WO2020111634A1 - Method for preparing conductive ink composition for inner electrode of layered ceramic capacitor, and method for manufacturing inner electrode of layered ceramic capacitor by using same - Google Patents

Method for preparing conductive ink composition for inner electrode of layered ceramic capacitor, and method for manufacturing inner electrode of layered ceramic capacitor by using same Download PDF

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WO2020111634A1
WO2020111634A1 PCT/KR2019/015889 KR2019015889W WO2020111634A1 WO 2020111634 A1 WO2020111634 A1 WO 2020111634A1 KR 2019015889 W KR2019015889 W KR 2019015889W WO 2020111634 A1 WO2020111634 A1 WO 2020111634A1
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internal electrode
ceramic capacitor
manufacturing
nickel
multilayer ceramic
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PCT/KR2019/015889
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French (fr)
Korean (ko)
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이정호
김석주
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솔브레인 주식회사
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Publication of WO2020111634A1 publication Critical patent/WO2020111634A1/en

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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor, a method of manufacturing an internal electrode of a multilayer ceramic capacitor using the conductive ink composition, and a method of manufacturing a multilayer ceramic capacitor including the internal electrode.
  • Nickel powder is used as a material of a capacitor that is an electronic component constituting an electronic circuit, and a material of a thick film conductor constituting an internal electrode of a multilayer ceramic component such as a multilayer ceramic capacitor (MLCC) or a multilayer ceramic substrate.
  • MLCC multilayer ceramic capacitor
  • the amount of the internal electrode paste used for forming the thick film conductor constituting the internal electrode of the multilayer ceramic capacitor has also increased significantly. Therefore, as a metal powder for the internal electrode paste, an expensive noble metal is replaced, and a low-cost non-metal such as nickel is mainly used.
  • a commercially available multilayer ceramic capacitor is briefly performed through the following process.
  • an internal electrode paste obtained by kneading a binder resin such as nickel powder or ethyl cellulose and an organic solvent such as terpineol is screen printed on a dielectric green sheet.
  • a laminated body is obtained by laminating and compressing the dielectric green sheet on which the internal electrode paste is printed so that the internal electrode paste and the dielectric green sheet alternately overlap each other.
  • the obtained laminate is cut to a predetermined size and heated to remove the binder resin (hereinafter referred to as "debinder treatment"), and then baked at a high temperature of about 1,300°C to obtain a ceramic molded body.
  • a multilayer ceramic capacitor can be obtained by providing an external electrode on the obtained ceramic formed body.
  • the binder removal process of the laminate should be performed under an extremely low oxygen concentration such as an inert atmosphere so that the non-metal does not oxidize.
  • the particle diameter of the nickel powder used in the internal electrode paste is also being refined, and a nickel powder having an average particle diameter of 0.5 ⁇ m or less is required, and a nickel powder having an average particle diameter of 0.3 ⁇ m or less is mainly used.
  • the present inventors were conducting research to achieve thinning of the internal electrode and dielectric of the multilayer ceramic capacitor, but instead of the method of screen printing the existing internal electrode paste on the dielectric green sheet, the conductivity for the internal electrode of the new multilayer ceramic capacitor It has been found that when the ink composition is inkjet printed on a dielectric green sheet to produce an internal electrode, the thickness of the thin film can be very thin as 0.1 ⁇ m or less. Accordingly, the present invention has been completed by discovering that the use of this can realize the miniaturization and large-capacity of the multilayer ceramic capacitor by realizing the number of internal electrode stacks than the conventional multilayer ceramic capacitor.
  • Korean Patent Publication No. 10-2007-0044109 discloses a multilayer ceramic electronic component and a manufacturing method thereof.
  • the present invention has been devised to solve the aforementioned problems, and an embodiment of the present invention provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor.
  • Another embodiment of the present invention provides a method of manufacturing an internal electrode of a multilayer ceramic capacitor.
  • Another embodiment of the present invention provides a method for manufacturing a ceramic capacitor.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; And mixing the prepared nickel precursor with a solvent and a thickener to prepare an ink; It provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor comprising a.
  • the nickel compound may include a material selected from the group consisting of nickel nitrate, nickel chloride, nickel acetate, nickel formate, and combinations thereof. have.
  • the compound containing the carboxyl group is from the group consisting of acetic acid, caproic acid, lauric acid, oleic acid, palmitic acid and combinations thereof. It may be to include a selected material.
  • the compound containing the amine group includes a material selected from the group consisting of ammonia, butylamine, isopropylamine, ethylenediamine, ethanolamine and combinations thereof. It may be.
  • the weight mixing ratio of the nickel compound and the compound containing a carboxyl group or a compound containing an amine group may be 1: 2 to 6.
  • the thickener may be cellulose-based.
  • the content of the nickel precursor compared to 100 parts by weight of the conductive ink composition for the internal electrode may be 5 parts by weight to 30 parts by weight, and the content of the thickener may be 1 part by weight to 10 parts by weight.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; And forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively, to provide a method for manufacturing the inner electrode of the multilayer ceramic capacitor. do.
  • the method of manufacturing the internal electrode of the multilayer ceramic capacitor may further include sintering the dielectric green sheet on which the internal electrode pattern is formed after forming the first internal electrode and the second internal electrode patterns.
  • the sintering may be performed for 1 minute to 20 minutes at a temperature of 100°C to 400°C.
  • the thickness of the dielectric green sheet on which the pattern is formed may be 50 nm to 1,000 nm.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively; Forming a ceramic laminate by stacking the dielectric green sheets on which the first internal electrode and the second internal electrode patterns are formed; And forming a first external electrode and a second external electrode on both side surfaces of the ceramic laminate.
  • the internal electrode of the multilayer ceramic capacitor is manufactured according to the above manufacturing method, inkjet printing is possible, so the thin film thickness is very thin to 0.1 ⁇ m or less, so that the existing internal electrode paste is screened on the dielectric green sheet. Compared to the printing method, more internal electrode stacks can be realized. Therefore, the multilayer ceramic capacitor manufactured by using it has a high utilization value in the industry because it can be miniaturized and large-capacity.
  • FIG. 1 is a schematic view showing a process of inkjet printing a conductive green ink composition for an internal electrode of a multilayer ceramic capacitor according to an embodiment of the present invention on a dielectric green sheet.
  • 2A is an SEM photograph showing an internal electrode screen-printed with a nickel paste according to a comparative example of the present invention on a dielectric green sheet.
  • FIG. 2B is a SEM photograph showing an internal electrode inkjet printed on a dielectric green sheet with a conductive ink composition for an internal electrode of a multilayer ceramic capacitor according to an embodiment of the present invention.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; And mixing the prepared nickel precursor with a solvent and a thickener to prepare an ink; provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor.
  • a method of manufacturing a conductive ink composition for an internal electrode of the multilayer ceramic capacitor comprises: preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group; It includes.
  • the nickel compound is from the group consisting of nickel nitrate, nickel chloride, nickel acetate, nickel formate, and combinations thereof. It may be to include a selected material.
  • the compound containing the carboxyl group is acetic acid, caproic acid, lauric acid, oleic acid, palmitic acid and It may be to include a material selected from the group consisting of these combinations.
  • the compound containing the amine group is ammonia, butylamine, isopropylamine, ethylenediamine, ethanolamine and combinations thereof It may include a material selected from the group consisting of.
  • the nickel compound, a compound containing a carboxyl group, or a compound containing an amine group may be a metal-ligand bond to each other to form a nickel precursor.
  • the weight mixing ratio of the nickel compound, the compound containing a carboxyl group, or the compound containing an amine group may be 1: 2 to 6, preferably 1: 3 to 5.
  • the weight mixing ratio of the compound containing the carboxyl group or the compound containing the amine group is less than 1 compared to the nickel compound 1 standard, the precursor may not be sufficiently bonded to the nickel compound, which may cause unstable problems. A large amount of unreacted material that is not present may cause problems such as an increase in the heat treatment time and the formation of a nickel coating film.
  • the method of manufacturing a conductive ink composition for an internal electrode of the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
  • the solvent may be a polar solvent or a non-polar solvent
  • the polar solvent may be, for example, alcohols, glycols, etc.
  • the non-polar solvent may be, for example, xylene, terpinol. , Toluene, and the like.
  • the thickener may be cellulose-based, for example, methyl cellulose (methyl cellulose, MC), hydroxypropyl methyl cellulose (hydroxy propyl methyl cellulose, HPMC), hydroxyethyl cellulose ( It may include a material selected from the group consisting of hydroxyethyl cellulose, HEC), ethylcellulose (EC), and combinations thereof.
  • the content of the nickel precursor relative to 100 parts by weight of the conductive ink composition for the internal electrode is 5 parts by weight to 30 parts by weight, and the content of the thickener may be 1 part by weight to 10 parts by weight.
  • the content of the nickel precursor is preferably 10 parts by weight to 20 parts by weight
  • the content of the thickener may be preferably 1 part by weight to 5 parts by weight.
  • the conductive ink composition for the internal electrode may not be properly mixed, and when the content of the thickener is more than 10 parts by weight, the viscosity of the conductive ink composition for the internal electrode increases too much, and inkjet printing It may not be easy.
  • the conductive ink composition for the internal electrode may further include a moisturizing agent, a leveler, an adhesion promoter, and the like.
  • the moisturizing agent is a natural moisturizing agent such as 1,2-hexanediol, glycerin, propylene glycol, butylene glycol, polyethylene glycol, sorbitol or trehalose, polyol, amino acid, urea, lactate, or PCA-Na.
  • Polymer moisturizers such as factor (NMF), hyaluronate, chondroitin sulfate, or hydrolyzed collagen may be used.
  • the leveler is an additive having a smoothing (leveling) action, and a compound containing nitrogen such as polyamine may be used.
  • the adhesion promoter is a silane coupling agent having both properties of an inorganic substance and an organic substance, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane ( ⁇ -(3,4- epoxycyclohexyl)ethyltrimethoysilane), gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and combinations thereof.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; And forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively, to provide a method for manufacturing the inner electrode of the multilayer ceramic capacitor. do.
  • the method of manufacturing an internal electrode of the multilayer ceramic capacitor includes a step of preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group.
  • the method of manufacturing the internal electrode of the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
  • the method of manufacturing the internal electrode of the multilayer ceramic capacitor is ink-jet-printed on the upper and lower portions of the dielectric green sheet, respectively, and the first internal electrode on the upper portion and the second internal portion on the lower portion. And forming an electrode pattern.
  • 1 is a schematic diagram of the inkjet printing.
  • the method of manufacturing the internal electrode of the multilayer ceramic capacitor comprises sintering the dielectric green sheet on which the internal electrode pattern is formed after forming the first internal electrode and the second internal electrode patterns. It may be further included.
  • the sintering may be performed for 1 minute to 20 minutes at a temperature of 100°C to 400°C, and preferably performed for 5 minutes to 15 minutes at a temperature of 200°C to 300°C. Can be.
  • the sintering is performed at a temperature of less than 100°C or for less than 1 minute, sintering may not be sufficiently performed, and when the temperature is exceeded at 400°C or for more than 20 minutes, the dielectric green sheet on which the internal electrode pattern is formed is damaged Can be.
  • the dielectric green sheet may be made of a ceramic material having a high dielectric constant, for example, barium titanate (BaTiO 3 )-based material, lead composite perovskite-based material, or strontium titanate (SrTiO 3) ) May be used.
  • barium titanate (BaTiO 3 )-based material barium titanate (BaTiO 3 )-based material, lead composite perovskite-based material, or strontium titanate (SrTiO 3) ) May be used.
  • the inkjet printing may be an inkjet printing method that is commonly used, and the ink produced above is used on the upper and lower portions of the dielectric green sheet through the inkjet printing. It may be to form a second internal electrode pattern on the 1 internal electrode and the lower portion. At this time, the dielectric green sheet in which the first internal electrode and the second internal electrode pattern are formed may be stacked as a set, and the first external electrode and the second external electrode may be stacked on both sides of the stacked body.
  • a multilayer ceramic capacitor may be manufactured by forming an external electrode.
  • the thin film thickness of the patterned dielectric green sheet may be 50 nm to 1,000 nm, and preferably 50 nm to 100 nm. That is, it is possible to realize a larger number of internal electrode stacks than the method of screen printing the existing internal electrode paste on the dielectric green sheet, and the multilayer ceramic capacitor manufactured using this can be miniaturized and large-capacity, and thus has industrial value. It can be very high.
  • Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively; Forming a ceramic laminate by stacking the dielectric green sheets on which the first internal electrode and the second internal electrode patterns are formed; And forming a first external electrode and a second external electrode on both side surfaces of the ceramic laminate.
  • the method of manufacturing the multilayer ceramic capacitor includes a step of preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group.
  • the method of manufacturing the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
  • the manufacturing method of the multilayer ceramic capacitor is inkjet printed on the upper and lower portions of the dielectric green sheet, respectively, so that the first internal electrode on the top and the second internal electrode pattern on the bottom It includes; forming a.
  • the step of preparing the nickel precursor; Preparing an ink; And forming an internal electrode pattern since the first and second aspects of the present application have been described, the following description will be omitted in the third aspect of the present application.
  • the method of manufacturing the multilayer ceramic capacitor includes: forming a ceramic laminate by stacking a dielectric green sheet on which the first internal electrode and the second internal electrode pattern are formed; And forming first and second external electrodes on both sides of the ceramic laminate.
  • the number of layers of the ceramic laminate may vary depending on the size of the multilayer ceramic capacitor to be manufactured, and the dielectric green sheet on which the internal electrode pattern of the present invention is formed has a thin film thickness of 1,000 nm or less. Because it is thin, it is possible to realize a higher number of stacks. Therefore, since the multilayer ceramic capacitor manufactured using the above can be miniaturized and large-capacity, the utilization value can be very high industrially.
  • the step of forming the laminate stacks a dielectric green sheet having a first internal electrode and a second internal electrode pattern, and compresses the internal electrode and the dielectric green sheet by pressing in the stacking direction.
  • a dielectric green sheet having a first internal electrode and a second internal electrode pattern
  • compresses the internal electrode and the dielectric green sheet by pressing in the stacking direction May be Through the above-described method, it may be to form a ceramic laminate in which internal electrodes and dielectric green sheets are alternately stacked.
  • the first external electrode and the second external electrode may be formed of a conductive metal, for example, copper, copper alloy, nickel, nickel alloy, silver, palladium, and combinations thereof It may be formed of a material selected from the group consisting of.
  • the first external electrode and the second external electrode may be electrically connected to the first internal electrode and the second internal electrode exposed to both sides of the ceramic laminate, and thereafter, nickel and tin on the surface of the external electrode. It may be a plating treatment such as.
  • Step 1 Preparation of a conductive ink composition for internal electrodes of a multilayer ceramic capacitor
  • a nickel precursor was prepared by mixing nickel chloride (nickel compound) and oleic acid (compound containing a carboxyl group) at a weight ratio of 1:4 and reacting.
  • a conductive ink composition for internal electrodes of a multilayer ceramic capacitor was prepared by mixing 30 wt% of the prepared nickel precursor, 68 wt% of terpineol (solvent), and 2 wt% of ethyl cellulose (thickener).
  • Step 2 manufacturing the internal electrode of the multilayer ceramic capacitor
  • the internal electrode of the multilayer ceramic capacitor was prepared by inkjet printing the conductive ink composition for the internal electrode of the multilayer ceramic capacitor prepared in step 1 above and below the barium titanate green sheet (dielectric green sheet). At this time, the thin film thickness of the prepared internal electrode was about 100 nm.
  • Step 3 Preparation of a multilayer ceramic capacitor
  • an external electrode is formed on both sides of the ceramic laminate using copper (Cu) paste to prepare a multilayer ceramic capacitor.
  • a multilayer ceramic capacitor was manufactured in the same manner as in Example 1, except that ethylene diamine (a compound containing an amine group) was mixed instead of oleic acid (a compound containing a carboxyl group) in Step 1 of Example 1.
  • FIG. 2a is a SEM photograph showing the surface of the internal electrode of the multilayer ceramic capacitor prepared in the comparative example
  • Figure 2b is a SEM photograph showing the surface of the internal electrode of the multilayer ceramic capacitor prepared in Example 1.
  • 2A and 2B in the case of the comparative example, the internal electrode was formed of nickel particles, whereas in the case of the example, it was confirmed that the internal electrode was formed of grain. Therefore, it was confirmed that the internal electrode of the multilayer ceramic capacitor manufactured in the embodiment of the present invention can have a very thin film thickness compared to the comparative example.

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Abstract

Disclosed are a method for preparing a conductive ink composition for an inner electrode of a stacked ceramic capacitor, a method for manufacturing an inner electrode of a stacked ceramic capacitor by using same, and a method for manufacturing a stacked ceramic capacitor including an inner electrode. Since the manufacturing method enables inkjet printing when the inner electrode of the layered ceramic capacitor is manufactured, the thickness of a thin film becomes very thin to no more than 0.1 μm so that the number of layered internal electrodes that can be implemented is greater than that of a conventional method for screen-printing an internal electrode paste on a dielectric green sheet.

Description

적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법 및 이를 이용한 적층형 세라믹 커패시터의 내부전극 제조방법Method for manufacturing conductive ink composition for internal electrode of multilayer ceramic capacitor and method for manufacturing internal electrode of multilayer ceramic capacitor using the same
본 발명은 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법, 상기 도전성 잉크 조성물을 이용한 적층형 세라믹 커패시터의 내부전극 제조방법 및 상기 내부전극을 포함하는 적층형 세라믹 커패시터의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor, a method of manufacturing an internal electrode of a multilayer ceramic capacitor using the conductive ink composition, and a method of manufacturing a multilayer ceramic capacitor including the internal electrode.
니켈 분말은 전자 회로를 구성하는 전자 부품인 커패시터의 재료, 특히 적층형 세라믹 커패시터(MLCC)나 다층 세라믹 기판 등의 적층 세라믹 부품의 내부전극 등을 구성하는 후막 도체의 재료로서 이용되고 있다. Nickel powder is used as a material of a capacitor that is an electronic component constituting an electronic circuit, and a material of a thick film conductor constituting an internal electrode of a multilayer ceramic component such as a multilayer ceramic capacitor (MLCC) or a multilayer ceramic substrate.
최근, 적층 세라믹 커패시터의 대용량화가 진행됨에 따라, 적층형 세라믹 커패시터의 내부전극을 구성하는 후막 도체의 형성에 이용되는 내부전극 페이스트의 사용량도 큰 폭으로 증가하고 있다. 따라서, 내부전극 페이스트용 금속 분말로서 고가의 귀금속을 대체하여 주로 니켈 등의 저가의 비금속이 사용되고 있다. Recently, as the capacity of the multilayer ceramic capacitor has increased, the amount of the internal electrode paste used for forming the thick film conductor constituting the internal electrode of the multilayer ceramic capacitor has also increased significantly. Therefore, as a metal powder for the internal electrode paste, an expensive noble metal is replaced, and a low-cost non-metal such as nickel is mainly used.
현재 상용화된 적층형 세라믹 커패시터의 제조는 간략하게 이하의 공정을 거치게 된다. 우선, 니켈 분말, 에틸셀룰로오스 등의 바인더 수지 및 테르피네올 등의 유기 용제를 혼련함으로써 얻어진 내부전극 페이스트를 유전체 그린시트상에 스크린 인쇄한다. 이어서, 상기 내부전극 페이스트가 인쇄된 유전체 그린시트를 내부전극 페이스트와 유전체 그린시트가 교대로 겹쳐지도록 적층해 압착함으로써 적층체를 얻는다. 그 후, 상기 얻어진 적층체를 소정의 크기로 커트하고 가열하여 바인더 수지를 제거(이하, 「탈바인더 처리」라고 한다)한 후, 1,300℃ 정도의 고온에서 소성함으로써, 세라믹 성형체를 얻을 수 있다. 마지막으로, 상기 얻어진 세라믹 성형체에 외부 전극을 설치함으로써, 적층형 세라믹 커패시터를 얻을 수 있다.The production of a commercially available multilayer ceramic capacitor is briefly performed through the following process. First, an internal electrode paste obtained by kneading a binder resin such as nickel powder or ethyl cellulose and an organic solvent such as terpineol is screen printed on a dielectric green sheet. Subsequently, a laminated body is obtained by laminating and compressing the dielectric green sheet on which the internal electrode paste is printed so that the internal electrode paste and the dielectric green sheet alternately overlap each other. Thereafter, the obtained laminate is cut to a predetermined size and heated to remove the binder resin (hereinafter referred to as "debinder treatment"), and then baked at a high temperature of about 1,300°C to obtain a ceramic molded body. Finally, a multilayer ceramic capacitor can be obtained by providing an external electrode on the obtained ceramic formed body.
이때, 내부전극 페이스트 중의 금속 분말로서 니켈 등의 비금속이 사용되기 때문에 상기 적층체의 탈바인더 처리는 비금속이 산화하지 않도록 불활성 분위기 등의 산소 농도가 극히 낮은 분위기 하에서 수행되어야 한다. At this time, since a non-metal such as nickel is used as a metal powder in the internal electrode paste, the binder removal process of the laminate should be performed under an extremely low oxygen concentration such as an inert atmosphere so that the non-metal does not oxidize.
한편, 적층형 세라믹 커패시터의 소형화 및 대용량화에 수반하여 최근 내부전극 및 유전체의 박막화가 함께 연구되고 있다. 이에 따라 내부전극 페이스트에 사용되는 니켈 분말의 입자 지름 또한 미세화가 진행되고 있으며, 평균 입경 0.5 μm 이하의 니켈 분말이 요구되어 주로 평균 입경 0.3 μm 이하의 니켈 분말이 사용되고 있다.On the other hand, with the miniaturization and large-capacity of the multilayer ceramic capacitor, thin films of internal electrodes and dielectrics have recently been studied together. Accordingly, the particle diameter of the nickel powder used in the internal electrode paste is also being refined, and a nickel powder having an average particle diameter of 0.5 μm or less is required, and a nickel powder having an average particle diameter of 0.3 μm or less is mainly used.
이에, 본 발명자들은 상기 적층형 세라믹 커패시터의 내부전극 및 유전체의 박막화를 달성하기 위하여 연구하던 중 기존의 내부전극 페이스트를 유전체 그린시트상에 스크린 인쇄하는 방법이 아닌 신규한 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물을 유전체 그린시트에 잉크젯 인쇄를 하여 내부전극을 제조하게 되면 박막 두께가 0.1 μm 이하로서 매우 얇아질 수 있음을 발견하였다. 따라서, 이를 이용하게 되면 기존의 적층형 세라믹 커패시터 보다 많은 내부전극의 적층 수를 구현하게 되어 적층형 세라믹 커패시터의 소형화 및 대용량화를 달성할 수 있음을 발견하여 본 발명을 완성하게 되었다.Accordingly, the present inventors were conducting research to achieve thinning of the internal electrode and dielectric of the multilayer ceramic capacitor, but instead of the method of screen printing the existing internal electrode paste on the dielectric green sheet, the conductivity for the internal electrode of the new multilayer ceramic capacitor It has been found that when the ink composition is inkjet printed on a dielectric green sheet to produce an internal electrode, the thickness of the thin film can be very thin as 0.1 μm or less. Accordingly, the present invention has been completed by discovering that the use of this can realize the miniaturization and large-capacity of the multilayer ceramic capacitor by realizing the number of internal electrode stacks than the conventional multilayer ceramic capacitor.
이와 관련하여, 대한민국 공개특허 제10-2007-0044109호는 적층 세라믹 전자부품 및 그 제조방법에 대하여 개시하고 있다.In this regard, Korean Patent Publication No. 10-2007-0044109 discloses a multilayer ceramic electronic component and a manufacturing method thereof.
본 발명은 전술한 문제를 해결하고자 안출된 것으로서, 본 발명의 일 실시예는 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법을 제공한다.The present invention has been devised to solve the aforementioned problems, and an embodiment of the present invention provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor.
본 발명의 다른 일 실시예는 적층형 세라믹 커패시터의 내부전극 제조방법을 제공한다.Another embodiment of the present invention provides a method of manufacturing an internal electrode of a multilayer ceramic capacitor.
본 발명의 또 다른 일 실시예는 세라믹 커패시터의 제조방법을 제공한다.Another embodiment of the present invention provides a method for manufacturing a ceramic capacitor.
본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 기술적 과제로 한정되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those having ordinary knowledge in the technical field to which the present invention belongs from the following description. There will be.
전술한 기술적 과제를 달성하기 위한 기술적 수단으로서, 본 발명의 일 측면은, As a technical means for achieving the above-described technical problem, one aspect of the present invention,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 및 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 를 포함하는 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; And mixing the prepared nickel precursor with a solvent and a thickener to prepare an ink; It provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor comprising a.
상기 니켈 화합물은 니켈 나이트레이트(nickel nitrate), 니켈 클로라이드(nickel chloride), 니켈 아세테이트(nickel acetate), 니켈 포메이트(nickel formate) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.The nickel compound may include a material selected from the group consisting of nickel nitrate, nickel chloride, nickel acetate, nickel formate, and combinations thereof. have.
상기 카르복실기를 포함하는 화합물은 아세트산(acetic acid), 카프로산(caproic acid), 라우르산(lauric acid), 올레산(oleic acid), 팔미트산(palmitic acid) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.The compound containing the carboxyl group is from the group consisting of acetic acid, caproic acid, lauric acid, oleic acid, palmitic acid and combinations thereof. It may be to include a selected material.
상기 아민기를 포함하는 화합물은 암모니아(ammonia), 부틸아민(butylamine), 이소프로필아민(isopropylamine), 에틸렌디아민(ethylenediamine), 에탄올아민(ethanolamine) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.The compound containing the amine group includes a material selected from the group consisting of ammonia, butylamine, isopropylamine, ethylenediamine, ethanolamine and combinations thereof. It may be.
상기 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물의 중량 혼합 비율은 1: 2 내지 6인 것일 수 있다.The weight mixing ratio of the nickel compound and the compound containing a carboxyl group or a compound containing an amine group may be 1: 2 to 6.
상기 증점제는 셀룰로오스 계열인 것일 수 있다.The thickener may be cellulose-based.
상기 내부전극용 도전성 잉크 조성물 100 중량부 대비 상기 니켈 전구체의 함량은 5 중량부 내지 30 중량부이고, 상기 증점제의 함량은 1 중량부 내지 10 중량부인 것일 수 있다.The content of the nickel precursor compared to 100 parts by weight of the conductive ink composition for the internal electrode may be 5 parts by weight to 30 parts by weight, and the content of the thickener may be 1 part by weight to 10 parts by weight.
또한, 본 발명의 다른 일 측면은, In addition, another aspect of the present invention,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 및 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;를 포함하는 적층형 세라믹 커패시터의 내부전극 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; And forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively, to provide a method for manufacturing the inner electrode of the multilayer ceramic capacitor. do.
상기 적층형 세라믹 커패시터의 내부전극 제조방법은 상기 제1 내부전극 및 제2 내부전극 패턴을 형성하는 단계 이후에, 상기 내부전극 패턴이 형성된 유전체 그린시트를 소결시키는 단계를 더 포함하는 것일 수 있다.The method of manufacturing the internal electrode of the multilayer ceramic capacitor may further include sintering the dielectric green sheet on which the internal electrode pattern is formed after forming the first internal electrode and the second internal electrode patterns.
상기 소결은 100℃ 내지 400℃의 온도에서 1 분 내지 20 분 동안 수행되는 것일 수 있다.The sintering may be performed for 1 minute to 20 minutes at a temperature of 100°C to 400°C.
상기 패턴이 형성된 유전체 그린시트의 박막 두께는 50 nm 내지 1,000 nm인 것일 수 있다.The thickness of the dielectric green sheet on which the pattern is formed may be 50 nm to 1,000 nm.
또한, 본 발명의 또 다른 일 측면은, In addition, another aspect of the present invention,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계; 상기 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트를 적층하여 세라믹 적층체를 형성하는 단계; 및 상기 세라믹 적층체의 양 측면에 제1 외부전극 및 제2 외부전극을 형성하는 단계;를 포함하는 적층형 세라믹 커패시터의 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively; Forming a ceramic laminate by stacking the dielectric green sheets on which the first internal electrode and the second internal electrode patterns are formed; And forming a first external electrode and a second external electrode on both side surfaces of the ceramic laminate.
본 발명의 일 실시예에 따르면 상기 제조방법에 따라 적층형 세라믹 커패시터의 내부전극을 제조하게 되면 잉크젯 인쇄가 가능하기 때문에 박막 두께가 0.1 μm 이하로 매우 얇아져 기존의 내부전극 페이스트를 유전체 그린시트 상에 스크린 인쇄하는 방법에 비하여 보다 많은 내부전극 적층 수를 구현할 수 있다. 따라서, 이를 이용하여 제조된 적층형 세라믹 커패시터는 소형화 및 대용량화가 가능하기 때문에 산업적으로 활용가치가 매우 높다.According to an embodiment of the present invention, if the internal electrode of the multilayer ceramic capacitor is manufactured according to the above manufacturing method, inkjet printing is possible, so the thin film thickness is very thin to 0.1 μm or less, so that the existing internal electrode paste is screened on the dielectric green sheet. Compared to the printing method, more internal electrode stacks can be realized. Therefore, the multilayer ceramic capacitor manufactured by using it has a high utilization value in the industry because it can be miniaturized and large-capacity.
본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.
도 1은 본 발명의 일 구현예에 따른 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물을 유전체 그린시트에 잉크젯 인쇄하는 과정을 나타낸 개략도이다.1 is a schematic view showing a process of inkjet printing a conductive green ink composition for an internal electrode of a multilayer ceramic capacitor according to an embodiment of the present invention on a dielectric green sheet.
도 2a는 본 발명의 일 비교예에 따른 니켈 페이스트를 유전체 그린시트에 스크린 인쇄한 내부전극을 나타낸 SEM 사진이다.2A is an SEM photograph showing an internal electrode screen-printed with a nickel paste according to a comparative example of the present invention on a dielectric green sheet.
도 2b는 본 발명의 일 실시예에 따른 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물을 유전체 그린시트에 잉크젯 인쇄한 내부전극을 나타낸 SEM 사진이다.FIG. 2B is a SEM photograph showing an internal electrode inkjet printed on a dielectric green sheet with a conductive ink composition for an internal electrode of a multilayer ceramic capacitor according to an embodiment of the present invention.
이하, 본 발명을 더욱 상세하게 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 의해 본 발명이 한정되지 않으며 본 발명은 후술할 청구범위의 의해 정의될 뿐이다.Hereinafter, the present invention will be described in more detail. However, the present invention may be implemented in various different forms, and the present invention is not limited by the examples described herein, and the present invention is only defined by the claims below.
덧붙여, 본 발명에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 발명의 명세서 전체에서 어떤 구성요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. 'Including' a component throughout the specification of the present invention means that other components may be further included instead of excluding other components, unless otherwise stated.
본원의 제 1 측면은,The first aspect of the present application,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 및 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;를 포함하는 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; And mixing the prepared nickel precursor with a solvent and a thickener to prepare an ink; provides a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor.
이하, 본원의 제 1 측면에 따른 상기 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법을 상세히 설명한다.Hereinafter, a method of manufacturing a conductive ink composition for an internal electrode of the multilayer ceramic capacitor according to the first aspect of the present application will be described in detail.
우선, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법은 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계;를 포함한다.First, in one embodiment of the present application, a method of manufacturing a conductive ink composition for an internal electrode of the multilayer ceramic capacitor comprises: preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group; It includes.
본원의 일 구현예에 있어서, 상기 니켈 화합물은 니켈 나이트레이트(nickel nitrate), 니켈 클로라이드(nickel chloride), 니켈 아세테이트(nickel acetate), 니켈 포메이트(nickel formate) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.In one embodiment of the present application, the nickel compound is from the group consisting of nickel nitrate, nickel chloride, nickel acetate, nickel formate, and combinations thereof. It may be to include a selected material.
본원의 일 구현예에 있어서, 상기 카르복실기를 포함하는 화합물은 아세트산(acetic acid), 카프로산(caproic acid), 라우르산(lauric acid), 올레산(oleic acid), 팔미트산(palmitic acid) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.In one embodiment of the present application, the compound containing the carboxyl group is acetic acid, caproic acid, lauric acid, oleic acid, palmitic acid and It may be to include a material selected from the group consisting of these combinations.
본원의 일 구현예에 있어서, 상기 아민기를 포함하는 화합물은 암모니아(ammonia), 부틸아민(butylamine), 이소프로필아민(isopropylamine), 에틸렌디아민(ethylenediamine), 에탄올아민(ethanolamine) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.In one embodiment of the present application, the compound containing the amine group is ammonia, butylamine, isopropylamine, ethylenediamine, ethanolamine and combinations thereof It may include a material selected from the group consisting of.
본원의 일 구현예에 있어서, 상기 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물은 서로 금속-리간드 결합을 하여 니켈 전구체를 형성하는 것일 수 있다.In one embodiment of the present application, the nickel compound, a compound containing a carboxyl group, or a compound containing an amine group may be a metal-ligand bond to each other to form a nickel precursor.
본원의 일 구현예에 있어서, 상기 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물의 중량 혼합 비율은 1: 2 내지 6인 것일 수 있으며, 바람직하게 1: 3 내지 5일 수 있다. 상기 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물의 중량 혼합 비율이 니켈 화합물 1 기준 대비 1 미만일 경우 니켈 화합물과의 충분한 결합을 하지 않아 전구체가 불안정한 문제가 발생할 수 있으며, 6 초과일 경우 반응에 참여하지 않는 다량의 미반응물이 존재해 열처리 시간 상승 및 니켈 도막 형성을 방해하는 문제가 발생할 수 있다.In one embodiment of the present application, the weight mixing ratio of the nickel compound, the compound containing a carboxyl group, or the compound containing an amine group may be 1: 2 to 6, preferably 1: 3 to 5. When the weight mixing ratio of the compound containing the carboxyl group or the compound containing the amine group is less than 1 compared to the nickel compound 1 standard, the precursor may not be sufficiently bonded to the nickel compound, which may cause unstable problems. A large amount of unreacted material that is not present may cause problems such as an increase in the heat treatment time and the formation of a nickel coating film.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법은 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;를 포함한다.Next, in one embodiment of the present application, the method of manufacturing a conductive ink composition for an internal electrode of the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
본원의 일 구현예에 있어서, 상기 용매는 극성용매 또는 비극성용매일 수 있으며, 상기 극성용매는 예를 들어, 알코올류, 글리콜류 등일 수 있고, 상기 비극성용매는 예를 들어, 자일렌, 터피놀, 톨루엔 등일 수 있다.In one embodiment of the present application, the solvent may be a polar solvent or a non-polar solvent, the polar solvent may be, for example, alcohols, glycols, etc., and the non-polar solvent may be, for example, xylene, terpinol. , Toluene, and the like.
본원의 일 구현예에 있어서, 상기 증점제는 셀룰로오스 계열인 것일 수 있으며, 예를 들어, 메틸 셀룰로오스(methyl cellulose, MC), 하이드록시프로필 메틸셀룰로오스(hydroxy propyl methyl cellulose, HPMC), 하이드록시에틸 셀룰로오스(hydroxyethyl cellulose, HEC), 에틸 셀룰로오스(ethylcellulose, EC) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.In one embodiment of the present application, the thickener may be cellulose-based, for example, methyl cellulose (methyl cellulose, MC), hydroxypropyl methyl cellulose (hydroxy propyl methyl cellulose, HPMC), hydroxyethyl cellulose ( It may include a material selected from the group consisting of hydroxyethyl cellulose, HEC), ethylcellulose (EC), and combinations thereof.
본원의 일 구현예에 있어서, 상기 내부전극용 도전성 잉크 조성물 100 중량부 대비 상기 니켈 전구체의 함량은 5 중량부 내지 30 중량부이고, 상기 증점제의 함량은 1 중량부 내지 10 중량부인 것일 수 있다. 이때, 상기 니켈 전구체의 함량은 바람직하게 10 중량부 내지 20 중량부이고, 상기 증점제의 함량은 바람직하게 1 중량부 내지 5 중량부인 것일 수 있다. 상기 니켈 전구체의 함량이 5 중량부 미만일 경우 제조되는 내부전극용 도전성 잉크 조성물의 도전성이 저하될 수 있으며, 30 중량부 초과일 경우 분산안정성에 문제가 있을 수 있다. 또한, 상기 증점제의 함량이 1 중량부 미만일 경우 상기 내부전극용 도전성 잉크 조성물이 적절히 혼합되지 않을 수 있으며, 10 중량부 초과일 경우 상기 내부전극용 도전성 잉크 조성물의 점도가 너무 많이 상승해 잉크젯 인쇄가 용이하지 않을 수 있다.In one embodiment of the present application, the content of the nickel precursor relative to 100 parts by weight of the conductive ink composition for the internal electrode is 5 parts by weight to 30 parts by weight, and the content of the thickener may be 1 part by weight to 10 parts by weight. At this time, the content of the nickel precursor is preferably 10 parts by weight to 20 parts by weight, the content of the thickener may be preferably 1 part by weight to 5 parts by weight. When the content of the nickel precursor is less than 5 parts by weight, the conductivity of the conductive ink composition for an internal electrode to be manufactured may be lowered, and if it exceeds 30 parts by weight, there may be a problem in dispersion stability. In addition, when the content of the thickener is less than 1 part by weight, the conductive ink composition for the internal electrode may not be properly mixed, and when the content of the thickener is more than 10 parts by weight, the viscosity of the conductive ink composition for the internal electrode increases too much, and inkjet printing It may not be easy.
본원의 일 구현예에 있어서, 상기 내부전극용 도전성 잉크 조성물은 보습제, 레벨러(leveler), 접착증진제 등을 더 포함하는 것일 수 있다.In one embodiment of the present application, the conductive ink composition for the internal electrode may further include a moisturizing agent, a leveler, an adhesion promoter, and the like.
본원의 일 구현예에 있어서, 상기 보습제는 1,2-hexanediol, 글리세린, 프로필렌 글리콜, 부틸렌 글리콜, 폴리에틸렌 글리콜, 소비톨 또는 트레할로스 등의 폴리올, 아미노산, 요소, 젖산염 또는 PCA-Na 등의 천연보습인자(NMF), 히아루론산염, 콘드로이친 황산염 또는 가수분해 콜라겐 등의 고분자 보습제 등이 사용될 수 있다.In one embodiment of the present application, the moisturizing agent is a natural moisturizing agent such as 1,2-hexanediol, glycerin, propylene glycol, butylene glycol, polyethylene glycol, sorbitol or trehalose, polyol, amino acid, urea, lactate, or PCA-Na. Polymer moisturizers such as factor (NMF), hyaluronate, chondroitin sulfate, or hydrolyzed collagen may be used.
본원의 일 구현예에 있어서, 상기 레벨러는 평활(레베링) 작용을 가진 첨가제로서, 폴리아민 등의 질소를 포함하는 화합물이 사용될 수 있다.In one embodiment of the present application, the leveler is an additive having a smoothing (leveling) action, and a compound containing nitrogen such as polyamine may be used.
본원의 일 구현예에 있어서, 상기 접착증진제는 무기물 성질과 유기물의 양쪽 특성을 가지고 있는 실란커플링제인 베타-(3,4-에폭시싸이클로헥실) 에틸트리메톡시실란(β-(3,4-epoxycyclohexyl)ethyltrimethoysilane), 감마-글리시드옥시프로필 메톡시실란(Gammaglycidoxypropyltrimethoxysilane), 감마-메타크릴옥시프로필트리메톡시실란(Gammamethacryloxypropyltrimethoxysilane) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.In one embodiment of the present application, the adhesion promoter is a silane coupling agent having both properties of an inorganic substance and an organic substance, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (β-(3,4- epoxycyclohexyl)ethyltrimethoysilane), gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and combinations thereof.
본원의 제 2 측면은,The second aspect of the present application,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 및 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;를 포함하는 적층형 세라믹 커패시터의 내부전극 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; And forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively, to provide a method for manufacturing the inner electrode of the multilayer ceramic capacitor. do.
본원의 제 1 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 본원의 제 1 측면에 대해 설명한 내용은 제 2 측면에서 그 설명이 생략되었더라도 동일하게 적용될 수 있다.The detailed description of parts overlapping with the first aspect of the present application is omitted, but the description of the first aspect of the present application may be equally applied even if the description is omitted in the second aspect.
이하, 본원의 제 2 측면에 따른 적층형 세라믹 커패시터의 내부전극 제조방법을 상세히 설명한다.Hereinafter, a method of manufacturing the internal electrode of the multilayer ceramic capacitor according to the second aspect of the present application will be described in detail.
우선, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극 제조방법은 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계;를 포함한다.First, in one embodiment of the present application, the method of manufacturing an internal electrode of the multilayer ceramic capacitor includes a step of preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극 제조방법은 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;를 포함한다.Next, in one embodiment of the present application, the method of manufacturing the internal electrode of the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
본원의 일 구현예에 있어서, 상기 니켈 전구체를 제조하는 단계; 및 잉크를 제조하는 단계;는 상기 본원의 제 1 측면에서 설명하였으므로 본원의 제 2 측면에서는 이하 설명을 생략하도록 한다.In one embodiment of the present application, the step of preparing the nickel precursor; And manufacturing the ink; since the first aspect of the present application has been described, the following description will be omitted in the second aspect of the present application.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극 제조방법은 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;를 포함한다. 상기 잉크젯 인쇄하는 개략도를 도 1에 간략하게 나타내었다.Next, in one embodiment of the present application, the method of manufacturing the internal electrode of the multilayer ceramic capacitor is ink-jet-printed on the upper and lower portions of the dielectric green sheet, respectively, and the first internal electrode on the upper portion and the second internal portion on the lower portion. And forming an electrode pattern. 1 is a schematic diagram of the inkjet printing.
본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 내부전극 제조방법은 상기 제1 내부전극 및 제2 내부전극 패턴을 형성하는 단계 이후에, 상기 내부전극 패턴이 형성된 유전체 그린시트를 소결시키는 단계를 더 포함하는 것일 수 있다.In one embodiment of the present application, the method of manufacturing the internal electrode of the multilayer ceramic capacitor comprises sintering the dielectric green sheet on which the internal electrode pattern is formed after forming the first internal electrode and the second internal electrode patterns. It may be further included.
본원의 일 구현예에 있어서, 상기 소결은 100℃ 내지 400℃의 온도에서 1 분 내지 20 분 동안 수행되는 것일 수 있으며, 바람직하게 200℃ 내지 300℃의 온도에서 5 분 내지 15 분 동안 수행되는 것일 수 있다. 상기 소결이 100℃ 미만의 온도 또는 1 분 미만 동안 수행될 경우 소결이 충분히 이루어지지 않을 수 있으며, 400℃ 초과의 온도 또는 20 분 초과 동안 수행될 경우 상기 내부전극 패턴이 형성된 유전체 그린시트가 손상될 수 있다.In one embodiment of the present application, the sintering may be performed for 1 minute to 20 minutes at a temperature of 100°C to 400°C, and preferably performed for 5 minutes to 15 minutes at a temperature of 200°C to 300°C. Can be. When the sintering is performed at a temperature of less than 100°C or for less than 1 minute, sintering may not be sufficiently performed, and when the temperature is exceeded at 400°C or for more than 20 minutes, the dielectric green sheet on which the internal electrode pattern is formed is damaged Can be.
본원의 일 구현예에 있어서, 상기 유전체 그린시트는 높은 유전율을 갖는 세라믹 재료로 이루어질 수 있으며, 예를 들어, 티탄산바륨(BaTiO3)계 재료, 납 복합 페로브스카이트계 재료 또는 티탄산스트론튬(SrTiO3)계 재료 등을 사용하는 것일 수 있다.In one embodiment of the present application, the dielectric green sheet may be made of a ceramic material having a high dielectric constant, for example, barium titanate (BaTiO 3 )-based material, lead composite perovskite-based material, or strontium titanate (SrTiO 3) ) May be used.
본원의 일 구현예에 있어서, 상기 잉크젯 인쇄는 통상적으로 사용되는 잉크젯 인쇄 방식을 사용하는 것일 수 있으며, 상기 잉크젯 인쇄를 통하여 유전체 그린시트의 상부 및 하부에 각각 상기 제조된 잉크를 이용하여 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 것일 수 있다. 이때, 상기 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트는 이를 한 세트(set)로 하여 적층되는 것일 수 있으며, 이를 적층하여 형성된 적층체의 양 측면에 제1 외부전극 및 제2 외부전극을 형성함으로써 적층형 세라믹 커패시터가 제조되는 것일 수 있다. 상기 제조된 적층형 세라믹 커패시터의 상기 제1 외부전극 및 제2 외부전극에 소정의 전압을 인가하면 서로 대향하는 제1 내부전극 및 제2 내부전극 사이에 전하가 축적되게 되고, 적층형 세라믹 커패시터의 정전용량을 서로 대향하는 제1 내부전극 및 제2 내부전극의 면적의 크기에 비례하는 것일 수 있다.In one embodiment of the present application, the inkjet printing may be an inkjet printing method that is commonly used, and the ink produced above is used on the upper and lower portions of the dielectric green sheet through the inkjet printing. It may be to form a second internal electrode pattern on the 1 internal electrode and the lower portion. At this time, the dielectric green sheet in which the first internal electrode and the second internal electrode pattern are formed may be stacked as a set, and the first external electrode and the second external electrode may be stacked on both sides of the stacked body. A multilayer ceramic capacitor may be manufactured by forming an external electrode. When a predetermined voltage is applied to the first external electrode and the second external electrode of the manufactured multilayer ceramic capacitor, electric charges are accumulated between the first internal electrode and the second internal electrode facing each other, and the capacitance of the multilayer ceramic capacitor It may be proportional to the size of the area of the first internal electrode and the second internal electrode facing each other.
본원의 일 구현예에 있어서, 상기 패턴이 형성된 유전체 그린시트의 박막 두께는 50 nm 내지 1,000 nm인 것일 수 있으며, 바람직하게 50 nm 내지 100 nm일 수 있다. 즉, 기존 내부전극 페이스트를 유전체 그린시트 상에 스크린 인쇄하는 방법에 비하여 보다 많은 내부전극 적층 수를 구현할 수 있으며, 이를 이용하여 제조된 적층형 세라믹 커패시터는 소형화 및 대용량화가 가능하기 때문에 산업적으로 활용가치가 매우 높을 수 있다.In one embodiment of the present application, the thin film thickness of the patterned dielectric green sheet may be 50 nm to 1,000 nm, and preferably 50 nm to 100 nm. That is, it is possible to realize a larger number of internal electrode stacks than the method of screen printing the existing internal electrode paste on the dielectric green sheet, and the multilayer ceramic capacitor manufactured using this can be miniaturized and large-capacity, and thus has industrial value. It can be very high.
본원의 제 3 측면은,The third aspect of the present application,
니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계; 상기 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트를 적층하여 세라믹 적층체를 형성하는 단계; 및 상기 세라믹 적층체의 양 측면에 제1 외부전극 및 제2 외부전극을 형성하는 단계;를 포함하는 적층형 세라믹 커패시터의 제조방법을 제공한다.Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively; Forming a ceramic laminate by stacking the dielectric green sheets on which the first internal electrode and the second internal electrode patterns are formed; And forming a first external electrode and a second external electrode on both side surfaces of the ceramic laminate.
본원의 제 1 측면 및 제 2 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 본원의 제 1 측면 및 제 2 측면에 대해 설명한 내용은 제 3 측면에서 그 설명이 생략되었더라도 동일하게 적용될 수 있다.The detailed description of parts overlapping with the first and second aspects of the present application is omitted, but the description of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .
이하, 본원의 제 3 측면에 따른 적층형 세라믹 커패시터의 제조방법을 상세히 설명한다.Hereinafter, a method of manufacturing a multilayer ceramic capacitor according to a third aspect of the present application will be described in detail.
우선, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 제조방법은 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계;를 포함한다.First, in one embodiment of the present application, the method of manufacturing the multilayer ceramic capacitor includes a step of preparing a nickel precursor by reacting a nickel compound with a compound containing a carboxyl group or a compound containing an amine group.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 제조방법은 상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;를 포함한다.Next, in one embodiment of the present application, the method of manufacturing the multilayer ceramic capacitor includes the steps of preparing the ink by mixing the prepared nickel precursor with a solvent and a thickener.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 제조방법은 상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;를 포함한다.Next, in one embodiment of the present application, the manufacturing method of the multilayer ceramic capacitor is inkjet printed on the upper and lower portions of the dielectric green sheet, respectively, so that the first internal electrode on the top and the second internal electrode pattern on the bottom It includes; forming a.
본원의 일 구현예에 있어서, 상기 니켈 전구체를 제조하는 단계; 잉크를 제조하는 단계; 및 내부전극 패턴을 형성하는 단계;는 상기 본원의 제 1 측면 및 제 2 측면에서 설명하였으므로 본원의 제 3 측면에서는 이하 설명을 생략하도록 한다.In one embodiment of the present application, the step of preparing the nickel precursor; Preparing an ink; And forming an internal electrode pattern; since the first and second aspects of the present application have been described, the following description will be omitted in the third aspect of the present application.
다음으로, 본원의 일 구현예에 있어서, 상기 적층형 세라믹 커패시터의 제조방법은 상기 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트를 적층하여 세라믹 적층체를 형성하는 단계; 및 상기 세라믹 적층체의 양 측면에 제1 외부전극 및 제2 외부전극을 형성하는 단계;를 포함한다.Next, in one embodiment of the present application, the method of manufacturing the multilayer ceramic capacitor includes: forming a ceramic laminate by stacking a dielectric green sheet on which the first internal electrode and the second internal electrode pattern are formed; And forming first and second external electrodes on both sides of the ceramic laminate.
본원의 일 구현예에 있어서, 상기 세라믹 적층체의 적층 수는 제조하고자 하는 적층형 세라믹 커패시터의 크기에 따라 달라질 수 있으며, 본 발명의 내부전극 패턴이 형성된 유전체 그린시트는 박막 두께가 1,000 nm 이하로서 매우 얇아 보다 많은 적층 수를 구현할 수 있다. 따라서, 이를 이용하여 제조된 적층형 세라믹 커패시터는 소형화 및 대용량화가 가능하기 때문에 산업적으로 활용가치가 매우 높을 수 있다.In one embodiment of the present application, the number of layers of the ceramic laminate may vary depending on the size of the multilayer ceramic capacitor to be manufactured, and the dielectric green sheet on which the internal electrode pattern of the present invention is formed has a thin film thickness of 1,000 nm or less. Because it is thin, it is possible to realize a higher number of stacks. Therefore, since the multilayer ceramic capacitor manufactured using the above can be miniaturized and large-capacity, the utilization value can be very high industrially.
본원의 일 구현예에 있어서, 상기 적층체를 형성하는 단계는 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트를 적층하고, 적층방향으로 가압하여 내부전극 및 유전체 그린시트를 서로 압착시키는 것일 수 있다. 상기와 같은 방법을 통하여 내부전극과 유전체 그린시트가 교대로 적층된 세라믹 적층체를 형성하는 것일 수 있다.In one embodiment of the present application, the step of forming the laminate stacks a dielectric green sheet having a first internal electrode and a second internal electrode pattern, and compresses the internal electrode and the dielectric green sheet by pressing in the stacking direction. May be Through the above-described method, it may be to form a ceramic laminate in which internal electrodes and dielectric green sheets are alternately stacked.
본원의 일 구현예에 있어서, 상기 제1 외부전극 및 제2 외부전극은 도전성 금속으로 형성되는 것일 수 있으며, 예를 들어, 구리, 구리 합금, 니켈, 니켈 합금, 은, 팔라듐 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질로 형성되는 것일 수 있다. 상기 제1 외부전극 및 제2 외부전극은 상기 세라믹 적층체의 양 측면으로 노출된 제1 내부전극 및 제2 내부전극과 전기적으로 연결되어 있는 것일 수 있으며, 이후, 외부전극의 표면에 니켈, 주석 등의 도금 처리를 실시하는 것일 수 있다.In one embodiment of the present application, the first external electrode and the second external electrode may be formed of a conductive metal, for example, copper, copper alloy, nickel, nickel alloy, silver, palladium, and combinations thereof It may be formed of a material selected from the group consisting of. The first external electrode and the second external electrode may be electrically connected to the first internal electrode and the second internal electrode exposed to both sides of the ceramic laminate, and thereafter, nickel and tin on the surface of the external electrode. It may be a plating treatment such as.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.
실시예. 잉크젯 인쇄를 이용한 적층형 세라믹 커패시터의 제조 1Example. Manufacturing of multilayer ceramic capacitors using inkjet printing 1
단계 1: 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조Step 1: Preparation of a conductive ink composition for internal electrodes of a multilayer ceramic capacitor
니켈 클로라이드(니켈 화합물) 및 올레산(카르복실기를 포함하는 화합물)을 중량비율 1:4로 혼합하고 반응시켜 니켈 전구체를 제조하였다. 상기 제조된 니켈 전구체 30 wt%, 테르피네올(terpinol, 용매) 68 wt% 및 에틸 셀룰로오스(증점제) 2 wt%를 혼합하여 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물을 제조하였다.A nickel precursor was prepared by mixing nickel chloride (nickel compound) and oleic acid (compound containing a carboxyl group) at a weight ratio of 1:4 and reacting. A conductive ink composition for internal electrodes of a multilayer ceramic capacitor was prepared by mixing 30 wt% of the prepared nickel precursor, 68 wt% of terpineol (solvent), and 2 wt% of ethyl cellulose (thickener).
단계 2: 적층형 세라믹 커패시터의 내부전극 제조Step 2: manufacturing the internal electrode of the multilayer ceramic capacitor
상기 단계 1에서 제조한 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물을 바륨 티타네이트 그린시트(유전체 그린시트)의 상부 및 하부에 각각 잉크젯 인쇄시켜 적층형 세라믹 커패시터의 내부전극을 제조하였다. 이때, 상기 제조한 내부전극의 박막 두께는 약 100 nm이었다.The internal electrode of the multilayer ceramic capacitor was prepared by inkjet printing the conductive ink composition for the internal electrode of the multilayer ceramic capacitor prepared in step 1 above and below the barium titanate green sheet (dielectric green sheet). At this time, the thin film thickness of the prepared internal electrode was about 100 nm.
단계 3: 적층형 세라믹 커패시터의 제조Step 3: Preparation of a multilayer ceramic capacitor
상기 단계 2에서 제조한 적층형 세라믹 커패시터의 내부전극을 적층시켜 세라믹 적층체를 제조한 후, 상기 세라믹 적층체의 양 측면에 구리(Cu) 페이스트를 이용하여 외부전극을 각각 형성하여 적층형 세라믹 커패시터를 제조하였다.After manufacturing the ceramic laminate by laminating the internal electrodes of the multilayer ceramic capacitor prepared in step 2, an external electrode is formed on both sides of the ceramic laminate using copper (Cu) paste to prepare a multilayer ceramic capacitor. Did.
실시예 2. 잉크젯 인쇄를 이용한 적층형 세라믹 커패시터의 제조 2Example 2. Preparation of a multilayer ceramic capacitor using inkjet printing 2
상기 실시예 1의 단계 1에서 올레산(카르복실기를 포함하는 화합물) 대신 에틸렌디아민(아민기를 포함하는 화합물)을 혼합한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 적층형 세라믹 커패시터를 제조하였다.A multilayer ceramic capacitor was manufactured in the same manner as in Example 1, except that ethylene diamine (a compound containing an amine group) was mixed instead of oleic acid (a compound containing a carboxyl group) in Step 1 of Example 1.
비교예. 내부전극용 페이스트를 이용한 적층형 세라믹 커패시터의 제조Comparative example. Manufacturing of multilayer ceramic capacitors using internal electrode paste
기존 사용되는 내부전극용 페이스트를 이용한 적층형 세라믹 커패시터를 제조하기 위해 상기 실시예 1의 단계 1 및 2 대신 평균입균 300 nm의 니켈 분말, 50 wt%, 바인더 수지로서 폴리비닐부티랄 2.5 wt% 및 용매로서 테르피네올을 사용하여 페이스트를 제조하고, 상기 페이스트를 바륨 티타네이트 그린시트(유전체 그린시트)에 스크린 인쇄한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 적층형 세라믹 커패시터를 제조하였다.In order to manufacture a multilayer ceramic capacitor using a paste for an internal electrode that is used in the past, instead of steps 1 and 2 of Example 1, the average particle size of 300 nm nickel powder, 50 wt%, polyvinyl butyral 2.5 wt% and solvent as a binder resin A paste was prepared using terpineol, and a multilayer ceramic capacitor was manufactured in the same manner as in Example 1, except that the paste was screen printed on a barium titanate green sheet (dielectric green sheet).
실험예. 적층형 세라믹 커패시터의 내부전극 표면 관찰Experimental example. Observation of the inner electrode surface of a multilayer ceramic capacitor
상기 실시예 1 및 비교예에서 제조한 적층형 세라믹 커패시터의 내부전극의 표면을 관찰하기 위해 SEM 사진을 찍어, 이를 도 2에 나타내었다. 도 2a는 상기 비교예에서 제조한 적층형 세라믹 커패시터의 내부전극의 표면을 나타낸 SEM 사진이며, 도 2b는 상기 실시예 1에서 제조한 적층형 세라믹 커패시터의 내부전극의 표면을 나타낸 SEM 사진이다. 도 2a 및 2b에 나타낸 바와 같이 비교예의 경우 니켈 입자로 내부전극이 형성된 반면, 실시예의 경우 그래인으로 내부전극이 형성되었음을 확인할 수 있었다. 따라서, 본 발명의 실시예에서 제조한 적층형 세라믹 커패시터의 내부전극은 비교예에 비하여 매우 얇은 박막 두께를 가질 수 있음을 확인할 수 있었다.SEM images were taken to observe the surfaces of the internal electrodes of the multilayered ceramic capacitors prepared in Example 1 and Comparative Example, and are shown in FIG. 2. Figure 2a is a SEM photograph showing the surface of the internal electrode of the multilayer ceramic capacitor prepared in the comparative example, Figure 2b is a SEM photograph showing the surface of the internal electrode of the multilayer ceramic capacitor prepared in Example 1. 2A and 2B, in the case of the comparative example, the internal electrode was formed of nickel particles, whereas in the case of the example, it was confirmed that the internal electrode was formed of grain. Therefore, it was confirmed that the internal electrode of the multilayer ceramic capacitor manufactured in the embodiment of the present invention can have a very thin film thickness compared to the comparative example.

Claims (12)

  1. 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; 및Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group; And
    상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener;
    를 포함하는 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.Method for manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor comprising a.
  2. 제1항에 있어서, According to claim 1,
    상기 니켈 화합물은 니켈 나이트레이트(nickel nitrate), 니켈 클로라이드(nickel chloride), 니켈 아세테이트(nickel acetate), 니켈 포메이트(nickel formate) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The nickel compound comprises a material selected from the group consisting of nickel nitrate, nickel chloride, nickel acetate, nickel formate, and combinations thereof. Method for manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor.
  3. 제1항에 있어서, According to claim 1,
    상기 카르복실기를 포함하는 화합물은 아세트산(acetic acid), 카프로산(caproic acid), 라우르산(lauric acid), 올레산(oleic acid), 팔미트산(palmitic acid) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The compound containing the carboxyl group is from the group consisting of acetic acid, caproic acid, lauric acid, oleic acid, palmitic acid and combinations thereof. Method for manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor comprising a material to be selected.
  4. 제1항에 있어서, According to claim 1,
    상기 아민기를 포함하는 화합물은 암모니아(ammonia), 부틸아민(butylamine), 이소프로필아민(isopropylamine), 에틸렌디아민(ethylenediamine), 에탄올아민(ethanolamine) 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The compound containing the amine group includes a material selected from the group consisting of ammonia, butylamine, isopropylamine, ethylenediamine, ethanolamine and combinations thereof. A method of manufacturing a conductive ink composition for internal electrodes of a multilayer ceramic capacitor.
  5. 제1항에 있어서,According to claim 1,
    상기 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물의 중량 혼합 비율은 1: 2 내지 6인 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor, wherein the weight mixing ratio of the nickel compound and a compound containing a carboxyl group or a compound containing an amine group is 1: 2 to 6.
  6. 제1항에 있어서, According to claim 1,
    상기 증점제는 셀룰로오스 계열인 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The thickener is a method of manufacturing a conductive ink composition for an internal electrode of a multilayer ceramic capacitor, which is a cellulose-based.
  7. 제1항에 있어서,According to claim 1,
    상기 내부전극용 도전성 잉크 조성물 100 중량부 대비 상기 니켈 전구체의 함량은 5 중량부 내지 30 중량부이고, 상기 증점제의 함량은 1 중량부 내지 10 중량부인 것인 적층형 세라믹 커패시터의 내부전극용 도전성 잉크 조성물의 제조방법.The content of the nickel precursor compared to 100 parts by weight of the conductive ink composition for the internal electrode is 5 parts by weight to 30 parts by weight, and the content of the thickener is 1 part by weight to 10 parts by weight. Method of manufacturing.
  8. 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group;
    상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계; 및Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener; And
    상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively;
    를 포함하는 적층형 세라믹 커패시터의 내부전극 제조방법.Method for manufacturing an internal electrode of a multilayer ceramic capacitor comprising a.
  9. 제8항에 있어서,The method of claim 8,
    상기 적층형 세라믹 커패시터의 내부전극 제조방법은 상기 제1 내부전극 및 제2 내부전극 패턴을 형성하는 단계 이후에,The method of manufacturing the internal electrode of the multilayer ceramic capacitor is performed after forming the first internal electrode and the second internal electrode patterns,
    상기 내부전극 패턴이 형성된 유전체 그린시트를 소결시키는 단계를 더 포함하는 것인 적층형 세라믹 커패시터의 내부전극 제조방법.A method of manufacturing an internal electrode of a multilayer ceramic capacitor, further comprising sintering the dielectric green sheet on which the internal electrode pattern is formed.
  10. 제9항에 있어서,The method of claim 9,
    상기 소결은 100℃ 내지 400℃의 온도에서 1 분 내지 20 분 동안 수행되는 것인 적층형 세라믹 커패시터의 내부전극 제조방법.The sintering is carried out for 1 minute to 20 minutes at a temperature of 100 ℃ to 400 ℃ internal electrode manufacturing method of a multilayer ceramic capacitor.
  11. 제8항에 있어서,The method of claim 8,
    상기 패턴이 형성된 유전체 그린시트의 박막 두께는 50 nm 내지 1,000 nm인 것인 적층형 세라믹 커패시터의 내부전극 제조방법.The thickness of the thin film of the dielectric green sheet on which the pattern is formed is 50 nm to 1,000 nm.
  12. 니켈 화합물과, 카르복실기를 포함하는 화합물 또는 아민기를 포함하는 화합물을 반응시켜 니켈 전구체를 제조하는 단계; Preparing a nickel precursor by reacting the nickel compound with a compound containing a carboxyl group or a compound containing an amine group;
    상기 제조된 니켈 전구체를 용매 및 증점제와 혼합하여 잉크를 제조하는 단계;Preparing an ink by mixing the prepared nickel precursor with a solvent and a thickener;
    상기 제조된 잉크를 유전체 그린시트의 상부 및 하부에 각각 잉크젯 인쇄시켜 상부에 제1 내부전극 및 하부에 제2 내부전극 패턴을 형성하는 단계;Forming the first inner electrode and the second inner electrode pattern on the upper portion by inkjet printing the prepared ink on the upper and lower portions of the dielectric green sheet, respectively;
    상기 제1 내부전극 및 제2 내부전극 패턴이 형성된 유전체 그린시트를 적층하여 세라믹 적층체를 형성하는 단계; 및Forming a ceramic laminate by stacking the dielectric green sheets on which the first internal electrode and the second internal electrode patterns are formed; And
    상기 세라믹 적층체의 양 측면에 제1 외부전극 및 제2 외부전극을 형성하는 단계;Forming a first external electrode and a second external electrode on both side surfaces of the ceramic laminate;
    를 포함하는 적층형 세라믹 커패시터의 제조방법.Method of manufacturing a multilayer ceramic capacitor comprising a.
PCT/KR2019/015889 2018-11-29 2019-11-19 Method for preparing conductive ink composition for inner electrode of layered ceramic capacitor, and method for manufacturing inner electrode of layered ceramic capacitor by using same WO2020111634A1 (en)

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