylene glycol Ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, ethylene glycol, acetone, methyl alcohol, methyl ethyl ketone, methyl ethyl ketone, Ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetamide N-methyl-2-pyrrolidone, hexane, chloro, trimethylbenzene, pyridine, nitromethane, acrylonitrile, octadecylamine, dimethylsulfoxide, methylenechlora, alpha-terpinol, dimethylformamide (NMP), and N-methylpyrrolidone (NMP).
The method of claim 1,
The non-oxidizing solvent in step (a) is an aromatic solvent,
Wherein the product of step (c) comprises 40 to 70 wt% of nano-carbon particles when dried.
The method of claim 6,
Wherein the aromatic solvent is at least one of toluene, benzene, nitrobenzene, aniline, phenol, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, naphthalene, xylene, xylene and anthracene. Gt;
The method of claim 1,
Wherein the non-oxidizing solvent in step (a) is a mixture of a non-aromatic solvent and an aromatic solvent.
The method of claim 1,
The doping element is added to the solvent of step (a)
Wherein the doping element is added to the product of step (c).
The method of claim 9,
Wherein the doping element is at least one of nitrogen, phosphorus, sulfur, and boron.
The method of claim 1,
(d) concentrating the product; Wherein the carbon noble metal nanoparticles are dispersed in the ink.
12. An ink in which metal nanoparticles are dispersed, wherein an additive is mixed in an ink base prepared by the method of any one of claims 1 to 11.
The method of claim 12,
The additive may be a binder, a monomer, a polymer, a resin, a copolymer, a ceramic precursor, a polyimide precursor, a metal binder, a ceramic binder, a nanoparticle binder, a surfactant, a functional material, a solvent, Characterized in that it is at least one of a base, a salt, an ionic species, a labeling agent, a pressure-sensitive adhesive, a nanoparticle, a metal nanowire, a metal nanoflake, a carbon nanotube, an oxide, a ceramic, a magnetic substance, Ink in which metal nanoparticles are dispersed.
The method of claim 13,
Wherein the binder is added in an amount of 1 to 50,000 parts by weight based on 100 parts by weight of the metal nanoparticles.
The method of claim 14,
Wherein the binder is at least one of a thermosetting resin, a photo-curable resin, a silane compound which causes a condensation reaction by hydrolysis, a thermoplastic resin, and a conductive polymer.
16. The method of claim 15,
Wherein the thermosetting resin is at least one of a urethane resin, an epoxy resin, a melamine resin, and a polyimide.
16. The method of claim 15,
The photo-curing resin may be at least one of an epoxy resin, a polyethylene oxide, a urethane resin, a reactive oligomer, a reactive monofunctional monomer, a reactive bifunctional monomer, a reactive trifunctional monomer,
Wherein the reactive oligomer is at least one of an epoxy acrylate, a polyester acrylate, a urethane acrylate, a polyether acrylate, a thiolate, an organosilicon polymer, and an organosilicon copolymer,
The reactive monofunctional monomer may be selected from the group consisting of 2-ethylhexyl acrylate, orthyldecyl acrylate, isodecyl acrylate, didecyl methacrylate, 2-phenoxyethyl acrylate, nonylphenol ethoxy lake monoacrylate, Acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, or hydroxybutyl methacrylate is used as the initiator. Or more,
The reactive bifunctional monomer may be selected from the group consisting of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Is at least one of pentyl glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol methacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate, and 1,6-hexanediol diacrylate,
Wherein the reactive trifunctional monomer is at least one of trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, glycidylpentatriacrylate, and glycidylpentatriacrylate,
Wherein the photoinitiator is at least one selected from the group consisting of benzophenone, benzyldimethylketal, acetophenone, anthraquinone, and thyugosanthone.
16. The method of claim 15,
The silane compound is any one or more of tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes,
The tetraalkoxysilanes may be any one or more of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane,
The trialkoxysilanes may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxy Silane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydride Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltri (Meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and the like.
Examples of the dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- Butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di- Di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, Wherein the metal nano-particles are dispersed in the ink, characterized in that the metal nanoparticles are at least one of diethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane .
16. The method of claim 15,
The thermoplastic resin may be at least one selected from the group consisting of polystyrene, polystyrene derivatives, polystyrene butadiene copolymers, polycarbonate, polyvinyl chloride, polysulfone, polyethersulfone, polyetherimide, polyacrylate, polyester, polyimide, polyamic acid, cellulose acetate, , Polyolefin, polymethyl methacrylate, polyether ketone, and polyoxyethylene. The ink according to claim 1, wherein the metal nanoparticles are dispersed in a solvent.
16. The method of claim 15,
Wherein the conductive polymer is at least one of a polythiophene based homopolymer, a polythiophene based copolymer, polyacetylene, polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene) Ink in which particles are dispersed.
The method of claim 12,
Wherein the metal nanowires are copper nanowires or silver nanowires.
The method of claim 12,
The dispersing agent may be at least one selected from the group consisting of BYK, block hollow bodies, BTK-Chemie, Triton X-100, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyvinylpyrrole, polyvinyl alcohol, Ganex, Wherein the metal nanoparticles are at least one selected from the group consisting of polysaccharides, sodium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, cetyltrimethylammonium 4-vinylbenzoate, pyrene-based derivatives, gum arabic, Dispersed ink.
The method of claim 12,
The surfactant may be at least one selected from the group consisting of LDS (Lithium Dodecyl Sulfate), CTAC (Cetyltrimethyl Ammonium Chloride), DTAB (Dodecyl-trimethyl Ammonium Bromide), nonionic C12E5 (Pentaoxoethylenedocyl ether), dextrin, PEO wherein the metal nanoparticles are dispersed in an organic solvent.

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