WO2022225361A1 - Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci - Google Patents

Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci Download PDF

Info

Publication number
WO2022225361A1
WO2022225361A1 PCT/KR2022/005768 KR2022005768W WO2022225361A1 WO 2022225361 A1 WO2022225361 A1 WO 2022225361A1 KR 2022005768 W KR2022005768 W KR 2022005768W WO 2022225361 A1 WO2022225361 A1 WO 2022225361A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
electronic component
particle diameter
photosensitive
conductive metal
Prior art date
Application number
PCT/KR2022/005768
Other languages
English (en)
Korean (ko)
Inventor
단성백
이승철
박규환
Original Assignee
주식회사 아모텍
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 아모텍 filed Critical 주식회사 아모텍
Publication of WO2022225361A1 publication Critical patent/WO2022225361A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/006—Apparatus or processes for applying terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/04—Drying; Impregnating
    • 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
    • H01G4/012—Form of non-self-supporting 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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • 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 for manufacturing a multilayer ceramic electronic component and to a multilayer ceramic electronic component implemented through the method.
  • elements such as capacitors, capacitors, varistors, suppressors, and MLCCs laminate several to hundreds of green sheets printed with electrode patterns, and then simultaneously sinter the electrodes and green sheets to form a single unit. It corresponds to a co-sintering type multilayer ceramic electronic component that implements a device, and many researches are being made so that these devices can also be miniaturized and high-capacity in line with the recent miniaturization and high performance of electronic devices.
  • the conventional method of printing the electrode pattern on the green sheet has used a screen printing method or a gravure printing method
  • the screen printing method or the gravure printing method has an advantage of low cost.
  • these methods can implement only the electrode line width and the inter-electrode spacing of 40 ⁇ 80 ⁇ m level, it is difficult to form a smaller and more sophisticated fine pattern with these methods.
  • the internal electrodes of highly laminated and miniaturized co-sintered multilayer ceramic electronic components can be fabricated using conventional screen printing or gravure methods. There is a problem in that it is difficult to form by the printing method.
  • the viscosity of the printing electrode composition must be greatly reduced, which causes problems in printing blur and lowering of print resolution.
  • the present invention has been devised in consideration of the above points, and a method for manufacturing a multilayer ceramic electronic component that can more easily and reliably realize ultra-thin and micro-patterning of the internal electrode required for realizing a large-capacity multilayer ceramic electronic component. And an object of the present invention is to provide a multilayer ceramic electronic component implemented through this.
  • the present invention is a multilayer ceramic electronic component manufacturing method that is implemented to have excellent thickness uniformity of an ultra-thin electrode and at the same time prevents shape deformation of a sintered body or separation between layers due to a difference in shrinkage characteristics between an internal electrode and a ceramic green sheet after sintering; Another object is to provide a multilayer ceramic electronic component implemented through this.
  • the present invention provides a step of (1) preparing a ceramic green sheet, (2) forming a positive or negative type photosensitive electrode material layer by electrospraying a photosensitive electrode composition on the entire upper surface of the ceramic green sheet. , (3) disposing a mask pattern layer on the positive or negative type photosensitive electrode material layer and exposing it, (4) treating the developer solution to remove the exposed or unexposed photosensitive electrode material layer portion to form the electrode pattern layer.
  • a method for manufacturing a multilayer ceramic electronic component comprising the steps of implementing, (5) laminating a plurality of ceramic green sheets provided with an electrode pattern layer and then press-sintering.
  • the ceramic green sheet may have an average thickness of 5.0 ⁇ m or less.
  • the manufactured multilayer ceramic electronic component is MLCC, and the number of stacked ceramic green sheets in step (5) may be 100 or more.
  • the photosensitive electrode composition includes a binder resin including a conductive metal powder, ceramic powder, and photosensitive resin having an average particle diameter of 150 nm or less, a monomer, a photoinitiator and a solvent to realize a photosensitive electrode material layer having an average thickness of 1.0 ⁇ m or less when dried.
  • a binder resin including a conductive metal powder, ceramic powder, and photosensitive resin having an average particle diameter of 150 nm or less, a monomer, a photoinitiator and a solvent to realize a photosensitive electrode material layer having an average thickness of 1.0 ⁇ m or less when dried.
  • the conductive metal powder may have an average particle diameter of 80 nm or less.
  • the number of particles having a particle diameter of 2 times or more of the average particle diameter is 20% or less of the total number of conductive metal powders, and the number of particles having a particle diameter of 0.5 times or less of the average particle diameter is 20 of the total number of conductive metal powders % or less.
  • the conductive metal powder may include at least one metal selected from the group consisting of Ni, Mn, Cr, Al, Ag, Cu, Pd, W, Mo and Co, an alloy including at least one of them, and at least one of them. It may include any one or more of mixed metals including two types.
  • the ceramic powder may include at least one ceramic powder selected from the group consisting of titania, alumina, silica, cordierite, mullite, spinel, barium titanate, calcium zirconia, and zirconia.
  • the conductive metal powder may be provided in an amount of 10 to 30% by weight based on the total weight.
  • the ceramic powder may have an average particle diameter of 0.1 to 0.5 times the average particle diameter of the conductive metal powder.
  • the ceramic powder may be included in an amount of 4 to 10 parts by weight based on 100 parts by weight of the conductive metal powder.
  • the total weight of the binder resin and the monomer may be included in an amount of 2 to 13 parts by weight based on 100 parts by weight of the conductive metal powder.
  • the ceramic powder may have an average particle diameter of 45 nm or less.
  • the photosensitive electrode composition is a negative type
  • the photosensitive resin is glycidyl methacrylate (GMA), methyl methacrylate (MMA), isobornyl methacrylate (IBOMA), benzyl methacrylate, methacrylic acid It may include an acrylate-based copolymer in which at least two monomers of (MMA), acrylic acid (AA), and styrene monomers are copolymerized.
  • 10 to 100 parts by weight of the monomer and 1 to 50 parts by weight of the photoinitiator may be included with respect to 100 parts by weight of the photosensitive resin.
  • the photosensitive resin is a copolymer of methacrylic acid, methyl methacrylate and isobornyl methacrylate, and contains 15.5 to 19.5 mol% of methacrylic acid, and an acrylate-based copolymer having a weight average molecular weight of 8000 to 15000. may include.
  • the monomer may be a polyfunctional monomer.
  • the binder resin may further include a polyvinyl butyral resin.
  • the photosensitive electrode composition may have a viscosity of 50 to 150 cps at 25°C.
  • the present invention provides a multilayer ceramic electronic component including a ceramic body and a plurality of internal electrodes disposed inside the body, wherein an average thickness of the internal electrode is 0.7 ⁇ m or less, and the thickness direction of the ceramic body among the plurality of internal electrodes is Provided is a multilayer ceramic electronic component having a minimum vertical distance between adjacent internal electrodes spaced apart from each other by 2.0 ⁇ m or less.
  • the method for manufacturing a multilayer ceramic electronic component according to the present invention can more easily and reliably realize the ultra-thin and micro-patterning of the internal electrode, which are required for realizing a large-capacity multilayer ceramic electronic component.
  • the provided internal electrode is made ultra-thin, it can be implemented to have excellent thickness uniformity, and after sintering, shape deformation of the sintered body or separation between layers due to a difference in shrinkage characteristics between the internal electrode and the ceramic green sheet can be prevented.
  • FIG. 1 is a process schematic diagram showing a method of manufacturing a multilayer ceramic electronic component according to an embodiment of the present invention
  • FIG. 2 is a SEM photograph of nickel powder having an average particle diameter of 75 nm as a conductive metal powder included in the photosensitive electrode composition for electrospray used in an embodiment of the present invention
  • FIG. 3 is an SEM photograph before the nickel powder according to FIG. 2 is wet classified
  • FIGS. 5 and 6 are photographs of an electrode composition for electrospray containing nickel powder according to FIGS. 2 and 3, respectively, and FIG. 5 is a photograph uniformly dispersed with ceramic powder without precipitation of nickel powder, FIG. 6 is nickel powder A photograph of ceramic powder and phase separation due to sedimentation, and
  • FIG. 7 and 8 are optical micrographs of an electrode pattern dried after the photosensitive electrode composition for electrospray used in an embodiment of the present invention is electrosprayed in a predetermined pattern
  • FIG. 7 is an electrode in the electrode pattern. It is a photograph of an electrode pattern having excellent formability of a continuous electrode surface without a formed portion
  • FIG. 8 is a photograph of an electrode pattern in which a continuous electrode surface is not partially formed due to the partial presence of a drop-out electrode in which an electrode is not formed in the electrode pattern.
  • a method of manufacturing a multilayer ceramic electronic component includes (1) preparing a ceramic green sheet 11 ((a) of FIG. 1), (2) ceramic green Forming a photosensitive electrode material layer 12a of a positive or negative type by electrospraying (2) the photosensitive electrode composition on the entire upper surface of the sheet 11 (FIG. 1 (b)), (3) Mask pattern layer 3 ) is disposed on the photosensitive electrode material layer 12a and exposed to light (FIG. 1 (c)), (4) treated with a developer to remove the exposed or unexposed photosensitive electrode material layer portion 12a to remove the electrode Implementing the pattern layer 12 ((d) of FIG. 1), (5) laminating a plurality of ceramic green sheets 10 provided with the electrode pattern layer 12, followed by pressure sintering (see FIG. 1) (e), (f)) is carried out.
  • the step of preparing the ceramic green sheet 11 (FIG. 1 (a)) is performed.
  • the ceramic green sheet 11 may be used without limitation in the case of a known ceramic green sheet used in manufacturing a multilayer ceramic electronic component or a ceramic green sheet in which a composition of a known ceramic green sheet is appropriately changed.
  • the ceramic green sheet 11 may be formed of a ceramic material suitable for realizing physical properties required for a desired use of a multilayer ceramic electronic component.
  • the ceramic green sheet may include a dielectric material commonly referred to as class I and/or class II.
  • MLCC high-capacity MLCC
  • it may be included as a main component of a dielectric material commonly referred to as class II, and for example, BaTiO 3 , (Ba,Ca)(Ti,Zr)O 3 , CaTiO 3 , SrTiO 3 , CaZrO 3 , etc. of ferroelectrics can be used.
  • a glassy component, a binder component for bonding the dielectric material, and a solvent may be further included as sub-components, and in addition, components other than the above-mentioned components included in manufacturing a conventional ceramic green sheet may be further included. and the present invention is not particularly limited thereto.
  • the glassy component is to increase the density of the body to ensure the mechanical strength of the body
  • Al, B, Si, Ca and Mg may include at least one metal or non-metal oxide selected from the group consisting of. .
  • the thickness of the ceramic green sheet 11 in order to realize a highly laminated high-capacity multilayer ceramic electronic component. It is preferable to use a dielectric material or a glassy component finely divided into 1 ⁇ m or less, more preferably 800 nm or less.
  • the ceramic green sheet 11 may be implemented by wet-mixing a dielectric material, a glassy component, a binder component, a solvent, etc. to prepare a ceramic slurry, then coating it to a predetermined thickness on the carrier film 1 and drying it.
  • the coating method of the ceramic slurry may use known methods and apparatuses according to known methods and methods, such as a die coater, a gravure coater, and a micro gravure coater, for example, a detailed description thereof will be omitted in the present invention.
  • the carrier film 1 may be a known film used in manufacturing a green sheet, for example, a PET film, and a release layer may be further included on one surface of the PET film.
  • the ceramic slurry coated on the carrier film 1 may be subjected to a drying process, and the drying process may be performed using known conditions in consideration of the type and content of the solvent, the thickness of the applied ceramic slurry, and the like. .
  • the manufactured ceramic green sheet 11 may have an average thickness of, for example, 0.1 to 5.0 ⁇ m, and preferably an average thickness of 0.1 to 0.5 ⁇ m in consideration of thinning for high lamination, but is not limited thereto.
  • the photosensitive electrode composition is electrically sprayed (2) on the upper entire surface of the ceramic green sheet 11 to form a positive or negative type photosensitive electrode material.
  • a step of forming the layer 12a is performed.
  • the coating thickness of the photosensitive electrode composition In order to realize an internal electrode having an ultra-thin thickness, it is important to control the coating thickness of the photosensitive electrode composition to be very thin. In the case of conventionally used screen printing or gravure printing, the thickness of the electrode after printing is typically 5 ⁇ m or more, which is due to the difficulty in forming a thin and uniform coating thickness of the electrode composition itself, such as an electrode paste.
  • the photosensitive electrode composition used in an embodiment of the present invention can realize a thinner and more uniform internal electrode by forming an electrode surface through electrospray.
  • the average thickness of the applied photosensitive electrode composition may be 1.5 ⁇ m or less, and through this, it is advantageous to satisfy the average thickness of the printed photosensitive electrode material layer 12a in a dried state is 1.0 ⁇ m or less, and a thinner thickness during sintering As it can be implemented as an electrode of , it may be advantageous to eventually realize a highly laminated multilayer ceramic electronic component.
  • the photosensitive electrode composition is electrosprayed, it is difficult to use a paste for manufacturing a conventional photosensitive internal electrode as it is.
  • the high electrical conductivity and viscosity of the electrode paste may inhibit electrospray, and it may not be possible to apply the electrode composition to a uniform and thin thickness.
  • the particle size or distribution of the metal powder contained in the conventional electrode paste is also large and wide, so it may be difficult to implement an ultra-thin film, specifically, the photosensitive electrode material layer 12a having an average thickness of 1.5 ⁇ m or less after application and 1.0 ⁇ m or less after drying.
  • the photosensitive electrode composition is suitable for the electrospray method and has an average particle diameter of 150 nm or less so as to realize an ultra-thin photosensitive electrode material layer 12a having an average thickness of 1.0 ⁇ m, preferably 0.6 ⁇ m or less when dried.
  • Powders, ceramic powders, binder resins including photosensitive resins, monomers, photoinitiators, and solvents may be used.
  • it since it is possible to implement an ultra-thin electrode suitable for forming an electrode on a green sheet, it may be particularly suitable for implementing an internal electrode of a multilayer ceramic component such as MLCC requiring high lamination.
  • the conductive metal powder imparts conductivity after sintering and forms the body of the electrode, and the conductive metal powder commonly used for manufacturing electrodes for electronic components can be used without limitation.
  • the conductive metal powder may include one metal selected from the group consisting of nickel, manganese, chromium, aluminum, silver, copper, palladium, molybdenum, tungsten and cobalt, an alloy containing at least one of these, and at least one of these It may include any one or more of mixed metals including two types.
  • At least one selected from the group consisting of palladium, silver-palladium alloy, silver, nickel and copper may be included, and more preferably in consideration of heat resistance, conductivity and material cost may include nickel.
  • the conductive metal powder may have an average particle diameter of 150 nm or less, preferably 100 nm or less, and more preferably 80 nm or less. Even when the average thickness of the photosensitive electrode material layer exceeds 1.0 ⁇ m, it is difficult for the implemented photosensitive electrode material layer to form a continuous electrode surface, or when the photosensitive electrode material layer with an average thickness of 1.0 ⁇ m or less is implemented, the thickness uniformity is very non-uniform. This can make it difficult to implement high-quality, highly laminated, laminated ceramic parts.
  • the conductive metal powder may have an average particle diameter of 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. , the material cost may increase.
  • the metal powder is finely divided, it is required to ensure dispersibility, but degreasing may not be easy due to organic compounds such as dispersants added to ensure dispersibility. Separation may occur.
  • dispersibility is reduced when the average particle diameter of the conductive metal powder is too small, and when agglomerated to form coarse secondary particles, the dried photosensitive electrode material layer is difficult to form a continuous electrode surface or , which is undesirable because there is a risk that the thickness non-uniformity may be aggravated.
  • the number of particles having a particle diameter of at least twice the average particle diameter is 20% or less of the total number of conductive metal powders, more preferably 15% or less, even more preferably 10% or less, more preferably is 5% or less, and the number of particles having a particle diameter of 0.5 times or less of the average particle diameter may have a particle size distribution of 20% or less, more preferably 10% or less, of the total number of conductive metal powders, through which it is supplied for electrospray It is suitable to minimize the formation of secondary particles by agglomeration of the conductive metal powder in the photosensitive electrode composition, and to minimize or prevent sedimentation of the conductive metal powder in the injection solution chamber in the electrospray device, through which the photosensitive electrode material layer It is advantageous to prevent the discontinuous electrode surface where the electrode does not exist partially due to the non-spray of the internal electrode composition, and it prevents the deterioration of the external electrode appearance quality such as non-uniformity of electrical characteristics such as resistance by position of the implemented
  • the shape of the conductive metal powder may have a variety of known shapes, but preferably a spherical or spherical polyhedron may be suitable.
  • the conductive metal powder may be included in an amount of 30% by weight or less, more preferably 10 to 30% by weight, and still more preferably 20 to 30% by weight based on the total weight of the photosensitive electrode composition. If the conductive metal powder is included in excess of 30 wt%, sedimentation or precipitation of the conductive metal powder in the photosensitive electrode composition supplied for electrospray may occur, and thus the conductive powder may be non-uniformly sprayed during electrospray. In addition, it may be difficult to control the thickness of the electrode implemented by electrospray. Furthermore, since exposure of the lower side of the photosensitive electrode material layer 12a is inhibited due to the high content of the conductive metal powder, an undercut phenomenon may occur after development.
  • the dried photosensitive electrode material layer or the sintered internal electrode may form an island such as a water droplet, thereby reducing the continuous formability of the electrode surface or non-uniform electrode thickness. It may be difficult to implement a desired electrode, such as disconnection.
  • the photosensitive electrode composition has high electrical conductivity, and electric spraying may be difficult due to the high electrical conductivity.
  • the photosensitive electrode composition may include ceramic powder, and through this, the photosensitive electrode composition may be adjusted to have an electrical conductivity suitable for electrospray.
  • the difference in sintering temperature between the electrode pattern layer 12 and the ceramic green sheet 11 generated when the electrode pattern layer 12 and the ceramic green sheet 11 are simultaneously sintered in step (5), which will be described later, and the shrinkage due to this It is possible to prevent shape deformation such as crushing of the sintered body due to the difference in characteristics.
  • the ceramic component derived from the ceramic powder moves toward the surface of the sintered electrode and can be separated from the conductive component derived from the sintered conductive metal powder, thereby increasing the dielectric constant, thereby contributing to the improvement of properties of multilayer ceramic electronic components. have.
  • the ceramic powder may have an average particle diameter of 100 nm or less, in another example 70 nm or less, 45 nm or less, or 1 to 30 nm.
  • ceramic powder having an appropriate average particle diameter in consideration of the average particle diameter of the conductive metal powder may be used.
  • the ceramic powder having a smaller average particle diameter of 0.5 times or less, more preferably 0.3 times or less of the average particle diameter of the conductive metal powder It can be used, and through this, it is advantageous to delay the shrinkage of the electrode faster than that of the ceramic green sheet during sintering.
  • the average particle diameter of the ceramic powder may be 20 nm or less.
  • the average particle diameter of the ceramic powder is smaller than 0.1 times the average particle diameter of the conductive metal powder, the amount of resin added may be increased due to the increase in the surface area of the particles, and the thickness unevenness of the dried and/or sintered electrode may be reduced. There is a risk of causing the problem, and the shrinkage rate of the electrode may be excessively increased during sintering. In addition, since the exposure of the lower side of the dry electrode is inhibited due to the ceramic powder having a small particle size during exposure, there is a risk that an undercut phenomenon may occur after development.
  • the ceramic powder may also be advantageous to maintain a uniform dispersed phase as the proportion of coarse particles having a particle diameter of two times or more compared to the average particle diameter is small. Accordingly, in the ceramic powder, the number of particles having a particle diameter of at least twice the average particle diameter may be 20% or less, more preferably 10% or less, and still more preferably 5% or less of the total number of ceramic powder particles.
  • the ceramic powder may be used without limitation in the case of known ceramic powders, but for example, at least one selected from the group consisting of titania, alumina, silica, cordierite, mullite, spinel, barium titanate, calcium zirconia and zirconia.
  • the above ceramic powder may be included.
  • the ceramic powder when used for forming an internal electrode by electrospraying the photosensitive electrode composition on the green sheet, it may be selected as a common component with the dielectric component of the green sheet, and through this, the ceramic green sheet and the electrode during co-sintering It may be easier to control the shrinkage characteristics between the pattern layers, and it may be advantageous to improve bonding and adhesion characteristics between the electrode pattern layer and the ceramic green sheet.
  • the ceramic powder may be included in an amount of 4 to 10 parts by weight, more preferably 4 to 7 parts by weight, based on 100 parts by weight of the conductive metal powder. If the amount of the ceramic powder is less than 4 parts by weight, the thickness of the electrode implemented Control can be difficult. In addition, it is difficult to control the shrinkage characteristics during simultaneous sintering with the ceramic green sheet, and cracks and peeling of the electrode realized after sintering may occur frequently. In addition, if the ceramic powder is contained in excess of 10 parts by weight, the electrical conductivity of the implemented electrode is lowered, and there is a fear that the degree of contraction of the electrode during sintering may be excessive.
  • the particle diameter of the conductive metal powder and ceramic powder included in the photosensitive electrode composition used in the present invention is a value based on particle size measurement by a dynamic light scattering method, and is a volume-based particle diameter, and the average particle diameter is D50 in the cumulative volume-based particle size distribution. means the corresponding particle size.
  • the measuring device may be a known measuring device capable of counting nano-sized powder particle size, for example, a measuring device such as a Zetasizer series or APS-100.
  • the conductive metal powder having an average particle diameter of 150 nm or less can be implemented using a dry plasma powder synthesis method such as PVD or CVD, which can be advantageous for producing a powder with a clean particle surface.
  • a dry plasma powder synthesis method such as PVD or CVD
  • the continuous centrifuge can control the average particle size by controlling the rotational speed and the input amount per minute of the centrifuge, and cause rapid sedimentation of the conductive metal powder in the electrode composition to inhibit uniform dispersion of coarse particles, for example, of the average particle diameter. It is possible to control so that the number ratio of the conductive metal powder having a particle diameter of twice or more is small. If the rotation speed of the centrifuge is too high, the production yield is greatly reduced, and if it is too low, the removal rate of coarse particles that hinders uniform dispersion is reduced. In addition, if the input amount is too large, the time for receiving centrifugal force in the centrifuge chamber is shortened, so it is not easy to remove large particles.
  • FIG. 2 is an SEM photograph of the conductive metal powder used in Example 4, and the particle size of the conductive metal powder as shown in FIG. 3 is adjusted so that the coarse particle ratio is low through wet classification through centrifugation. As shown in, it can be confirmed that the photosensitive electrode composition has a good dispersion state. On the other hand, when there are many coarse particles of the conductive metal powder, as shown in FIG. 6 , it can be confirmed that the conductive metal powder has a lot of sedimentation and phase separation from the ceramic powder has occurred.
  • the ceramic powder can be prepared by appropriately utilizing a known powder technology and a particle control technology to have a desired particle size distribution using a commercially available ceramic powder, and as a specific means, various known grinding and classification methods, related devices and the same It can be manufactured by adjusting factors such as the grinding conditions used and the grinding time.
  • a pulverizer use either a mechanical pulverizer employing a blade mill or a super rotor, or an airflow pulverizer that pulverizes particles by colliding each other against a wall using a high-speed airflow of high-pressure air.
  • the grinding level can be adjusted by putting it back into another grinder and grinding it.
  • a classifier for classifying the pulverized material such as a centrifugal wind power disperser, a disperser using a physical dispersing force such as a high-speed air flow to prevent agglomeration of fine particles, or a wet classification method to have a desired particle size distribution through a centrifugal separation method.
  • a classifier for classifying the pulverized material such as a centrifugal wind power disperser, a disperser using a physical dispersing force such as a high-speed air flow to prevent agglomeration of fine particles, or a wet classification method to have a desired particle size distribution through a centrifugal separation method.
  • the photosensitive electrode composition includes a binder resin including a photosensitive resin, a photosensitive composition including a monomer, and a photoinitiator together with the above-described conductive metal powder and ceramic powder.
  • the photosensitive composition may be of a positive type or a negative type.
  • the binder resin includes a photosensitive resin, and the photosensitive resin serves as a binder of components in the photosensitive electrode composition to maintain bonding strength of the dried electrode and to impart solubility to a developer.
  • the photosensitive resin may be cured by intermolecular crosslinking under the action of active energy such as ultraviolet rays or electron beams to form a cured coating film, or may be dissolved in a developer by breaking intermolecular crosslinking.
  • the photosensitive resin may be used without limitation if it is a photosensitive resin commonly used in the field of photosensitive electrode paste. In addition, it may be a positive type or negative type photosensitive resin.
  • a photosensitive binder resin used in the photosensitive resin composition such as acrylate-based, cellulose-based, novolac acrylic-based, water-soluble polymer, polyimide, or a precursor thereof may be used.
  • the photosensitive resin may preferably be an acrylate-based photosensitive binder.
  • the acrylate-based photosensitive binder examples include a resin having an ethylenically unsaturated bond such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, or a photosensitive functional group such as a propargyl group, for example, an ethylenically unsaturated group in the side chain.
  • a resin having an ethylenically unsaturated bond such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group
  • a photosensitive functional group such as a propargyl group
  • Various conventionally well-known photosensitive resins (photosensitive prepolymer) such as the acrylic copolymer which has, the unsaturated carboxylic acid-modified epoxy resin, or the resin which added polybasic acid anhydride further to it, can be used.
  • the photosensitive resin is glycidyl methacrylate (GMA), methyl methacrylate (MMA), isobornyl methacrylate (IBOMA), benzyl methacrylate, methacrylic acid (MMA), acrylic acid (AA) and It may include an acrylate-based copolymer in which at least two monomers of the styrene monomo are copolymerized.
  • the photosensitive resin may include glycidyl methacrylate-methyl methacrylic acid copolymer, glycidyl methacrylate-methyl methacrylic acid- methyl methacrylate-isobornyl methacrylate copolymer, and methyl methacrylic acid. It may be a late-benzyl methacrylate-methacrylic acid copolymer.
  • the photosensitive resin according to an embodiment of the present invention is a copolymer of methacrylic acid, methyl methacrylate and isobornyl methacrylate, and contains 15.5 to 19.5 mol% of methacrylic acid, and a weight average molecular weight of 8000 to It may include an acrylate-based copolymer of 15000, more preferably 25 to 40 mol% of methyl methacrylate, and may be a copolymer containing isobornyl methacrylate as a residual amount, through which better quality and resolution , it may be advantageous to implement an electrode pattern in which residues are prevented with photosensitivity.
  • the acrylate-based copolymer may be introduced by reacting a compound having an epoxy or isocyanate functional group to a carboxy functional group in the acrylate-based copolymer to control the acid value.
  • the compound having the epoxy group may include, for example, at least one of a methylene functional group, a vinyl functional group, and an allyl functional group at the terminal, and specifically may be allyl glycidyl ether.
  • the compound having the isocyanate functional group may be, for example, 2-acryloyloxyethyl isocyanate.
  • the acrylate-based copolymer with the acid value controlled may have an acid value of 25 to 100 mgKOH/g, thereby exhibiting excellent photosensitivity and developability.
  • the glass transition temperature of the photosensitive resin as the acrylate-based copolymer may be 20 ⁇ 150 °C.
  • polyimide or a precursor thereof may be included in addition to the acrylate-based photosensitive resin.
  • the polyimide or its precursor content may be included in an amount of 10 to 60 parts by weight based on 100 parts by weight of the acrylate-based resin, which may be more advantageous in achieving the object of the present invention.
  • the binder resin may further include polyvinyl butyral resin.
  • the binder resin made of only the photosensitive resin may have poor adhesion to the ceramic green sheet, which is the surface to be electrosprayed. Accordingly, polyvinyl butyral resin may be further included, and improved adhesion and adhesion to the ceramic green sheet may be achieved.
  • the polyvinyl butyral resin may be contained in 10 to 50% by weight of the binder resin, and if it is included in an amount exceeding 50% by weight, there is a risk that defects such as residues during development after exposure may increase, and the content is less than 10% by weight. When contained, the effect of improving adhesion to the surface of the ceramic green sheet may be insignificant.
  • the monomer contains a carbon double bond, and the double bond is converted into a single bond by radicals excited by active energy such as ultraviolet rays or electron beams to polymerize to form a cured structure in the photosensitive electrode composition.
  • the monomer is not particularly limited as long as it is a monomer commonly used in the field of photosensitive paste.
  • the monomer may be, for example, a polyfunctional monomer such as bifunctional, trifunctional, or tetrafunctional.
  • an acrylic ester system selected from trimethylolpropane triacrylate, trimethylolpropane ethoxylated triacrylate, pentaerythritol tri-acrylate or pentaerythritol tetra-acrylate may be used.
  • an acrylic ester system selected from trimethylolpropane triacrylate, trimethylolpropane ethoxylated triacrylate, pentaerythritol tri-acrylate or pentaerythritol tetra-acrylate may be used.
  • the present invention is not limited thereto.
  • the monomer may be included in an amount of 10 to 100 parts by weight based on 100 parts by weight of the photosensitive resin. If the content of the monomer is less than 10 parts by weight, the curing density of the exposure pattern may become weak, and if it exceeds 100 parts by weight, the pattern characteristics may be deteriorated, and resistance may increase due to residual organic matter after curing, or the laminated green There is a fear that separation between the sheet layers may occur.
  • an oligomer may be further included as a component for forming a cured structure by radicals.
  • the oligomer may be an oligomer commonly used in the photosensitive electrode composition without limitation, and may be, for example, an acrylate having a molecular weight of 1000 or less.
  • the oligomer may be contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the photosensitive resin, but is not limited thereto.
  • the photoinitiator is a compound that causes a chemical reaction by generating radicals upon irradiation with active energy such as ultraviolet rays or electron beams, and is not particularly limited as long as it is a photopolymerization initiator commonly used in the field of photosensitive electrode compositions.
  • active energy such as ultraviolet rays or electron beams
  • acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds including monophenyl, oxime compounds, carbazole compounds, diketone compounds, sulfonium borate compounds , a diazo-based compound, a biimidazole-based compound, and the like can be used as the photoinitiator.
  • the photoinitiator is benzophenone, o-benzoylbenzoate methyl, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2 -methyl Propiophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, 4-azidobenzalacetophenone , 2,6-bis(p-azidobenzylidene)cyclohexanone, 6-bis(
  • the photoinitiator may include 1 to 50 parts by weight based on 100 parts by weight of the binder resin. If the content of the photoinitiator is less than 1 part by weight, there is a fear that the cured density of the exposed portion may decrease, and the cured coating film may be affected in the developing process. In addition, if the content of the photoinitiator exceeds 50 parts by weight, it may be difficult to form a desired pattern due to excessive light absorption in the upper part of the dry coating film.
  • an azide-based photocrosslinker compound more specifically, a compound in which an azide group, which is a photocrosslinkable functional group, is substituted at both ends of a linear alkylene group having 4 to 20 carbon atoms.
  • the same compound can be crosslinked without a photoinitiator, thereby reducing the content of the photoinitiator.
  • Specific types thereof include 1,4-diadobutane, 1,5-diadopentane, 1,6-diadohexane, 1,7-diadoheptane, 1,8-diadooctane, and 1,10-diazidotane. decane, 1,12-diazododecane, or mixtures thereof.
  • the total weight of the binder resin and the monomer including the photosensitive resin described above may be included in an amount of 13 parts by weight or less, more preferably 10 parts by weight or less, more preferably 2 to 10 parts by weight based on 100 parts by weight of the conductive metal powder. . If the total weight of the binder resin and monomer exceeds 13 parts by weight, there is a risk that cracks may occur in the electrode pattern layer during sintering in step (5) or separation between the laminated green sheet layers may occur. In addition, when the total weight of the binder resin and the monomer is less than 2 parts by weight, there is a risk of sedimentation of the metal powder or ceramic powder in the photosensitive electrode composition or the dispersibility is impaired. There is a possibility that this peels off.
  • the specific types of binder resin, monomer, and photoinitiator including the above-described photosensitive resin and their contents are determined by the manufacturing method through electrospray, the use of the internal electrode of the laminated ceramic part, the thickness, line width, and width of the internal electrode to be implemented. It should be noted that it can be determined by comprehensively considering the distance, the material and particle size of the metal powder and ceramic powder.
  • the photosensitive electrode composition includes a solvent, and the solvent can be employed in the spray solution during electrospray and has no effect such as infringing on the ceramic green sheet, which is the surface to be electrosprayed, and the conductive metal powder and ceramic powder described above.
  • the solvent used in the known photosensitive electrode composition capable of dissolving the binder resin may be selected without limitation.
  • dihydroterpineol dihydroterpineol acetate, terpineol, octanol, n-paraffin, decanol, tridecanol, dibutylphthalate, butyl acetate, butylcarbitol, butylcarbitol acetate, di Propylene glycol methyl ether, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutylate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, butyl acetate, hexyl acetate, etc.
  • One or more organic solvents may be used, preferably a mixed solvent of dihydroterpineol and dihydroterpineol acetate or a mixed solvent of dihydroterpineol acetate and ethyl acetate.
  • the photosensitive electrode composition may further include additives such as a dispersant, a plasticizer, a leveling agent, a thixotropic agent, a slip agent, and a curing accelerator in addition to the above-described components, and the additive is limited in the case of additives contained in known electrode compositions. Since it can be used without it, the present invention is not specifically limited thereto.
  • additives such as a dispersant, a plasticizer, a leveling agent, a thixotropic agent, a slip agent, and a curing accelerator in addition to the above-described components, and the additive is limited in the case of additives contained in known electrode compositions. Since it can be used without it, the present invention is not specifically limited thereto.
  • the dispersing agent is included to provide dispersion stability of the metal powder and the ceramic powder, and is not particularly limited as long as it is a dispersant commonly used in the photosensitive electrode composition.
  • the dispersant is preferably oleic acid, polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, amine oxide and poly 12 - At least one selected from the group consisting of hydroxystearic acid may be used.
  • the additive including the dispersant may be included in an amount of 10 to 50 parts by weight based on 100 parts by weight of the photosensitive resin. If the additive is included in less than 10 parts by weight, it may be difficult to achieve a desired effect through the additive. In addition, when it exceeds 50 parts by weight, there is a fear that physical properties such as developability, printability, and conductivity of the photosensitive electrode composition may be deteriorated.
  • the photosensitive electrode composition containing the above-described components may have a viscosity of 50 to 150 cps, more preferably 70 to 100 cps at 25° C., and is suitable for electrospraying, and after electrospraying, an ultra-thin photosensitive electrode material layer And it is advantageous to implement a sintered internal electrode. If the viscosity is less than 50 cps, precipitation of the dispersed conductive metal powder and ceramic powder may occur rapidly, and there is a risk that the dispersibility may be deteriorated. In addition, if the viscosity exceeds 150cps, it may be difficult to precisely control the thickness through electrospray, and it may be difficult to manufacture a thin electrode. On the other hand, the viscosity here is the result of measurement with a Brookfield rotational viscometer LV based on ISO 554 under the conditions of a temperature of 25° C. and a relative humidity of 65% and 10 rpm.
  • the photosensitive electrode composition described above may be implemented by mixing the conductive metal powder, ceramic powder, binder resin and solvent, and then dispersing the conductive metal powder and ceramic powder. At this time, since a lot of heat is generated due to the fine powder during mixing and dispersing, it may be more advantageous to mix and disperse using a high-pressure dispersing device or a bead mill.
  • the electrospray (2) may be performed by injecting the photosensitive electrode composition as an injection solution into a known electrospray device.
  • the conditions at the time of electrospray may be performed by appropriately changing known electrospray conditions.
  • the stirring device may be a known stirring device such as an impeller, so the present invention is not particularly limited thereto.
  • step (3) as shown in (c) of FIG. 1 , the mask pattern layer 3 is disposed on the photosensitive electrode material layer 12a and then exposed to light.
  • the mask pattern layer 3 may have a pattern corresponding to the electrode pattern layer 12 to be implemented or a pattern inverse of the corresponding pattern. That is, when a positive type photoresist is used, a mask pattern layer corresponding to the pattern of the desired electrode pattern layer 12 can be used, and when a negative type photoresist is used, the pattern of the desired electrode pattern layer 12 is reversed. A mask pattern layer corresponding to may be used.
  • the exposure can use a known method for the photosensitive electrode composition, it can be carried out through irradiation of actinic ray or radiation, specifically, infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc. , an ultrahigh pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, an F2 excimer laser, an X-ray, an electron beam, etc. may be used as an example for this.
  • the type of light during exposure is UV
  • the exposure amount may be 100 mJ to 700 mJ, but is not limited thereto, and may be appropriately changed in consideration of the types of components contained in the photosensitive electrode composition, the thickness of the photosensitive electrode material layer, and the like.
  • step (4) as shown in (d) of FIG. 1, by treating the developer to remove the exposed or unexposed photosensitive electrode material layer portion to implement the electrode pattern layer 12 carry out
  • the developer may be used without limitation in the case of a known developer in the photolithography process, and an alkaline developer may be used, for example.
  • the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and piperidine; Alkaline aqueous solution, such as these can be used.
  • the alkali developer may be used.
  • the concentration of the alkali developer may be 0.1 to 5% by weight.
  • the developing time may be 20 to 100 seconds, but is not limited thereto, and may be changed in consideration of the specific type of the developer, the area to be removed, the thickness, and the like.
  • the portion removed through the developer varies depending on the type of the photosensitive electrode composition used.
  • the exposed portion is removed.
  • the unexposed portion may be removed, and in the case of FIG. 1(d), the electrode pattern layer 12 formed by removing the unexposed portion using the negative-type photosensitive electrode composition.
  • step (5) of the present invention a plurality of ceramic green sheets 10 , 20 , 30 provided with an electrode pattern layer 12 are stacked and then pressure sintered is performed.
  • the number of laminated ceramic green sheets 10 , 20 , and 30 may be determined in consideration of the type of multilayer ceramic electronic component to be implemented and the size of the electronic component.
  • the number of layers may be 100 or more, and more preferably, 150 or more, which may be advantageous for realizing a large-capacity MLCC.
  • the laminated ceramic green sheets 10, 20, and 30 are sintered while being pressurized.
  • the pressure can be appropriately adjusted in consideration of the thickness and the number of laminated ceramic green sheets, so the present invention is not particularly limited thereto.
  • the sintering condition may be appropriately adjusted in consideration of the thermal characteristics of the electrode pattern layer and the ceramic green sheet in the ceramic green sheets 10 , 20 , and 30 provided with the electrode pattern layer 12 .
  • the multilayer ceramic electronic component 100 implemented through the manufacturing method according to an embodiment of the present invention described above is disposed inside the ceramic body 110 and the body as shown in FIG. 1(f), and the electrode pattern layer It includes a plurality of internal electrodes having an average thickness of 0.7 ⁇ m or less, preferably 0.5 ⁇ m or less.
  • an external electrode (not shown) formed on the outer surface of the ceramic body 110 and electrically connected to the internal electrode may be further provided.
  • Some of the plurality of internal electrodes may be spaced apart from each other by a predetermined interval in the thickness direction when the stacking direction of the ceramic green sheet is based on the thickness direction of the ceramic body 110, and some of the internal electrodes have the thickness. It may be disposed to be spaced apart from each other at a predetermined distance in a plane direction perpendicular to the direction.
  • the ceramic green sheet in the limited volume of the ceramic body 110 has at least 100 layers, preferably 150 layers or more, in another example 200 layers or more, 300 layers or more, 400 layers or more, 500 layers or more, 600 layers or more. , 700 or more or 1000 or more layers may be laminated.
  • the average thickness of the internal electrodes is 0.7 ⁇ m or less, preferably 0.5 ⁇ m or less, and the minimum value of the vertical distance between adjacent internal electrodes spaced apart in the thickness direction of the ceramic body 110 is 2.0 ⁇ m or less. satisfied, and such a multilayer ceramic electronic component may be, for example, an MLCC.
  • a ceramic green sheet and a photosensitive electrode composition for electrospray were prepared, respectively.
  • the ceramic green sheet contains 10 parts by weight of a polyvinylbutylal binder resin in 100 parts by weight of a ceramic component, which is barium titanate, and a ceramic slurry having a viscosity of 300 cps prepared by mixing butyl carbitol acetate as a solvent.
  • a plurality of ceramic green sheets were prepared by drying after treatment so as to have a thickness of 5 ⁇ m manufactured using a conventional method.
  • nickel powder having an average particle diameter of 438 nm was specifically prepared through dry plasma. Afterwards, the prepared nickel powder was subjected to wet classification through centrifugal separation, with an average particle diameter of 75.0 nm, and particles having a particle diameter more than twice the average particle diameter were 9% of the total nickel powder, and particles having a particle diameter less than 0.5 times the average particle diameter were A conductive metal powder having a particle size distribution of 7% of the total nickel powder was prepared.
  • the average particle diameter is 21.8 nm through wet classification through centrifugation, and particles having a particle diameter twice or more of the average particle diameter
  • a ceramic powder having a particle size distribution in which 8.8% of the total ceramic powder and particles having a particle diameter of 0.5 times or less of the average particle diameter were 7.6% of the total ceramic powder was prepared.
  • dihydroterpineol and dihydroterpineol acetate are mixed in a mixed solvent in a weight ratio of 1:1, and the above-mentioned particle size is controlled nickel as conductive metal powder, ceramic powder, and photosensitive resin with a weight average molecular weight of about Polyvinyl butyral resin having a weight average molecular weight of about 70,000 and 75% by weight of an acrylate-based copolymer copolymerized with 10,000, 19.5 mol% of methacrylic acid, 38.5 mol% of methyl methacrylate and 42 mol% of isobornyl methacrylate A binder resin containing 25% by weight, 13 parts by weight of pentaerythritol tri-acrylate as a polyfunctional monomer, and azobisisobutyronitrile as a photoinitiator with respect to 100 parts by weight of the photosensitive resin were mixed, specifically Mix so that the total weight of the ceramic powder is 6.8 parts by weight, the binder
  • the viscosity of the prepared electrode composition for electrospray is the result of measurement with a Brookfield rotary viscometer LV according to ISO 554 under the conditions of a temperature of 25° C. and a relative humidity of 65% and a rotation speed of 10 rpm.
  • the photosensitive electrode composition for electrospray was applied on the prepared ceramic green sheet using an electrospray device under the condition of 18°C and 30% relative humidity. Under the conditions of 24 cm and applied voltage of 70 kV, electrospray was performed so that the thickness was within 1.0 ⁇ m when dried, dried at 65° C. for minutes, and then a dried photosensitive electrode material layer was implemented.
  • a mask pattern layer is placed on the photosensitive electrode material layer to have a predetermined electrode line pattern, and then exposed to UV at an intensity of 550 mJ, and development is performed for 30 seconds through a developer, which is a 3 wt% Na 2 CO 3 solution.
  • a pattern layer was implemented. After laminating 115 ceramic green sheets with electrode pattern layers, pressurized, heated in an atmospheric atmosphere, degreased, sintered at 1200 ° C. for 2 hours in a reducing atmosphere, and then reoxidized at 1100 ° C. in N 2 atmosphere for 2 hours. A multilayer ceramic part was manufactured.
  • the manufactured multilayer ceramic part had a good appearance without any external abnormalities such as deformation or cracking so that any part of the exterior was dented. No electrode damage such as short circuit of the inner electrode or electrode peeling such as a spaced gap between the inner electrode and the sintered body was observed. In addition, as a result of examining the thickness of single internal electrodes when observed under an optical microscope, the thickness was uniform.
  • the electrospray photosensitivity is as follows. The characteristics of the photosensitive electrode material layer and the sintered electrode pattern layer in a dried state realized by changing the composition of the electrode composition were examined.
  • the nickel powder which is a conductive metal powder
  • the nickel powder had an average particle diameter of 147.1 nm through wet classification through centrifugation, and a particle diameter that was more than twice the average particle diameter.
  • the average particle diameter is 65.8 nm, and particles having a particle diameter of more than twice the average particle diameter are 10% of the total ceramic powder, and particles having a particle diameter less than 0.5 times the average particle diameter are 9% of the total ceramic powder.
  • the preparation was carried out in the same manner as in Example 1, but the content, average particle diameter, particle size distribution, content of ceramic powder, average particle diameter, and/or the viscosity of the electrode composition of the prepared electrospray photosensitive electrode composition are shown in the table below.
  • a ceramic sheet provided with a sintered electrode pattern layer as shown in Table 1 or Table 2 was prepared by changing as shown in Table 1 or Table 2.
  • the ceramic powder used has a particle size distribution such that particles having a particle diameter of 2 times or more of the average particle diameter are within 10% of the total ceramic powder, and particles having a particle diameter of 0.5 times or less of the average particle diameter are within 10% of the total ceramic powder.
  • Ceramic powder whose particle size was controlled through wet classification was used.
  • the photosensitive electrode composition for electrospray used in Example 4 was the same as that used in Preparation Example 1.
  • the photosensitive electrode composition is electrosprayed and dried after the photosensitive electrode material layer (hereinafter also referred to as 'dry electrode') or after exposure, development and sintering
  • 'dry electrode' the photosensitive electrode material layer
  • 'sintered electrode' The following physical properties were measured for the electrode pattern layer (hereinafter also referred to as 'sintered electrode'), and the results are shown in Table 1 or Table 2 below.
  • the average thickness was measured using an alpha-step (Dektak 150, Bruker), which is a stylus-type surface step measuring instrument.
  • the average thickness of each of the 5 regions is measured.
  • the standard deviation was calculated to calculate the thickness uniformity according to Equation 1 below.
  • Thickness uniformity (%) [Standard deviation for the average thickness of 5 regions (nm) / Average value for the average thickness of 5 regions (nm)] ⁇ 100
  • the photosensitive electrode material layer was observed with an optical microscope, counting the number of parts where no electrode was formed, and measuring the area, and evaluated as 0 to 5 points according to the following criteria.
  • the number of parts where electrodes are not formed is 1 to 2 and the area of parts where electrodes are not formed is within 2% of the total area of the observed electrode: 4 points
  • the number of parts where electrodes are not formed is more than 2 and less than 5, and the non-electrode area is less than 5% of the total area of the observed electrode: 3 points
  • the number of non-electrode areas exceeds 20 and the non-electrode area exceeds 15% of the observed total area of the electrode: 0 points
  • the shrinkage ratio of the sintered electrode pattern layer was measured, and the shrinkage degree of the other examples was expressed as a relative percentage based on the shrinkage ratio value of Example 4 as 100.
  • the shrinkage ratio was calculated by measuring the average thickness of the electrode pattern layer before sintering and the average thickness of the electrode pattern layer after sintering, and the value calculated by Equation 2 below was used as the shrinkage ratio.
  • Shrinkage (%) (Average thickness of electrode pattern layer after sintering (nm)/Average thickness of electrode pattern layer before sintering (nm)) ⁇ 100
  • thickness uniformity is obtained by dividing the electrode surface into 5 non-overlapping areas for the electrode surface on which the thickness is measured, then measuring the average thickness for each of the 5 areas, and then measuring the average thickness of the 5 electrode areas and The standard deviation was calculated and the thickness uniformity was calculated according to Equation 1 above.
  • 'Ratio A' and 'Ratio B' are the ratio of particles having a particle diameter of at least twice the average particle diameter of the conductive metal powder and 0.5 times or less of the average particle diameter of the total number of conductive metal powders, respectively. It means the proportion of particles.
  • the 'ratio C' means a value obtained by dividing the average particle diameter of the ceramic powder by the average particle diameter of the conductive metal powder.
  • the content of the conductive metal powder is a content ratio based on the total weight of the electrode composition for electrospray, and the content of the ceramic powder is the content based on 100 parts by weight of the conductive metal powder.
  • Example 15 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 conductive metal powder type/ Content (wt%) 25 25 25 25 25 25 25 25 25 average particle diameter (nm) 160.3 147.1 142.2 98.0 75.0 75.0 75.0 Ratio A (%) 10 15 26 12 9 9 9 9 Ratio B (%) 8 18 23 9 7 7 7 7 Ceramic powder (type/content) Type/content (parts by weight) 6.8 6.8 6.8 6.8 6.8 6.8 6.8 average particle diameter (nm) 75 65.8 65.8 42.2 21.8 31.1 6.5 39.8 Ratio C 0.47 0.45 0.46 0.43 0.29 0.41 0.087 0.53 Viscosity (cps) 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80
  • Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 conductive metal powder type/ Content (wt%) 35 10 8 25 25 25 25 Average particle diameter (nm) 75.0 75.0 75.0 75.0 75.0 75.0 75.0 Ratio A (%) 9 9 9 9 9 9 9 9 9 9 Ratio B (%) 7 7 7 7 7 7 7 ceramic powder type/ Content (parts by weight) 4.2 6.8 6.8 9.7 11.5 4 2.5 Average particle diameter (nm) 21.8 21.8 21.8 21.8 21.8 21.8 21.8 21.8 Ratio C 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 Viscosity (cps) 94 72 71 84 85 79 79 Dry electrode average thickness (nm) 440 446 408 450 441 442 428 Dry electrode thickness uniformity (%) 16.9 10.3 25.1 9.4 9.8 9.5 19.2 in dry electrode Maximum thickness ( ⁇ m) within 1.0 within 1.0 within 1.0 within 1.0 within 1.0 within 1.0 within 1.0 within
  • Example 15 using the photosensitive electrode composition containing the conductive metal powder having an average particle diameter of more than 150 nm, the average thickness of the dry electrode satisfies within 1.0 ⁇ m, but the thickness uniformity is very poor at 30.15%. It can be seen that it is difficult to implement a thin internal electrode even if the thickness exceeds 1.0 ⁇ m and is sintered.
  • the maximum thickness of the dry electrode formed after electrospraying was 1.0 ⁇ m or less, but in Example In case of 2, particles with a particle size more than twice the average particle diameter amount to 26% of the conductive metal powder, resulting in a large number of coarse particles.
  • the continuous electrode surface formability is significantly lowered compared to Example 1.
  • the quality of the implemented electrode is deteriorated because the undercut is deepened because exposure to the lower side of the electrode is not performed properly.
  • Example 3 in the case of Examples 3 and 4 using the photosensitive electrode composition having the average particle diameter of the conductive metal powder to be 100 nm or less, the average thickness of the dry electrode realized when electrospraying under the same conditions was higher than in Example 1. It can be seen that the thickness uniformity of the dry electrode and the formability of the continuous electrode surface are increased while being implemented thin.
  • the proportion of particles that are more than twice the average particle diameter of the conductive metal powder is further reduced, so that the conductive metal powder sprayed during electric spraying.
  • the thickness uniformity of the dry electrode, the continuous electrode surface formation, and the shrinkage and thickness uniformity of the sintered electrode are improved. It can be seen that it is implemented very well.
  • Example 6 using a photosensitive electrode composition in which a ceramic powder having an average particle diameter of less than 0.1 times the average particle diameter of the conductive metal powder was mixed, the thickness uniformity of the dry electrode was lowered compared to that of Example 4, and the sintered electrode was It can be seen that the shrinkage characteristics and thickness uniformity are lowered.
  • Example 7 using the photosensitive electrode composition mixed with ceramic powder having an average particle diameter exceeding 0.5 times the average particle diameter of the conductive metal powder, it can be seen that the shrinkage characteristic of the sintered electrode was greatly reduced.
  • Example 8 using the photosensitive electrode composition in which the content of the conductive metal powder exceeds 30% by weight, the increased electrical conductivity of the photosensitive electrode composition affects the electrospray, and the continuous electrode surface formability is lowered compared to Example 4. , it can be seen that the thickness uniformity of the dry electrode is also lowered. In addition, it can be seen that the undercut is deepened because exposure of the lower side of the electrode is not performed properly.
  • Example 10 using the photosensitive electrode composition containing less than 10% by weight of the conductive metal powder, the continuous electrode surface formability and uniformity of dry thickness were lowered compared to Example 9.
  • Example 12 using the photosensitive electrode composition containing more than the preferred range with respect to the content of the ceramic powder, the shrinkage of the sintered electrode was significantly increased compared to that of Example 4, and the photosensitive electrode containing the ceramic powder below the preferred range It can be seen that the thickness uniformity of the dry electrode implemented in Example 14 using the composition was insignificant compared to that of Example 13.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Ceramic Capacitors (AREA)

Abstract

L'invention concerne un procédé de fabrication de composant électronique en céramique multicouche. Le procédé de fabrication de composant électronique en céramique multicouche selon un mode de réalisation de la présente invention : plus facilement et de manière fiable, une électrode interne peut être mise en œuvre sous la forme d'un film ultra-mince et d'un micromotif, qui est nécessaire pour une grande capacité ; permet à l'électrode interne fournie d'avoir une excellente uniformité d'épaisseur même lorsqu'elle est formée sous la forme d'un film ultra-mince ; et peut empêcher la déformation ou le délaminage interfacial d'un corps fritté en raison de la différence entre les propriétés de retrait de l'électrode interne et d'une feuille de céramique crue après frittage.
PCT/KR2022/005768 2021-04-22 2022-04-22 Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci WO2022225361A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2021-0052236 2021-04-22
KR20210052236 2021-04-22

Publications (1)

Publication Number Publication Date
WO2022225361A1 true WO2022225361A1 (fr) 2022-10-27

Family

ID=83723080

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/005768 WO2022225361A1 (fr) 2021-04-22 2022-04-22 Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci

Country Status (2)

Country Link
KR (1) KR102622934B1 (fr)
WO (1) WO2022225361A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060000784A (ko) * 2004-06-29 2006-01-06 전자부품연구원 감광성 도전체 페이스트의 조성물 및 그의 제조방법
KR101807641B1 (ko) * 2010-04-14 2017-12-11 도레이 카부시키가이샤 네거티브형 감광성 수지 조성물, 그것을 사용한 보호막 및 터치 패널 부재
KR20180102712A (ko) * 2017-03-07 2018-09-18 희성전자 주식회사 패턴 구조의 투명전극 제조 방법
KR20190111776A (ko) * 2018-03-23 2019-10-02 가부시키가이샤 노리타케 캄파니 리미티드 감광성 조성물, 복합체, 전자 부품, 및 전자 부품의 제조 방법
WO2020067363A1 (fr) * 2018-09-27 2020-04-02 住友金属鉱山株式会社 Pâte conductrice, composant électronique et condensateur à base de céramique multicouche

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100320928B1 (ko) 1999-07-14 2002-02-06 이형도 적층칩콘덴서의 제조방법
KR101538046B1 (ko) * 2013-02-15 2015-07-21 주식회사 아모텍 세라믹 소자 제조방법 및 세라믹 소자
KR101366023B1 (ko) * 2013-03-08 2014-02-24 주식회사 아모그린텍 전극의 제조방법
JP7176227B2 (ja) * 2017-05-23 2022-11-22 住友金属鉱山株式会社 導電性ペースト、電子部品及び積層セラミックコンデンサ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060000784A (ko) * 2004-06-29 2006-01-06 전자부품연구원 감광성 도전체 페이스트의 조성물 및 그의 제조방법
KR101807641B1 (ko) * 2010-04-14 2017-12-11 도레이 카부시키가이샤 네거티브형 감광성 수지 조성물, 그것을 사용한 보호막 및 터치 패널 부재
KR20180102712A (ko) * 2017-03-07 2018-09-18 희성전자 주식회사 패턴 구조의 투명전극 제조 방법
KR20190111776A (ko) * 2018-03-23 2019-10-02 가부시키가이샤 노리타케 캄파니 리미티드 감광성 조성물, 복합체, 전자 부품, 및 전자 부품의 제조 방법
WO2020067363A1 (fr) * 2018-09-27 2020-04-02 住友金属鉱山株式会社 Pâte conductrice, composant électronique et condensateur à base de céramique multicouche

Also Published As

Publication number Publication date
KR20220145787A (ko) 2022-10-31
KR102622934B1 (ko) 2024-01-09

Similar Documents

Publication Publication Date Title
US4613560A (en) Photosensitive ceramic coating composition
JP4769803B2 (ja) 光パターン化方法において使用するための水性の現像可能な光画像形成性前駆組成物
KR100887013B1 (ko) 양이온 중합성 광화상형성가능 후막 조성물, 전극, 및 이를형성하는 방법
JP2723975B2 (ja) 感光性セラミックコーテイング組成物
KR100803498B1 (ko) 흑색 전도성 조성물, 흑색 전극 및 그의 형성 방법
KR100768647B1 (ko) 감광성 후막 유전체 페이스트 조성물 및 이를 사용한절연층 제조 방법
JP3311735B2 (ja) ポリカーボネートポリマーを含む感光性セラミック組成物
WO2022225361A1 (fr) Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci
KR100803476B1 (ko) 기판 적용 ｌｔｃｃ 감광성 테이프에 유용한 전도체 조성물
WO2022216136A1 (fr) Composition d'électrode pour électropulvérisation
US7674403B2 (en) Composition, an electrode transfer film including the same, a display panel, and a method of forming an electrode
KR100874281B1 (ko) 유전체 및 유전체를 구비한 디스플레이 장치 및 유전체의제조 방법
EP1837914A2 (fr) Diélectrique, dispositif d'affichage avec ce diélectrique et méthode de fabrication du diélectrique
WO2022225360A1 (fr) Procédé de fabrication d'un composant électronique céramique multicouche et composant électronique céramique multicouche mis en œuvre à l'aide de celui-ci
JP4411940B2 (ja) 無機材料ペースト、およびプラズマディスプレイ部材ならびにプラズマディスプレイ
KR102611513B1 (ko) 전기분사용 감광성 전극조성물
WO2017135619A1 (fr) Joint organique enrobé d'argent, son procédé de préparation, et composition de pâte d'argent utilisant un joint organique enrobé d'argent pour cellule solaire
WO2016171323A1 (fr) Composition de pâte d'électrode pour composant à puce
WO2018147713A1 (fr) Résistance à couche épaisse sans plomb et composant électronique contenant celle-ci
WO2017183740A1 (fr) Composition de pâte d'électrode durcie par uv pour liaison interne, et procédé de production d'un composant de puce qui utilise la composition de pâte d'électrode
WO2019066468A1 (fr) Procédé de fabrication d'une bobine d'induction de puce ayant une largeur de ligne à pas fin et matériau photosensible utilisé à cet effet
WO2020184996A2 (fr) Précurseur de cuivre de frittage de lumière, son procédé de fabrication et son procédé de frittage de lumière
KR20220140441A (ko) 전기분사용 전극조성물
KR20090115251A (ko) Ｐｄｐ 전극용 도전성 페이스트 조성물 및 이의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22792059

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22792059

Country of ref document: EP

Kind code of ref document: A1