KR101433639B1 - Conductive nano ink using copper nano gel composition and prepration method of the same - Google Patents
Conductive nano ink using copper nano gel composition and prepration method of the same Download PDFInfo
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- KR101433639B1 KR101433639B1 KR1020130023498A KR20130023498A KR101433639B1 KR 101433639 B1 KR101433639 B1 KR 101433639B1 KR 1020130023498 A KR1020130023498 A KR 1020130023498A KR 20130023498 A KR20130023498 A KR 20130023498A KR 101433639 B1 KR101433639 B1 KR 101433639B1
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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- C—CHEMISTRY; METALLURGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
Description
The present invention relates to a conductive copper nano ink using a copper nano-gel composition and a method for producing the same. More specifically, a copper nano-particle is formed into a gel-like shape by forming a film of a polymeric binder in a synthesis step, thereby further improving the dispersion characteristics of the copper nano-particles and forming a conductive copper nano ink having high oxidation stability even in the air- ≪ / RTI >
Electronic devices printed with electronic circuits have advantages of substrate flexibility, low cost, ease of processing, etc. One of the main components of such electronic devices is conductive lines and thin films. Especially, in the formation of the conductive line, the stability and conductivity of the material constituting the conductive line must be high, and the line forming technique must be elaborated. Conductive polymers can be applied to form conductive lines, but the conductivity and stability of conductive polymers are generally lower than metallic ones. Thus, metal-based nanoinks have recently been introduced to mitigate these drawbacks.
Nano ink is an ink-like electronic material in which conductive nano-sized particles are dispersed. It is necessary to print electrodes and circuits of RFID and flexible printed circuit board (FPCB) by ink jet method. Material. Conventionally, a lithography technique has been applied to form a conductive line of an electronic circuit. However, this technique has a disadvantage in that the process is complicated, the cost is high, and the selection of the substrate is also limited. However, by using nano ink, various printing methods such as inkjet, roll-to-roll gravure, screen printing and the like can be applied to the formation of a line, and a semiconductor circuit line can be more precisely implemented. As a result, the probability of failure is reduced by half and the cost is reduced, and development of nano ink is becoming more and more active because it can be applied to a wide range of fields such as barcode, biochip, and anti-counterfeit money production.
In the production of nano ink, metal particles should be sintered at a low temperature when patterns are formed, and patterns having uniform and high conductivity should be formed in order to reduce the process cost and simplify the process. Among the metal particles having such a characteristic, silver is the most representative, and the use of silver nano ink for dispersing silver nanoparticles is increasing. However, in the case of silver nanoparticles, the dispersibility due to the solvent is low, and the price of silver itself is high, which is a hindrance to the cost reduction of the device. In this regard, copper, which is inexpensive and has excellent conductivity, is attracting attention as a material that can solve the problems of silver. However, when copper is used as nanoparticles, there are problems with conductivity only in the heat treatment conditions in an inert gas such as nitrogen or argon because of the problem of being easily oxidized in the air.
Conventional patent technologies related to nano ink include Korean Patent Laid-Open Publication No. 10-2006-0012545, a low-temperature sintered conductive nano ink, a method of manufacturing the same, a Korean Patent Registration No. 10-0860446, a dispersion assistant for metal nanoparticles, Metal nano ink, Korean Patent No. 10-0996650, and a method of producing a low melting point nano ink. Korean Patent No. 10-0890928 discloses that a polymer dispersant composed of at least one of PVP (polyvinylpyrolidone), PVA (polyvinylalcohol) and a cationic water-based emulsion and a copper nitrate are added to deionized water and stirred to disperse copper ions And a method of producing a copper nano ink including a step of preparing a mixture is disclosed in Korean Patent No. 10-1020844 by using a reducing agent containing formic acid or acetic acid and an alcohol having 1 to 3 carbon atoms or an ether, There is known a method of reducing and sintering copper nanoparticles that can be sintered at a low temperature of less than < RTI ID = 0.0 > There are some conventional technologies related to copper nano ink, and there is a technology capable of low-temperature sintering. However, using the copper nano-gel composition formed with the polymer binder film in an optimal state as in the present invention, There is no technology related to the increased copper nano ink.
Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.
In the case of silver applied to existing metal nano ink, the dispersibility to the solvent is low and the silver itself is expensive, which has been a hindrance to the cost reduction of the device. As such problems have arisen, nano ink has been manufactured by selecting copper having a low unit cost and excellent conductivity instead of silver. However, in the case of copper, there is a disadvantage that it must be heat-treated in an inert gas such as nitrogen or argon because of the problem of being easily oxidized in the air.
Therefore, the present invention can form a pattern having uniform and high conductivity even when sintered at a low temperature of 100 to 200 ° C by using a copper nano-gel composition in which a polymeric binder film is formed in an optimal state, And a conductive copper nano ink.
The problems to be solved by the present invention are not limited to the above-mentioned technical problems, and other technical problems which are not mentioned can be clearly understood by those skilled in the art from the following description.
It is an object of the present invention to provide a conductive copper nanoink containing a copper nanogel composition.
The inventors of the present invention have recognized and solved the problem that the copper nano ink is rapidly oxidized by sintering and the conductivity is lowered so that when copper nano ink is manufactured using the copper nano-gel composition in which the polymer binder film is formed optimally The polymer binder film formed by the contact of copper with oxygen even when sintered in the air is shielded and the oxidation stability is excellent and the heat treatment can be performed even at a low temperature of 100 to 200 ° C and a pattern having uniform and high conductivity can be formed And completed the present invention.
Hereinafter, the conductive copper nanoink of the present invention will be described.
Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which the present invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.
According to an aspect of the present invention, there is provided a conductive copper nano ink comprising copper nano-gel composition dispersed in an organic solvent in a copper nano ink having excellent oxidation stability even in air sintering.
The term " sintering " in this specification means that when the powder is heated to a temperature close to the melting point, the powder particles are mutually bonded and solidified. That is, the copper nanoparticles present in the copper nanoink according to the present invention have a momentary phase change under a certain temperature, and the bonding surfaces of the particles adhere to each other to form a pattern. More specifically, the present invention means that the nanoparticles of the present invention are melted and softened and then the surface area is widened. The nanoparticles and the polymer can be understood as meaning different from thermosetting which forms a film by firmly adhering nanoparticles and polymers.
The term oxidation stability in this specification means that a substance undergoes little or no oxidation reaction under the influence of temperature or time in the presence of air or oxygen to bind to oxygen or lose electrons. Since the resistance increases as the oxidation proceeds, that is, the copper is changed to copper oxide, the criterion for determining the oxidation stability in the present invention is the amount of the copper oxide and the thickness of the oxide film on the surface. If the oxidation stability is excellent, it means that the amount of copper oxide produced as a result of sintering is small and the thickness of the oxide film on the surface is thin. However, in the case of dried copper nanoparticles, it is impossible to observe the oxide film with the naked eye. Therefore, it is possible to confirm the progress of oxidation by XRD (see FIG. 6).
According to a preferred embodiment of the present invention, the copper nano-gel composition is obtained by dissolving a copper precursor in a mixed solvent of distilled water and ethylene glycol to prepare a solution, adding a polymer binder and a reducing agent to the solution, . In the present invention, the copper nano-gel composition is a very important factor. Generally, copper nanoparticles in powder form are prepared and used in copper nano ink. In the present invention, a copper nano-gel having a colloidal state in which nanoparticles are dispersed in a solvent, This is because it is applied to ink. Particularly, the copper nanoparticles in a colloidal state in the present invention have a film formed of a polymeric binder, thereby preventing contact between copper particles and oxygen, so that oxidation does not easily occur even after ink is sintered in air. Therefore, in the present invention, the copper nano-gel composition is not merely different from the conventional copper nano ink, but includes a feature that the polymer binder forms a film on the particles contained in the gel state. Therefore, The problem of unresolved oxidation stability can be greatly improved.
According to a preferred embodiment of the present invention, the copper precursor is at least one selected from the group consisting of copper nitrate (Cu (NO 3) 2), copper chloride (CuCl 2 ), copper sulfate (CuSO 4 ), copper acetate ((CH 3 COO) 2 Cu) (copper (ⅱ) acetylacetonate), stearic acid, copper (copper (ⅱ) stearate), perchlorate, copper (copper (ⅱ) perchlorate), ethylenediamine copper (copper (ⅱ) ethylenediamine), and copper hydroxide comprises a (Cu (OH) 2) characterized in that at least one member selected from the group eugun to, more preferably of copper nitrate (Cu (NO3) 2), copper chloride (CuCl 2), copper sulfate (CuSO 4), copper acetate ((CH 3 COO) 2 Cu) and copper hydroxide (Cu (OH) 2), and wherein the at least one selected from the group eugun containing, and most preferably copper nitrate (Cu (NO3) 2), copper chloride (CuCl 2), ethyl And at least one selected from the group consisting of copper ((CH 3 COO) 2 Cu and copper hydroxide (Cu (OH) 2 )
According to a preferred embodiment of the present invention, the mixed solvent of distilled water and ethylene glycol is characterized in that the mixed volume ratio of the distilled water and the ethylene glycol is 1: 1. In the present invention, the mixing ratio of distilled water and ethylene glycol is very important. When the ratio of distilled water is higher than that of ethylene glycol or vice versa, nanoparticles are formed to have a size of 100 nm or more, resulting in disadvantages such as poor dispersibility and failure to prevent heat and explosion caused by reduction of the copper precursor Because. This is a very important factor because the kinds and mixing ratios of the solvents used in the solvent mixing in forming the copper nanoparticles of the present invention can affect the results of the present invention. It is of great importance in the present invention that the inventors of the present invention have found an important role of mixed solvents in the formation of copper nanogel compositions. Examples of the solvent that can be used in the above-mentioned mixed solvent include alcohols including methanol, ethanol, isopropanol and butanol, glycols including glycerin, ethyl acetate, butyl acetate, and carbitol acetate. Ethers including acetates, diethyl ether, tetrahydrofuran and dioxane, ketones including methyl ethyl ketone and acetone, aromatic hydrocarbons including benzene and toluene including hexane and heptane, Chloroform, methylene chloride, carbon tetrachloride and the like can be utilized. However, according to a preferred embodiment of the present invention, a 1: 1 mixed solvent of distilled water and ethylene glycol exhibits the best effect.
According to a preferred embodiment of the present invention. When the copper precursor is dissolved in a mixed solvent of distilled water and ethylene glycol, the dissolution temperature is 50 to 70 캜, more preferably 55 to 65 캜, and most preferably 60 캜. In the present invention, it is very important to dissolve the copper precursor by adjusting the temperature of the mixed solvent to 60 ° C before and after 60 ° C. If the temperature is lower than 50 ° C, the copper nanoparticles tend to be larger and the dispersibility is lowered, so that it becomes difficult to produce the ink. When the temperature is higher than 70 ° C, the particles are small and the dispersibility can be excellent. However, And is vulnerable to oxidation stability. The inventors of the present invention have found that the dissolution temperature conditions are also very important in the present invention since copper nanoparticles are excellent in oxidation stability and the dispersion is also optimized.
According to a preferred embodiment of the present invention, the polymer binder may be any of conventional polymeric binders useful for producing copper nanoparticles, but preferably includes polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA), acrylic resin , At least one member selected from the group consisting of urethane resin, polyester resin, polyvinylpyrrolidone (PVP), methyl cellulose, ethyl cellulose, hydroxypropylmethyl cellulose (HPMC) and polyethylene oxide (PEO) do. Among the polymeric binders, an organic polymer having a carbonyl group or an amine group is more preferably used, and a polymer having a carbamido group or an amide group is most preferably used. This is because, in the case of a polymer binder into which a carbamate group or an amide group is introduced, it is advantageous to produce stable and monodisperse copper nanoparticles.
According to a preferred embodiment of the present invention, the reducing agent includes hydrazine (N 2 H 4 ), sodium borohydride (NaBH 4 ), formaldehyde, an amine compound, a glycol compound, glycerol, dimethylformamide, tannic acid, citrate and glucose , More preferably at least one member selected from the group consisting of hydrazine (N 2 H 4 ), sodium borohydride (NaBH 4 ), amine compounds, and tannic acid And most preferably at least one of hydrazine (N 2 H 4 ), sodium borohydride (NaBH 4 ), and an amine compound. In the present invention, the reducing agent serves to reduce the copper precursor to copper particles.
According to a preferred embodiment of the present invention, the organic solvent is at least one selected from the group consisting of an alcohol solvent, a glycol ether solvent and a sulfoxide solvent. In an embodiment of the present invention, the alcohol solvent may be selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Propanol, 1-hexanol, cyclopentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-butanol, Butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, Heptanol, 1-heptanol, 2-ethyl-1-hexanol, 2,6-dimethyl-4-heptanol Methyl cyclohexanol, 4-methylcyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol, wherein the glycol ether solvent Include triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene glycol monopropyl ether and dipropylene glycol methyl ether. The sulfoxide The solvent is characterized by containing dimethyl sulfoxide (DMSO), di-n-butyl sulfoxide, tetramethylene sulfoxide and methylphenyl sulfoxide. Accordingly, the organic solvent is at least one selected from the group consisting of all the solvents listed above.
According to a preferred embodiment of the present invention, the copper nanogel is dispersed in the organic solvent at a stirring rate of 1000 to 2000 rpm for 10 to 60 minutes, more preferably at a stirring rate of 1200 to 1800 rpm, 40 minutes, and most preferably, it is dispersed for 30 minutes at a stirring speed of 1500 to 1600 rpm. If the particle size is less than the above range, dispersion can not be uniformly performed. If the particle size exceeds the above range, unnecessary dispersion occurs. Therefore, in the present invention, copper nanoparticles sufficiently dispersed in the above range can be confirmed. Additionally, The use of high frequency sonication during stirring is the most preferable method for obtaining uniformly dispersed copper ink.
According to a preferred embodiment of the present invention, the copper nano-ink further comprises 1 to 10 parts by weight of polyvinylpyrrolidone (PVP) as an additive, more preferably 3 to 7 parts by weight, relative to 100 parts by weight of the copper nano- By weight, most preferably 5 parts by weight. The additives added in the present invention are further characterized in that they are added during the production of the copper nano-ink, and when the copper nano-gel is dispersed in the solvent. The addition of additives in the present invention is very important. It is possible to confirm that the conductivity, oxidative stability and dispersibility of the ink become excellent when the additive is additionally added (see Production Example 2 and Experimental Example 1). In the present invention, polyvinylpyrrolidone (PVP) is added as a dispersant, but is added to prevent oxidation when added additionally as an additive. Therefore, in the present specification, when PVP is added as a role of dispersion, it is described as a polymer binder and added as a role of prevention of oxidation is described as an additive. Since the polymeric binder PVP as an additive added to the copper nano-gel is combined with copper ions reduced in the copper oxide to form a film, the oxidation stability of the copper nano ink is ultimately improved, so that the polymer binder as an additive in the present invention There is a very important meaning.
According to a preferred embodiment of the present invention, the copper nanogel is characterized in that the average particle diameter (particle diameter or size) of the particles is 30 to 150 nm, more preferably 50 to 100 nm, and most preferably 70 to 90 nm can do. In the present invention, the reason why the average particle diameter of the copper nanoparticles is specifically limited is that 30 to 150 nm is most advantageous for forming a uniform and elaborate copper thin film pattern. The copper nanoparticles are formed by dissolving the copper oxide in a mixed solvent of distilled water and ethylene glycol and then reacting the copper oxide with a reducing agent. At this time, the mixing ratio of the mixed solvent, the mixing temperature, and the particle size of the polymeric binder . The size of the copper nanoparticles can be controlled according to the above conditions. When the thickness is less than 30 nm, the oxidation stability is greatly deteriorated in spite of the excellent dispersibility. In the case of 150 nm, the copper nanoparticle is weakly dispersed due to gelation.
According to a preferred embodiment of the present invention, the conductive copper nano-ink is characterized by low-temperature sintering at a low temperature of 100 to 300 ° C, more preferably at a temperature of 150 to 250 ° C, And sintering at 150 ° C for 1 minute or 200 ° C for 30 seconds. In the present invention, it can be said that the reasons for not being oxidized even in the low-temperature sintering in the air are as follows. First, the mixing ratio of distilled water to ethylene glycol, the temperature condition of the second mixed solvent, the third ratio of copper oxide, the polymer binder, the reducing agent, the rate of the fourth reducing agent addition, the dispersing condition in the ink preparation and the additive polyvinylpyrrolidone (PVP) The addition amount. Among the above five conditions, the first, second and fifth conditions are most important, but when the above five conditions are satisfied, a polymer film is formed on the copper nanoparticles within a range that does not disturb the conductivity, Ink can be produced. According to a preferred embodiment of the present invention, in the production of the copper nanoink of the present invention, the mixing ratio of distilled water to ethylene glycol is 1: 1, the temperature of the second mixed solvent is 60 ° C, and the third is the copper oxide, the polymer binder, The ratio of the reducing agent was 37 mL / min, the rate of the reducing agent was 37 mL / min, and the fifth ink was dispersed at 0 ° C and 1200 rpm for 15 hours or more while adding 5% by weight of polyvinylpyrrolidone (PVP) Copper nano ink having excellent oxidation stability is produced even in low-temperature sintering in the air if the conditions are all satisfied. In particular, when the paste is thermally cured at 150 ° C for 1 minute or at 200 ° C for 30 seconds at sintering, a pattern having excellent conductivity is formed.
The conductive copper nano ink of the present invention is applied onto a substrate by a method such as inkjet, roll-to-roll gravure, screen printing, etc., and can be formed by sintering the substrate coated with ink with heat in the air, have. According to the embodiment of the present invention, the conductive copper nano ink of the present invention can be most suitably applied to the screen printing method. When screen printing is performed, as the screen mesh becomes smaller, that is, as the size of the screen net becomes larger, the amount of ink transferred increases, so that the thickness of the ink is relatively thick, and a pattern having excellent conductivity can be formed.
According to a preferred embodiment of the present invention, the conductive copper nano-ink has a resistivity value of 10 to 100 m? / Sq / mil. However, the higher the resistivity value, the more excellent the conductivity and the resistivity value is 10 m? / Sq / mil The closer the distance is, the more preferable. In the present invention, the range of the resistivity value is very important. If the resistivity value is expressed in the above range, it is excellent to use as a conductive line of an electronic device. In this specification, sq at mΩ / sq / mil, which is used as the unit of resistivity value, is a unit to correct the value obtained by dividing the length by the line width at which the resistance value is measured. The mil is about 25 μm thick and is used as the thickness unit of the wire. Means a unit for correcting the thickness. That is, the resistivity and the thickness can be used as uΩ (resistance) .cm (thickness) in the unit mΩ (resistance) / sq (length) / mil (thickness) of the resistivity value.
The features and advantages of the present invention are summarized as follows:
(a) The present invention provides a conductive copper nano ink comprising a copper nanogel composition dispersed in an organic solvent;
(b) The conductive copper nanoink of the present invention can be sintered by heat treatment at a relatively low temperature of 100 to 300 캜, and is excellent in dispersibility;
(c) The conductive copper nanoink of the present invention can form a copper pattern having excellent conductivity by not oxidizing even if it is heat-treated in air; And
(d) According to the present invention, since the conventional copper oxidation problem does not require a process line for shutting off the air, the process can be simplified and the cost can be reduced.
1 is a photograph showing a copper nano-gel of the present invention.
2 is a photograph showing an SEM image of a copper nano-gel.
3 is a photograph showing a pattern in which conductive copper nano ink is screen printed.
4 is a graph showing a change in resistivity of the conductive copper nano ink according to time and temperature.
FIG. 5 is an XPS measurement value after 150 degrees and 250 degrees thermal curing of the copper printed coating.
FIG. 6 is an XRD measurement value after 1 minute, 5 minutes, and 10 minutes thermal curing at 150 degrees of the copper printed coating film.
Fig. 7 is a graph showing changes in resistivity according to additives, curing temperature, and curing time of the copper-plated coating film.
Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. It will be self-evident. The present invention is defined only by the scope of the claims, however, the advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below.
In addition, throughout the present specification, the percentages used to denote the concentration of a specific substance are as follows: solid / solid (weight / weight), solid / liquid (weight / volume) The liquid / liquid is (vol / vol)%.
Example
[ Manufacturing example 1-1: Preparation of copper nano-gel composition]
Manufacturing example 1-1 (Preparation of Copper Nanogel Composition-Control)
A mixed solvent of 1600 ml of distilled water and 1600 ml of ethylene glycol (DAE JUNG) was heated to 60 ° C, and 120 g of Cu (NO 3 ) 2 (DAE JUNG0) was dissolved to prepare a solution. 60 g of polymer binder polyvinylpyrrolidone (PVP MW72000, BASF) was added to the solution, and the mixture was stirred with a mechanic stirrer (Heidolph, RZR2021) so as to be uniformly dispersed. 200 ml of hydrazine (SFC) was injected into the dispersed solution at a rate of 37 ml / min, stirred for 1 hour, and then separated by centrifugal separator (Hitachi, Hitachi-3000) at 5000 rpm for 10 minutes to obtain 32 g of a precipitate . As a result, it was possible to obtain a gel-like composition in which copper nanoparticles were dispersed, and SEM (Bruker, S-4800) was coated to examine the diameter of the particles. As a result, it was confirmed that the average diameter of the copper nanoparticles was 80 nm 2).
Manufacturing example 1-2 (Preparation of copper nano-gel composition according to mixed solvent temperature)
The same method as in Preparation Example 1-1 was used except that the temperature of the mixed solvent was changed to 40 캜 in the preparation of the conductive copper nano-gel composition. As a result, copper nanoparticles having an average size of 180 nm were prepared in powder form. That is, in this case, since the size of the copper nanoparticles was relatively larger than that of Production Example 1-1, it was confirmed that the dispersion was not excellent and the gelation did not occur.
Manufacturing example 1-3 (Preparation of copper nano-gel composition according to mixed solvent temperature)
The same method as in Preparation Example 1-1 was used except that the temperature of the mixed solvent was changed to 80 캜 in the preparation of the conductive copper nano-gel composition. As a result, copper nanoparticles having an average size of 45 nm were prepared in gel form. In this case, since the size of the copper nanoparticles was smaller than that of Production Example 1-1, the dispersibility was not a problem, but the oxidation resistance after the thermal curing was remarkably low.
Manufacturing example 1-4 (Preparation of Copper Nanogel Composition According to Solvent Mixing Ratio)
The same procedure as in Preparation Example 1-1 was carried out except that 1500 ml of distilled water and 500 ml of ethylene glycol were used in the preparation of the conductive copper nano-gel composition. As a result, copper nanoparticles having an average size of 120 nm were prepared in gel form, but they were found to be very dangerous because they could not prevent the heat and explosion caused by the reduction of the copper precursor.
Manufacturing example 1-5 (Preparation of Copper Nanogel Composition According to Addition of Polymeric Binder)
A copper nanogel composition having an average particle size of 100 nm was prepared in the same manner as in Preparation Example 1-1, except that 50 g of polyvinyl pyrrolidone (PVP) was used in the preparation of the conductive copper nano-gel composition.
Manufacturing example 1-6 (Preparation of Copper Nanogel Composition According to Addition of Polymeric Binder)
A copper nano-gel composition having an average particle size of 80 nm was prepared in the same manner as in Preparation Example 1-1, except that 77 g of polyvinyl pyrrolidone (PVP) was used in the preparation of the conductive copper nano-gel composition.
Manufacturing example 1-7 (Preparation of Copper Nanogel Composition According to Addition of Polymeric Binder)
A copper nano-gel composition having an average particle size of 75 nm was prepared in the same manner as in Preparation Example 1-1 except that 90 g of polyvinyl pyrrolidone (PVP) was used in the preparation of the conductive copper nano-gel composition.
Manufacturing example 1-8 (Preparation of Copper Nanogel Composition According to Addition of Polymeric Binder)
A copper nano-gel composition having an average particle size of 60 nm was prepared in the same manner as in Preparation Example 1-1, except that 100 g of polyvinyl pyrrolidone (PVP) was used in the preparation of the conductive copper nano-gel composition.
Manufacturing example 1-9 (Preparation of Copper Nanogel Composition According to Addition of Polymeric Binder)
A copper nano-gel composition having an average particle size of 40 nm was prepared in the same manner as in Preparation Example 1-1 except that 120 g of polyvinyl pyrrolidone (PVP) was used in the preparation of the conductive copper nano-gel composition.
Table 1 below summarizes the characteristics and manufacturing conditions of the copper nano-gel compositions of Production Examples 1-1 to 1-11.
Composition
Mixing ratio
(Volume ratio)
Addition amount (g)
Size (nm)
1) distilled water: mixing ratio of ethylene glycol
2) Polyvinylpyrrolidone (PVP)
According to the measurement results, when the mixing ratio of the solvent is not 1: 1, the nanoparticles are prepared in the form of a gel, but the copper precursor is reduced and heat and explosion are prevented It appeared to be very dangerous. Further, as a result of the comparison of Production Examples 1-1 to 1-3, it was found that when the mixing temperature was low or high when the solvent was mixed, nanoparticles of the proper size were not produced. Finally, when the proportion of the polymeric binder was smaller than that of the control group (Preparation Example 1-1) (Production Example 1-5), the size of the nanoparticles became larger, and when the ratio became larger (Production Examples 1-6 to 1-9) And it was confirmed that it was small. The nanoparticles have the highest oxidation stability at 80 nm and have high conductivity. Therefore, the ratio of copper precursor, polymer binder and reducing agent should be controlled as 2: 1: 3.3.
[ Manufacturing example 2: Preparation of Conductive Copper Nano Ink]
Manufacturing example 2-1 (Preparation of Conductive Copper Nano Ink _ Control)
120 g of the copper nano-gel prepared in Preparation Example 1-1, 6 g of polyvinyl pyrrolidone (PVP) and 24 g of ethylene glycol were added to a 250 cc container to prevent oxidation due to heat generated during the dispersion process (GLOBAL LAB_S-41 Direct Driven Stirrer) for at least 15 hours at 0 ° C and 1200 rpm, or uniformly dispersed copper ink using a centrifugal agitator (THINKY_THINKY Mixer ARE-310) at 2000 rpm for 30 minutes at room temperature Respectively.
Manufacturing example 2-2 (Preparation of Conductive Copper Nano Ink)
Copper nano ink having an average particle size of 80 nm was prepared by the same method as Preparation Example 2-1 except that 1 wt% of NANOBYK-3600 (BYK) was used as an additive for improving scratch resistance in the production of conductive copper nanoink .
Manufacturing example 2-3 (Preparation of Conductive Copper Nano Ink)
Copper nano ink having an average particle size of 80 nm was prepared in the same manner as in Preparation Example 2-1 except that DISPERBYK-192 (BYK) was used in an amount of 5 wt% as a wetting and dispersing additive in the production of conductive copper nanoink.
Manufacturing example 2-4 (Preparation of Conductive Copper Nano Ink)
Copper nano ink having an average particle size of 80 nm was prepared by the same method as Preparation Example 2-1, except that the additive polyvinyl pyrrolidone (PVP) was not added in the production of conductive copper nano ink.
Manufacturing example 2-5 (Preparation of Conductive Copper Nano Ink)
Except that 9.6 g (8% by weight) of an additive polyvinylpyrrolidone (PVP) was added in the production of conductive copper nano ink, the same procedure as in Production Example 2-1 was carried out to obtain a copper nano ink .
[ Experimental Example 1: Evaluation of Electrical Properties of Conductive Copper Nano Ink]
The electrical properties of the conductive copper nanoink Production Examples 2-1 to 2-5 prepared in Preparation Example 2 were evaluated. The pattern forming method was a screen printing method, and a pattern having a width of 1 mm and a length of 930 mm was formed using a screen printing plate of 150 mesh each (see FIG. 3). Then, they were thermally cured in air at 150 ° C and 200 ° C in one minute, respectively, and then resistivity values were measured using a resistance meter (KEITHLEY, 2000 Multimeter). In the same manner, the screen was adjusted to 80 mesh to form a pattern, and the conductivity was measured.
As can be seen from the results of Production Example 2-1, the conductivity of the pattern was excellent when the screen mesh was small, and it was understood that curing at 200 ° C for 30 seconds was the best condition (see Tables 2 and 4) ). The smaller the screen mesh is, the larger the screen mesh is, and therefore, the larger the amount of ink to be transferred, and the larger the thickness of the printed ink, the higher the screen mesh is. As shown in FIG. 4, which is a graph showing a change in resistivity according to the time and temperature of the conductive copper nano ink, the copper nano ink had an initial measured resistivity value of 20 mΩ / sq / In the case of copper nanoinks thermally cured for 30 seconds at 200 ° C, the initial resistivity of 10 mΩ / sq / mil was maintained within 15 mΩ / sq / mil over time, with the mils maintained within 40 mΩ / sq / mil . That is, in the case of the conductive copper nano ink using the copper nano-gel composition, it was confirmed that the conductive property was further improved when cured at 200 ° C, and the durability against conductivity was also high.
On the other hand, according to the above Table 2, the resistivity value of Preparation Example 2-3 was measured to be very high, which was unsuitable as a conductive material and the specific resistance value was low in Production Example 2-2. 1, respectively. In the case of Production Example 2-4, the coating film was broken after thermosetting because the additive polyvinylpyrrolidone (PVP) was not added. In the case of X (no conductivity) in Production Example 2-5, polyvinylpyrrolidone (PVP) There is too much conductivity.
In general, the mixing ratio of distilled water to ethylene glycol is 1: 1, the temperature of the second mixed solvent is 60 ° C, and the ratio of the copper precursor, the polymer binder, and the reducing agent is 2: 1 The conditions for addition of 5% by weight of additive polyvinylpyrrolidone (PVP) in the dispersion condition (0 ° C, stirring at 1200 rpm for 15 hours or more) during the preparation of the ink, , It was found that the best conductivity was obtained by thermosetting at 150 ° C for 1 minute or 200 ° C for 30 seconds.
While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (13)
A copper nanogel composition dispersed in an organic solvent,
The copper nano-gel composition is a reaction product obtained by dissolving a copper conductor in a mixed solvent of distilled water and ethylene glycol, adding a polymer binder and a reducing agent,
The mixing ratio of distilled water to ethylene glycol was 1: 1,
When the copper precursor is dissolved in a mixed solvent of distilled water and ethylene glycol, the dissolution temperature is 50 to 70 ° C,
Wherein the copper nano ink further comprises 1 to 10 parts by weight of polyvinyl pyrrolidone (PVP) relative to 100 parts by weight of the copper nano-gel as an additive for preventing oxidation of the copper nano ink.
The copper precursor may be at least one selected from the group consisting of copper nitrate (Cu (NO 3) 2), copper chloride (CuCl 2 ), copper sulfate (CuSO 4 ), copper acetate ((CH 3 COO) 2 Cu), copper (II) acetylacetonate, One selected from the group comprising copper stearate, copper (Ⅱ) stearate, copper (Ⅱ) perchlorate, copper (Ⅱ) ethylenediamine and copper hydroxide (Cu (OH) 2 ) By weight based on the weight of the conductive copper nano-ink.
The polymer binder may be selected from the group consisting of polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA), acrylic resin, urethane resin, polyester resin, polyvinylpyrrolidone (PVP), methylcellulose, ethylcellulose, (HPMC), and polyethylene oxide (PEO). ≪ Desc / Clms Page number 19 >
The reducing agent may be at least one selected from the group consisting of hydrazine (N 2 H 4 ), sodium borohydride (NaBH 4 ), formaldehyde, amine compounds, glycol compounds, glycerol, dimethylformamide, tannic acid, citric acid and glucose Lt; RTI ID = 0.0 > copper < / RTI > ink.
Wherein the organic solvent is at least one selected from the group consisting of an alcohol solvent, a glycol ether solvent and a sulfoxide solvent.
Wherein the copper nano-gel is dispersed in the organic solvent at a stirring speed of 1000 to 2000 rpm for 10 to 60 minutes.
Wherein the copper nano-gel has an average particle diameter of 30 to 150 nm.
Wherein the conductive copper nano ink is sintered at a temperature of 100 to 300 캜.
Wherein the conductive copper nano ink has a specific resistance value of 10 to 100 m? / Sq / mil.
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| CN103722179A (en) * | 2013-12-19 | 2014-04-16 | 中国科学院深圳先进技术研究院 | Preparation method of nano copper paste for conductive ink |
| WO2018134411A1 (en) | 2017-01-23 | 2018-07-26 | Francisco Albero S.A.U. | Stretchable conductive ink |
| KR20200110539A (en) * | 2019-03-14 | 2020-09-24 | 한양대학교 산학협력단 | Copper precursor for intense pulsed light sintering, manufacturing method for thereof, and intense pulsed light sintering method for thereof |
| CN111822696A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院深圳先进技术研究院 | Monodisperse nano-copper particles for conductive ink and preparation method and application thereof |
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| JP2002256178A (en) | 2001-03-01 | 2002-09-11 | Mitsubishi Pencil Co Ltd | Process for producing gel ink composition |
| KR100727451B1 (en) * | 2005-04-26 | 2007-06-13 | 주식회사 잉크테크 | Metal-based inks |
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| CN103722179A (en) * | 2013-12-19 | 2014-04-16 | 中国科学院深圳先进技术研究院 | Preparation method of nano copper paste for conductive ink |
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| KR102242532B1 (en) | 2019-03-14 | 2021-04-21 | 한양대학교 산학협력단 | Copper precursor for intense pulsed light sintering, manufacturing method for thereof, and intense pulsed light sintering method for thereof |
| CN111822696A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院深圳先进技术研究院 | Monodisperse nano-copper particles for conductive ink and preparation method and application thereof |
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