WO2012165801A2 - Complexe particulaire de cuivre destiné à l'électronique imprimée et pâte de cuivre - Google Patents

Complexe particulaire de cuivre destiné à l'électronique imprimée et pâte de cuivre Download PDF

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Publication number
WO2012165801A2
WO2012165801A2 PCT/KR2012/004083 KR2012004083W WO2012165801A2 WO 2012165801 A2 WO2012165801 A2 WO 2012165801A2 KR 2012004083 W KR2012004083 W KR 2012004083W WO 2012165801 A2 WO2012165801 A2 WO 2012165801A2
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WO
WIPO (PCT)
Prior art keywords
copper
fine particle
complex
particle complex
parts
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PCT/KR2012/004083
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English (en)
Korean (ko)
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WO2012165801A3 (fr
Inventor
정인범
이병윤
정순철
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(주)창성
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Publication of WO2012165801A2 publication Critical patent/WO2012165801A2/fr
Publication of WO2012165801A3 publication Critical patent/WO2012165801A3/fr

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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
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys

Definitions

  • the present invention relates to a copper particulate complex material having a small particle size, uniformity, and sintering at low temperature. More specifically, the present invention relates to a field of printed electronics such as a reactor LCD electrode material, an RFID antenna, and a flexible printed circuit board (PCB). The present invention relates to a copper particulate complex material used in the invention.
  • a metal fine particle dispersion is used when forming a fine wiring or a thin film using the screen printing method.
  • the manufacturing cost can be lowered compared to gold, but when the wiring width and the space between the wirings are narrowed, they become disconnected due to electron migration. There is a problem.
  • the use of the paste which consists of a microparticle complex which uses copper as a main raw material is examined.
  • copper not only has high conductivity such as gold and silver, but also has excellent ductility but low unit cost, and the mobility of electrons is much less than that of silver.
  • NDA is an abbreviation of NeoDecanoic Acid and is neodecanoic acid.
  • the copper fine particle complex obtained in the prior art has a wide particle size distribution, a uniform shape, and a large particle size, when the copper paste is manufactured using the same, it is difficult to secure dispersibility and is poor in wettability and printability. There was a problem that it is difficult to obtain a copper thin film.
  • the copper fine particle complex obtained in the prior art has a problem that the sintering temperature is 400 ° C or more, and sintering is possible only in a reducing atmosphere, which makes it difficult to apply to a flexible substrate.
  • An object of the present invention is to solve the above problems, specifically, to provide a copper fine particle complex having a narrow particle size distribution, a uniform shape, and a particle size of 1 ⁇ m or less.
  • Another object of the present invention is to provide a copper fine particle complex which can obtain a fine copper thin film with good dispersibility, wettability, and printability using the copper fine particle complex as described above.
  • an object of the present invention is to provide a copper paste that can be applied to a flexible substrate by sintering in an inert atmosphere and a temperature range of 250 ⁇ 300 ° C.
  • the said fine copper particle complex is obtained by making it react with formic acid using a copper salt as a precursor, and the said copper fine particle complex contains the anhydrous copper (II) formate (Cu (COOH) 2 ) and copper (Cu) whose particle diameter is 1 micrometer or less. Copper fine particle complex characterized by the above-mentioned.
  • the copper fine particle complex includes copper metal particles in a weight ratio of 5 to 30% and anhydrous copper (II) formate in a weight ratio of 70 to 95%.
  • the copper salt complex is copper oxide, copper hydroxide, copper nitrate, copper carbonate, copper sulfate, copper chloride, or copper acetate complex.
  • said copper salt and said formic acid reaction are in a closed vessel with non-reactive balls, said closed vessel being rotated during the reaction.
  • the non-reactive ball is a copper fine particle complex, characterized in that the zirconium ball having a particle diameter of 2 mm or less.
  • the copper fine particle complex is 50 to 90 parts by weight based on 100 parts by weight of the conductive composition
  • the solvent is 10 to 50 parts by weight based on 100 parts by weight of the conductive composition
  • the additive is conductive Conductive composition, characterized in that mixed in 0.1 to 3 parts by weight with respect to 100 parts by weight of the composition.
  • the solvent comprises at least one component selected from ethylene glycol, polyethylene glycol, butyl carbitol acetate, tepinol, methyl amine, hexyl amine, cyclohexyl amine, diethanol amine, triethanol amine, and glycerin Conductive composition.
  • the additive composition comprises at least one component selected from malic acid, citric acid, tartaric acid, and polyethylene glycol.
  • the present invention can produce a copper fine particle complex having a narrow particle size distribution, a uniform particle shape, and a particle size of 1 ⁇ m or less by producing a copper fine particle complex using a mechanical chemical reaction method.
  • the copper paste is manufactured using the copper fine particle complex of the present invention prepared using the above mechanical chemical reaction method, it is possible to pyrolyze at a nitrogen atmosphere and below 300 ° C, and the fine copper complex is deteriorated during the sintering process.
  • the thermal decomposition by the reduction to the copper particles a dense copper thin film can be formed, and the layer separation phenomenon of the copper thin film layer and the copper powder layer without adhesion has an effect that is significantly reduced.
  • the copper face has the effect of ensuring dispersibility and printability and having sufficient applicability as a paste for RFID antenna tag manufacturing.
  • FIG. 1 shows electron micrographs of a copper fine particle complex (a) obtained using a conventional liquid phase method and a copper fine particle complex (b) obtained by applying a mechanical chemical reaction method as in the present invention.
  • Figure 2 shows the results of X-ray diffraction analysis of the copper fine particle complex obtained using the mechanical chemical reaction method of the embodiment of the present invention.
  • FIG. 6 shows a TG / DSC thermal analysis (Thermogravimetric / Differential Scanning Calorimeter) of the copper paste prepared in the embodiment of the present invention.
  • FIG. 7 shows the results of measuring the sheet resistance in the embodiment of the present invention.
  • FIG 8 shows the sintering process over time of the copper particulate complex of an embodiment of the present invention.
  • powder synthesis methods can be roughly divided into a gas phase method, a liquid phase method, and a solid phase method.
  • a copper fine particle complex is synthesized using a liquid phase method.
  • the copper fine particle complex obtained by the liquid phase method has a wide particle size distribution, a non-uniform particle shape, and a large particle size. Therefore, when manufacturing a copper paste using the copper fine particle complex obtained by the liquid phase method, it is difficult to obtain a dense copper thin film because of the particle size distribution, particle shape, and particle size as described above.
  • grains of narrow particle size distribution and particle size of 1 micrometer or less was manufactured using the mechanochemical reaction method which applied the solid-phase method.
  • a copper fine particle complex having a particle size of 1 ⁇ m or less and a narrow particle size distribution can be obtained.
  • the present invention obtained by the above mechanical chemical reaction method is obtained by reacting copper fine particle complex with formic acid using copper oxide (I) (Cu 2 O) as a precursor, and the copper fine particle complex is copper (Cu) and anhydrous copper. (II) formate (Cu (COOH) 2 ).
  • Such a copper fine particle complex of the present invention contains copper metal particles in a weight ratio of 3 to 30%, and anhydrous copper (II) formate in a weight ratio of 70 to 97%.
  • the copper fine particle complex obtained by the conventional liquid phase method contains only anhydrous copper (II) formate, the ratio of the mass of copper to the total mass of the complex is lower than that of the copper fine particle complex of the present invention.
  • the copper fine particle complex in the Examples of the present invention is obtained by reacting an excess of formic acid with a copper salt as a precursor by a Mechano-chemical reaction.
  • Such copper salts are copper oxide, copper hydroxide, copper nitrate, copper carbonate, copper sulfate, copper chloride, or copper acetate, preferably copper oxide (I) (Cu 2 O).
  • the mechanochemical reaction method after 600 g of zirconium balls having a diameter of 0.8 mm are put in the reaction vessel, 50 g of Cu 2 O is mixed with 150 g of formic acid, and after the reaction vessel is sealed, the reaction vessel is rotated at 300 rpm. Let it react for about 1 hour. In this case, the average particle diameter of the obtained copper complex is about 850 nm.
  • the bonding and grinding process between the powder particles can be repeated repeatedly.
  • the copper fine particle complex in a comparative example is obtained by reacting excess formic acid by using copper neodecanoate as a precursor by a liquid phase method.
  • Fig. 1 shows electron micrographs of a copper fine particle complex (a) obtained by using a liquid phase method as in the comparative example, which is a conventional technique, and a copper fine particle complex (b) obtained by applying a mechanical chemical reaction method as in the present invention.
  • a copper fine particle complex obtained by using a liquid phase method as in the comparative example, which is a conventional technique
  • a copper fine particle complex (b) obtained by applying a mechanical chemical reaction method as in the present invention.
  • the particle size distribution and particle diameter of the resulting powder is quite different.
  • the copper fine particle complex obtained by using the liquid phase method as in the comparative example has a wide particle size distribution and a large particle size, but the copper fine particle complex obtained by applying the mechanical chemical reaction method as in the embodiment of the present invention has a narrow particle size distribution and It is also small in size.
  • the copper fine particle complex obtained by using the liquid phase method as in the comparative example has a wide particle size distribution and a large particle size, it is difficult to secure dispersibility when preparing a paste, and it is difficult to obtain a dense thin film due to poor wettability and printability.
  • the copper fine particle complex of the embodiment of the present invention contains anhydrous copper (II) formate and copper particles.
  • Anhydrous copper (II) formate is consistent with JCPDS file number 32-0332 and can be seen to be a tetragonal structure. You can also see the XRD patterns on the (1 0 0), (2 0 0), and (2 2 0) planes at 43.3 °, 50.4 °, and 74.1 °, which correspond to JCPDS card number 04-0836 The copper particle which forms the structure is shown.
  • the copper fine particle complex obtained in the embodiment of the present invention contains not only anhydrous copper (II) formate (Cu (COOH) 2 ) but also copper particles, and thus has an advantage of increasing the content of copper during paste production. .
  • the pattern is consistent with JCPDS card number 32-0332, which means an anhydrous copper (II) formate in an orthorhombic structure. do. That is, in the comparative example, since the product does not contain copper and consists only of anhydrous copper (II) formate, the content of copper is inevitably lower than that of the embodiment of the present invention.
  • FIG. 4 shows the thermal analysis results of the copper fine particle complexes obtained in the examples of the present invention.
  • the thermal analysis of the copper fine particle complex of the example was performed while raising the temperature by 10 degrees per minute in a nitrogen atmosphere.
  • pyrolysis starts at 200 ° C., and pyrolysis is terminated in a relatively short time at around 230 degrees, and the copper content is about 54%.
  • FIG. 5 shows the thermal analysis result of the copper fine particle complex obtained by the comparative example.
  • the thermal analysis of the copper fine particle complex of the comparative example was performed while raising the temperature by 10 degrees C per minute in nitrogen atmosphere.
  • pyrolysis starts at 200 ° C. and pyrolysis is terminated after more time at a higher temperature in comparison with the embodiment at 250 ° C., and the copper content is about 41%.
  • a copper paste was prepared by using the copper fine particle complex synthesized in the above embodiment for printing on a polyimide substrate using a screen printing method.
  • the manufacturing method of such a copper paste is as follows.
  • a copper complex having an average particle diameter of 850 nm 19 parts by weight of ethylene glycol as a solvent and 1 part by weight of malic acid as an additive are added, followed by dispersion using 3 roll milling to obtain a conductive composition.
  • This conductive composition is applied to a polyimide substrate using screen printing.
  • the coated substrate is baked at 300 degrees for 30 minutes under a nitrogen gas stream to obtain a thin copper film on the polyimide substrate. It was confirmed that the volume resistance of the obtained copper thin film was about 8.5 X 10 -6 cm.
  • the solvent preferably comprises at least one component selected from ethylene glycol, polyethylene glycol, butyl carbitol acetate, tepinol, methyl amine, hexyl amine, cyclohexyl amine, diethanol amine, triethanol amine, and glycerin can do.
  • the additive may also comprise one or more components, preferably selected from malic acid, citric acid, tartaric acid, and polyethylene glycol.
  • the copper face was manufactured from the copper fine particle complex synthesized in the comparative example by the same method, but it was confirmed that the powder form was inferior in adhesion with the polyimide substrate.
  • the TG / DSC thermal analysis (Thermogravimetric / Differential Scanning Calorimeter) of the copper paste prepared in Example of the present invention was measured by raising the temperature to 10 degrees per minute in a nitrogen gas atmosphere. As can be seen in FIG. 6, the weight loss starts at about 110 ° C and the weight loss is terminated at about 240 ° C, where the overlap of the weight loss rates occurs because the decomposition of the solvent and the thermal decomposition of copper (II) formate occur at the same time. to be. As the temperature rises to around 170 ⁇ C, Tepino used as a solvent decreases by 20% and when the temperature rises further, the copper (II) formate decomposes by about 40% as a result of pyrolysis. It can confirm that it is degree.
  • the surface resistance is measured and shown in FIG. It was.
  • the unit of the sheet resistance of the vertical axis is m ⁇ / square, and as shown in FIG. 7, the sheet resistance is no longer lowered at about 50 m ⁇ / square even if given enough time according to each temperature, and thus analyzed as the minimum resistance of the sintered copper thin film. do.
  • the thermal decomposition of the copper fine particle complex starts until about 25 minutes and the minimum resistance is confirmed after the heat treatment for about 35 minutes .
  • heat treatment at 300 ⁇ C pyrolysis starts in about 10 minutes and finally sintering is finished after 20 minutes.
  • 350 ⁇ C it is confirmed that sintering is finished in 10 minutes.
  • the sintering time is required about 35 minutes at 250 ⁇ C, 20 minutes at 300 ⁇ C, and 10 minutes at 350 ⁇ C.
  • the copper complex of the embodiment of the present invention can be sintered within 40 minutes even at 250 ° C, which is unlike the conventional copper complex that is sintered at 400 ° C or more heat resistance temperature is less than 300 ° C Since it is secured, it can be applied to a flexible substrate.
  • FIG. 8 shows the sintering process over time of the copper complex of the embodiment of the present invention. Specifically, FIG. 8 shows 250 immediately after (a), after 20 minutes (b), after 23 minutes (c), after 25 minutes (d), after 30 minutes (e), and after 35 minutes (f).
  • the copper complex particles appear to be formed relatively densely.
  • the particles begin to form pores, which are produced by the generation of carbon dioxide and hydrogen gas, which are produced by the pyrolysis of copper (II) formate.
  • the copper fine particles complex is reduced to relatively small copper particles, and after about 30 minutes, the reduced copper particles are connected to each other. After 35 minutes of sintering time, it can be confirmed that copper particles are sintered as a whole to form a dense copper thin film.
  • the copper fine particle complex obtained by using the liquid phase method as in the prior art and the comparative example has a problem of dispersibility in the manufacture of copper paste because the particle size distribution is very wide and the particle size is large.
  • the copper fine particle complex obtained in the embodiment of the present invention has a narrow particle size distribution and particles having a size of 1 ⁇ m or less, dispersibility and printability can be secured during paste production, and are separated into a powder layer without adhesion to the copper thin film. Significantly decreased. This is because the particle size distribution is narrow and small particles are used, so that a thinner thin film is printed at the time of printing, which significantly reduces the delamination during the sintering process.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention a trait à un complexe particulaire de cuivre utilisé lors de la préparation d'une pâte de cuivre, ce complexe particulaire de cuivre étant obtenu grâce à la mise en réaction d'un sel de cuivre, qui sert de précurseur, avec de l'acide formique. Ledit complexe particulaire de cuivre comporte du cuivre (Cu) ainsi que du formiate de cuivre (II) anhydre (Cu(COOH)2) présentant une dimension des particules inférieure ou égale à 1 μm.
PCT/KR2012/004083 2011-05-27 2012-05-23 Complexe particulaire de cuivre destiné à l'électronique imprimée et pâte de cuivre WO2012165801A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110050737A KR101258402B1 (ko) 2011-05-27 2011-05-27 전자 인쇄용 구리 미립자 콤플렉스 및 구리 페이스트
KR10-2011-0050737 2011-05-27

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WO2012165801A2 true WO2012165801A2 (fr) 2012-12-06
WO2012165801A3 WO2012165801A3 (fr) 2013-01-24

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KR102233293B1 (ko) * 2014-01-15 2021-03-29 (주)창성 구리포메이트-아민 컴플렉스를 포함하는 잉크 조성물의 제조방법
KR101782799B1 (ko) 2015-08-11 2017-09-28 (주)창성 구리-아민 코-콤플렉스의 제조방법 및 이를 포함하는 전도성 이온 잉크 및 이를 이용한 미세 패턴전극의 제조방법

Citations (3)

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Publication number Priority date Publication date Assignee Title
KR100693970B1 (ko) * 2003-02-06 2007-03-12 뷜러 파르텍 게엠베하 관능성 콜로이드의 화학기계적 제조 방법
JP2007258123A (ja) * 2006-03-27 2007-10-04 Sumitomo Metal Mining Co Ltd 導電性組成物及び導電膜形成方法
KR20080032625A (ko) * 2007-11-12 2008-04-15 삼성전기주식회사 구리 나노입자의 제조방법 및 그에 의해 제조된 구리나노입자

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Publication number Priority date Publication date Assignee Title
JPH03100109A (ja) * 1989-09-12 1991-04-25 Mitsubishi Gas Chem Co Inc 微細銅粉の製造法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100693970B1 (ko) * 2003-02-06 2007-03-12 뷜러 파르텍 게엠베하 관능성 콜로이드의 화학기계적 제조 방법
JP2007258123A (ja) * 2006-03-27 2007-10-04 Sumitomo Metal Mining Co Ltd 導電性組成物及び導電膜形成方法
KR20080032625A (ko) * 2007-11-12 2008-04-15 삼성전기주식회사 구리 나노입자의 제조방법 및 그에 의해 제조된 구리나노입자

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KR101258402B1 (ko) 2013-05-02
KR20120132115A (ko) 2012-12-05
WO2012165801A3 (fr) 2013-01-24

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