CN116113671A - Conductive paste for gravure printing, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste for gravure printing, electronic component, and multilayer ceramic capacitor Download PDFInfo
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- CN116113671A CN116113671A CN202180062800.4A CN202180062800A CN116113671A CN 116113671 A CN116113671 A CN 116113671A CN 202180062800 A CN202180062800 A CN 202180062800A CN 116113671 A CN116113671 A CN 116113671A
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- gravure printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Abstract
The invention provides a conductive paste for gravure printing, which can reduce the waviness of the surface of a dry film. The conductive paste for gravure printing comprises a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the organic solvent comprises a first organic solvent, and the first organic solvent is at least one selected from the group consisting of isobornyl acetate, methyl isobutyl ketone, and diisobutyl ketone.
Description
Technical Field
The invention relates to a conductive paste for gravure printing, an electronic component, and a multilayer ceramic capacitor.
Background
With miniaturization and higher performance of electronic devices such as mobile phones and digital devices, miniaturization and higher capacity are also demanded for electronic components including multilayer ceramic capacitors. The multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and by thinning the dielectric layers and the internal electrode layers, miniaturization and high capacity can be achieved.
The multilayer ceramic capacitor is manufactured, for example, as follows. First, barium titanate (BaTiO) 3 ) And printing conductive paste for internal electrodes on the surface of the ceramic green sheet of the dielectric powder and the binder resin in a predetermined electrode pattern, and drying to form a dried film. Next, the dried film and the ceramic green sheet were stacked alternately to obtain a laminate. Then, the laminate is integrated by thermocompression bonding to form a bonded body. The pressed body is cut, subjected to organic binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, external electrode paste is applied to both end portions of the fired chip, and after firing, nickel plating or the like is applied to the external electrode surface to obtain a multilayer ceramic capacitor.
As a printing method used for printing the conductive paste on the dielectric green sheet, a screen printing method has been generally used in the past, but in view of the demands for miniaturization, thinning, and improvement in productivity of electronic devices, it is demanded to print finer electrode patterns with higher productivity.
As one of printing methods of the conductive paste, a gravure printing method is proposed as a continuous printing method, in which a conductive paste is filled in a recess provided in a plate making process, and the conductive paste is transferred from the plate making process by pressing the recess against a surface to be printed. The gravure printing method is high in printing speed and excellent in productivity. When the gravure printing method is used, it is necessary to appropriately select a binder resin, a dispersant, a solvent, and the like in the conductive paste, and adjust the characteristics such as viscosity to a range suitable for gravure printing.
For example, patent document 1 describes a conductive paste for forming an internal conductor film by gravure printing, which is an internal conductor film in a laminated ceramic electronic component including a plurality of ceramic layers and an internal conductor film extending along a specific interface between the ceramic layers, the conductive paste including 30 to 70% by weight of a solid component containing a metal powder, 1 to 10% by weight of an ethylcellulose resin component having an ethoxy content of 49.6% or more, 0.05 to 5% by weight of a dispersant, and the balance of a solvent component, the conductive paste having a shear rate of 0.1 (s -1 ) Viscosity η at time 0.1 Is 1 Pa.s or more and has a shear rate of 0.02 (s -1 ) Viscosity η at time 0.02 Thixotropic fluids satisfying the conditions expressed by specific formulas.
Patent document 2 describes a conductive paste for forming an internal conductor film by gravure printing, which contains 30 to 70 wt% of a solid component containing a metal powder, 1 to 10 wt% of a resin component, 0.05 to 5 wt% of a dispersant, and the balance of a solvent component, and has a shear rate of 0.1(s) -1 ) Thixotropic fluids having a viscosity of 1 Pa.s or more at a shear rate of 0.1 (s -1 ) When the viscosity at the time was used as a reference, the shear rate was 10 (s -1 ) The viscosity change rate at the time of the preparation is 50% or more.
According to patent documents 1 and 2, the conductive paste has a shear rate of 0.1 (s -1 ) A thixotropic fluid having a viscosity of 1 Pa.s or more can provide stable continuous printability at high speed in gravure printing, and can produce a multilayer ceramic electronic component such as a multilayer ceramic capacitor with good production efficiency.
Patent document 3 describes a conductive paste for internal electrodes of multilayer ceramic capacitors, which contains a conductive powder (a), an organic resin (B) composed of polyvinyl butyral having a polymerization degree of 10000 or more and 50000 or less and ethylcellulose having a weight average molecular weight of 10000 or more and 100000 or less, an organic solvent (C) composed of any one of propylene glycol monobutyl ether, a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, and a mixed solvent of propylene glycol monobutyl ether and mineral spirits, an additive (D) composed of a separation inhibitor and a dispersant, and the additive (D) composed of a composition containing a polycarboxylic acid polymer or a polycarboxylate as the separation inhibitor. According to patent document 3, the conductive paste has a viscosity suitable for gravure printing, and can improve uniformity and stability of the paste and has good drying property.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2003-187638
Patent document 2: japanese patent laid-open publication No. 2003-242835
Patent document 3: japanese patent application laid-open No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
In the electroconductive paste for gravure printing, low viscosity is required. However, in the conductive paste with low viscosity, the waviness of the film surface tends to be large when forming a dry film, as compared with the conductive paste with high viscosity for screen printing or the like. When the internal electrode layer of the multilayer ceramic capacitor is formed using such conductive paste, variations in the thickness of the obtained internal electrode layer occur, and the reliability of the multilayer ceramic capacitor is lowered.
In view of the above, an object of the present invention is to provide a conductive paste for gravure printing, which has a low waviness on the surface of a dry film.
Means for solving the problems
In a first aspect of the present invention, there is provided a conductive paste for gravure printing, comprising a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the organic solvent contains at least one selected from the group consisting of isobornyl acetate, methyl isobutyl ketone, and diisobutyl ketone.
Further, the conductive paste preferably further contains 0.05 mass% or more and less than 3.0 mass% of a dicarboxylic acid relative to the entire conductive paste. Preferably, the conductive paste contains an organic solvent in an amount of 10 mass% or more and 60 mass% or less relative to the entire conductive paste. Further, the conductive paste preferably contains a dispersant in an amount of 0.01 to 3.0 mass% based on the entire conductive paste. In addition, the dispersant preferably includes an acid-based dispersant. In addition, preferably, the conductive powder contains at least one metal powder selected from the group consisting of Ni, pd, pt, au, ag, cu and an alloy thereof. Further, the conductive powder preferably has an average particle diameter of 0.05 μm or more and 1.0 μm or less. In addition, preferably, the ceramic powder contains barium titanate. Preferably, the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less. Preferably, the conductive paste contains 1 mass% or more and 20 mass% or less of ceramic powder relative to the entire conductive paste. In addition, the binder resin preferably contains a cellulose-based resin. In addition, the conductive paste preferably has a shear rate of 100sec -1 The viscosity at the time of the reaction is 3 Pa.S or less, and the shear rate at the time of the reaction is 10000sec -1 The viscosity at the time is 1 Pa.S or less. Further, it is preferable that the average height (Wc) of the waviness curve elements of the dry film obtained by gravure printing the conductive paste at a printing speed of 30m/min and a film thickness of 0.50 μm or more and 2 μm or less is 0.5 μm or less.
In a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.
In a third aspect of the present invention, there is provided a multilayer ceramic capacitor comprising a laminate of at least a dielectric layer and an internal electrode layer, the internal electrode layer being formed using the electroconductive paste for gravure printing.
Effects of the invention
The conductive paste of the present invention can reduce waviness of the surface of a dried film even when the dried film is formed by gravure printing. In addition, the internal electrode layer formed using the conductive paste of the present invention can produce a highly reliable multilayer ceramic capacitor with high productivity even when forming a thin-film electrode.
Drawings
Fig. 1 is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.
Detailed Description
[ conductive paste ]
The conductive paste of the present embodiment contains a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent. The components are described in detail below.
(conductive powder)
The conductive powder is not particularly limited, and a metal powder may be used, and for example, one or more kinds of powder selected from Ni, pd, pt, au, ag, cu and an alloy thereof may be used. Among them, from the viewpoints of conductivity, corrosion resistance, and cost, a powder of Ni or an alloy thereof (hereinafter, sometimes referred to as "Ni powder") is preferable. As the Ni alloy, for example, an alloy of Ni and at least one or more elements selected from the group consisting of Mn, cr, co, al, fe, cu, zn, ag, au, pt and Pd can be used. The Ni content in the Ni alloy is, for example, 50 mass% or more, and preferably 80 mass% or more. In addition, the Ni powder may contain about several hundred ppm of the element S in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin during the binder removal process.
The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. When the average particle diameter of the conductive powder is in the above range, the conductive powder can be suitably used as a paste for internal electrodes of a laminated ceramic capacitor (laminated ceramic component) having a thin film, for example, the smoothness of a dried film and the density of the dried film are improved. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is an average value (SEM average particle diameter) obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 10,000.
The content of the conductive powder is preferably 30 mass% or more and less than 70 mass%, more preferably 40 mass% or more and 60 mass% or less, relative to the entire conductive paste. When the content of the conductive powder is within the above range, the conductive property and dispersibility are excellent.
(ceramic powder)
The ceramic powder is not particularly limited, and for example, in the case of being a paste for an internal electrode of a multilayer ceramic capacitor, a known ceramic powder is appropriately selected according to the type of the multilayer ceramic capacitor to be used. As the ceramic powder, for example, a perovskite oxide containing Ba and Ti, preferably barium titanate (BaTiO 3 )。
As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent may be used. The oxide includes Mn, cr, si, ca, ba, mg, V, W, ta, nb and oxides of one or more rare earth elements. As the ceramic powder, for example, barium titanate (BaTiO 3 ) The Ba atoms and Ti atoms of the ceramic powder are replaced with other atoms such as Sn, pb, zr, etc.
When the ceramic powder is used as the electroconductive paste for the internal electrode, a powder having the same composition as that of the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor (electronic component) can be used. Thereby, it is possible to suppress the occurrence of shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering process Is formed by the cracking of the steel sheet. Examples of the ceramic powder include ZnO, ferrite, and PZT, baO, al in addition to the above 2 O 3 、Bi 2 O 3 R (rare earth element) 2 O 3 、TiO 2 、Nd 2 O 3 And the like. The ceramic powder may be used singly or in combination of two or more.
The average particle diameter of the ceramic powder is, for example, in the range of 0.01 μm to 0.5 μm, preferably 0.01 μm to 0.3 μm. When the average particle diameter of the ceramic powder is within the above range, a sufficiently thin and uniform internal electrode can be formed when the ceramic powder is used as a slurry for internal electrodes. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is an average value (SEM average particle diameter) obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 50,000 times.
The content of the ceramic powder is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, relative to the entire conductive paste. When the content of the ceramic powder is within the above range, dispersibility and sinterability are excellent.
The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the conductive powder.
(adhesive resin)
The binder resin is not particularly limited, and a known resin can be used. Examples of the binder resin include cellulose resins such as methyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, butyral resins such as acrylic resins, and polyvinyl butyral resins. Among them, from the viewpoints of solubility in a solvent, combustion degradability, and the like, the cellulose-based resin is preferably contained, and ethylcellulose is more preferably contained.
In addition, when the resin composition is used as a paste for internal electrodes, the resin composition may contain a butyral resin or a butyral resin may be used alone from the viewpoint of improving the adhesive strength with a green sheet. When the binder resin contains a butyral based resin, the viscosity suitable for gravure printing can be easily adjusted, and the adhesive strength with the green sheet can be further improved. The binder resin may contain, for example, 20 mass% or more of a butyral based resin, or 30 mass% or more of the binder resin as a whole.
When the binder resin contains a cellulose resin and a butyral resin, the binder resin may contain an acetal (acetate) resin in an amount of 20 mass% or more and 80 mass% or less, 30 mass% or more and 80 mass% or less, or 30 mass% or more and 60 mass% or less, based on the total content (100 mass%) of the cellulose resin and the butyral resin.
The polymerization degree and weight average molecular weight of the binder resin may be appropriately adjusted within the above-mentioned ranges according to the viscosity of the desired conductive paste.
For example, when a cellulose-based resin is included as a binder resin, the weight average molecular weight (Mw) may be 1 to 30 ten thousand, may be 3 to 20 ten thousand, or may be 5 to 15 ten thousand. When the Mw of the cellulose resin is in the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and the waviness of the surface of the dried film can be reduced.
The hydroxyl value of the cellulose resin is not particularly limited, but is preferably from 0.1 to 15mgKOH/g, more preferably from 0.5 to 7mgKOH/g, and even more preferably from 1.5 to 3 mgKOH/g. When the hydroxyl value of the cellulose resin is in the above range, the conductive powder and the ceramic powder are excellent in dispersibility, and therefore, the cellulose resin can be suitably used for a conductive paste for gravure printing. The hydroxyl value is a value measured in accordance with JIS K0070, and is a value indicating the mg number of potassium hydroxide corresponding to the hydroxyl group in 1g of the sample.
The ethoxy group content of the cellulose resin is not particularly limited, and may be, for example, 40 mass% or more and 55 mass% or less, 45 mass% or more and 52 mass% or less, or 48 mass% or more and 50 mass% or less.
For example, when a butyral based resin is included as a binder resin, the weight average molecular weight (Mw) may be 3 to 30 ten thousand, may be 5 to 20 ten thousand, or may be 10 to 15 ten thousand. When the Mw of the butyral based resin is in the above range, the viscosity of the conductive paste can be adjusted to a suitable range, and the waviness of the surface of the dried film can be reduced.
The content of the binder resin is preferably 0.5 mass% or more and 10 mass% or less, more preferably 1 mass% or more and 7 mass% or less, with respect to the entire conductive paste. When the content of the binder resin is in the above range, the electric conductivity and dispersibility are excellent.
The content of the binder resin is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 14 parts by mass or less, based on 100 parts by mass of the conductive powder.
(organic solvent)
The conductive paste according to the present embodiment contains at least one selected from the group consisting of isobornyl acetate (IBA), methyl isobutyl ketone (MIBK), and diisobutyl ketone (DIBK) (hereinafter, referred to as "first organic solvent") as an organic solvent, preferably contains one or both of isobornyl acetate and diisobutyl ketone, and more preferably contains isobornyl acetate. The conductive paste can reduce waviness of the film surface when forming a dry film by containing the above-mentioned organic solvent (hereinafter, also referred to as "first organic solvent"). The first organic solvent may be used singly or in combination. In addition, in the case where two or more kinds of the first organic solvents are contained, isobornyl acetate and diisobutyl ketone may be contained.
The content of the first organic solvent may be 3 mass% or more and 60 mass% or less, or may be 5 mass% or more and 40 mass% or less, or may be 10 mass% or more and 30 mass% or less, or may be 10 mass% or more and 20 mass% or less, relative to the total amount of the conductive paste. In addition, even if the content of the first organic solvent is 5 mass% or more and 10 mass% or less, the waviness of the dried film surface can be reduced.
In the case where the first organic solvent contains isobornyl acetate (IBA), the content of isobornyl acetate is preferably 4 mass% or more, more preferably 5 mass% or more, and even more preferably 8 mass% or more, relative to the total amount of the conductive paste. When the content of isobornyl acetate is within the above range, the waviness of the film surface at the time of forming the dried film can be further reduced. The content of isobornyl acetate may be 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less, based on the total amount of the conductive paste.
In the case where the first organic solvent contains diisobutyl ketone (DIBK), the content of diisobutyl ketone is preferably 4 mass% or more, more preferably 5 mass% or more, based on the total amount of the conductive paste. When the diisobutyl ketone content is within the above range, the waviness of the film surface at the time of forming a dry film can be further reduced, and further, the viscosity suitable for gravure printing can be easily adjusted. Further, when diisobutyl ketone (DIBK) is contained, the drying property is excellent, and the step of applying the electroconductive paste to the green sheet by gravure printing and drying (film forming step) can be made short. The diisobutyl ketone content may be 30 mass% or less, 20 mass% or less, 10 mass% or less, or 7 mass% or less, based on the total amount of the conductive paste.
The organic solvent may contain an organic solvent other than the first organic solvent. The organic solvent (other organic solvent) other than the first organic solvent is not particularly limited, and a known organic solvent capable of dissolving the binder resin may be used. Examples of the other organic solvents include glycol ether solvents, acetate solvents, ketone solvents, terpene solvents, and petroleum hydrocarbon solvents including aliphatic hydrocarbon solvents. It should be noted that one or two or more other organic solvents may be used.
Examples of the glycol ether solvents include (di) glycol ethers such as diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, diethylene glycol monomethyl ether, and the like, and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether (PNB), and the like.
Examples of the acetate-based solvent include glycol ether acetates such as isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxypropyl-2-acetate, ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate.
Examples of the ketone solvent include methyl ethyl ketone.
Examples of the terpene-based solvent include terpineol, dihydroterpineol (DHT), and dihydroterpineol acetate.
Examples of the petroleum hydrocarbon solvent including an aliphatic hydrocarbon solvent include solvents including tridecane, nonane, cyclohexane, and the like, mineral spirits (MA), and cycloalkane solvents. Of these, mineral spirits are preferably contained, and mineral spirits may be contained as a main component (the most abundant solvent among the petroleum hydrocarbon solvents). The mineral spirits may contain chain saturated hydrocarbons as a main component, or may contain 20 mass% or more of chain saturated hydrocarbons with respect to the entire mineral spirits.
The other organic solvent may include, for example, a terpene-based solvent and an aliphatic hydrocarbon solvent, or may include only a terpene-based solvent or only an aliphatic hydrocarbon solvent. In addition, in the case where the terpene-based solvent is included as the other organic solvent, the content of the terpene-based solvent may be 5 mass% or more and 40 mass% or less, or may be 10 mass% or more and 25 mass% or less, with respect to the total amount of the conductive paste. In the case where the aliphatic hydrocarbon solvent is contained, for example, the content of the aliphatic hydrocarbon solvent may be 5 mass% or more and 25 mass% or less, or may be 5 mass% or more and 15 mass% or less, based on the total amount of the conductive paste.
The content of the organic solvent (as a whole) is preferably 20 mass% or more and 60 mass% or less, more preferably 25 mass% or more and 45 mass% or less, with respect to the total amount of the conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
The content of the organic solvent is preferably 50 parts by mass or more and 130 parts by mass or less, more preferably 60 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the conductive powder. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(dispersant)
As the dispersant, a known dispersant can be used. As the dispersant, for example, an acid-based dispersant may be contained. Further, as the acid-based dispersant, a dispersant having a carboxyl group other than the dicarboxylic acid described later and the like may be included. In the present specification, as will be described later, dicarboxylic acid and dispersant are defined separately from each other, focusing on the separation suppressing effect of the conductive powder and ceramic powder that dicarboxylic acid has.
For example, in the case of using a comb-type carboxylic acid as the dispersant, the dispersibility of the conductive paste is improved by containing the comb-type carboxylic acid. One kind of dispersant may be used, or two or more kinds may be used. The conductive paste according to the present embodiment includes a dispersant, thereby improving dispersibility.
The dispersant may include, for example, an acid dispersant having a hydrocarbon group. Examples of such acid dispersants include acid dispersants such as higher fatty acids and polymeric surfactants, and phosphoric acid dispersants. These dispersants may be used singly or in combination of two or more.
The higher fatty acid may be an unsaturated carboxylic acid or a saturated carboxylic acid, and is not particularly limited, and examples thereof include higher fatty acids having 11 or more carbon atoms such as stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid. Among them, oleic acid or stearic acid is preferable.
The other acid-based dispersants are not particularly limited, and examples thereof include alkyl monoamine salt type represented by monoalkylamine salt.
The alkyl monoamine type is preferably, for example, oleoyl sarcosine which is a compound of glycine and oleic acid, or an amide compound using a higher fatty acid such as stearic acid or lauric acid instead of oleic acid.
The dispersant may contain a dispersant other than an acid-based dispersant. Examples of the dispersant other than the acid-based dispersant include alkali-based dispersants, nonionic dispersants, and amphoteric dispersants. These dispersants may be used singly or in combination of two or more.
Examples of the alkali-based dispersant include aliphatic amines such as laurylamine, abietylamine, spermine, myristylamine, and stearylamine. When the conductive paste contains the acid-based dispersant and the alkali-based dispersant, the dispersibility is more excellent and the viscosity stability over time is also excellent.
The dispersant is preferably contained in an amount of 3 mass% or less relative to the entire conductive paste. The upper limit of the content of the dispersant is preferably 2 mass% or less, more preferably 1 mass% or less. The lower limit of the content of the dispersant is not particularly limited, and is, for example, 0.01 mass% or more, preferably 0.05 mass% or more. When the content of the dispersant is within the above range, the dispersibility of the conductive paste can be improved, the paste viscosity can be adjusted to an appropriate range, deterioration of drying property after printing can be prevented, and further sheet erosion and peeling failure of the green sheet can be suppressed.
The dispersant is preferably contained in an amount of 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.4 to 3 parts by mass, per 100 parts by mass of the conductive powder. When the content of the dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the dried electrode surface after coating are more excellent, the viscosity of the conductive paste can be adjusted to an appropriate range, deterioration of the drying property after printing can be prevented, and further sheet erosion and peeling failure of the green sheet can be suppressed. The dispersant may also contain an acid-based dispersion and a base-based dispersant. When the acid-based dispersion and the alkali-based dispersion are contained as the dispersion agent, the content of the acid-based dispersion is preferably larger than the content of the alkali-based dispersion, and for example, the content of the alkali-based dispersion may be 0.1 times or more and less than 1 time, 0.3 times or more and 0.8 times or less relative to the content of the acid-based dispersion.
(dicarboxylic acid)
The conductive paste according to the present embodiment may contain a dicarboxylic acid as an additive. In the electroconductive paste for gravure printing, by containing the dicarboxylic acid in a specific amount, separation of the electroconductive powder and the ceramic powder can be suppressed, and occurrence of offset of the white separation layer containing the ceramic powder in the upper portion can be suppressed when the electroconductive paste is produced. In addition, when the internal electrode layer is formed using the conductive paste according to the present embodiment, a high coverage can be obtained.
Dicarboxylic acids are carboxylic acid-based additives having two carboxyl groups (COO-groups). Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2, 6-naphthalene dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and azelaic acid; dibasic acids produced by dimerization of unsaturated fatty acids having 12 to 28 carbon atoms such as dimer acids; alicyclic dicarboxylic acids such as hydrogenated dimer acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxyl hydrogenated bisphenol A, dicarboxyl hydrogenated bisphenol S, hydrogenated naphthalene dicarboxylic acid, and tricyclodecane dicarboxylic acid; and their derivatives, among which succinic acid derivatives are preferred.
The average molecular weight of the dicarboxylic acid is not particularly limited, and may be 1000 or less, 500 or less, or 400 or less, for example. When the average molecular weight of the dicarboxylic acid is within the above range, a high separation suppressing effect can be obtained. The average molecular weight of the dicarboxylic acid may be, for example, 100 or more, or 200 or more.
The conductive paste according to the present embodiment may contain 0.05 mass% or more and less than 3.0 mass% of dicarboxylic acid, and preferably 0.1 mass% or more and 1.0 mass% or less, relative to the entire conductive paste. The upper limit of the content of dicarboxylic acid may be 0.5 mass% or less. When the dicarboxylic acid content is 3.0 mass% or more, the drying becomes insufficient in the printing and drying steps, and the internal electrode layer may be in a soft state, resulting in a lamination shift in the subsequent lamination step, vaporization of the dicarboxylic acid remaining during firing, internal stress due to the vaporized gas component, or structural failure of the laminate.
When the conductive paste contains a dispersant (excluding dicarboxylic acid) and dicarboxylic acid, the total content of the dispersant and dicarboxylic acid may be 0.05 mass% or more and 3.0 mass% or less, 0.1 mass% or more and 2.0 mass% or less, or 0.1 mass% or more and 1.0 mass% or less, based on the entire conductive paste.
The conductive paste according to the present embodiment may not contain a dicarboxylic acid. Even when the conductive paste according to the present embodiment does not contain a dicarboxylic acid, the waviness of the surface of the dried film can be reduced by containing a specific organic solvent as described above.
(other additives)
The conductive paste of the present embodiment may contain other additives than the above components as necessary. As the other additives, conventionally known additives such as an antifoaming agent, a plasticizer, a surfactant, and a thickener can be used.
(conductive paste)
The method for producing the conductive paste according to the present embodiment is not particularly limited, and a conventionally known method can be used. For example, the above-described components may be stirred and kneaded by a three-roll mill, a ball mill, a mixer, or the like to produce a conductive paste. The dicarboxylic acid (separation inhibitor) is preferably weighed and added at the time of stirring and kneading by a mixer or the like as in the other materials, but the same separation inhibiting effect can be obtained even if the dicarboxylic acid (separation inhibitor) is added as a separation inhibitor to the material after the completion of stirring and kneading (dispersion).
The conductive paste had a shear rate of 100sec -1 The viscosity at the time is preferably 3 Pa.S or less. At a shear rate of 100sec -1 When the viscosity is within the above range, the conductive paste can be suitably used for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. Shear rate of 100sec -1 The lower limit of the viscosity is not particularly limited, and is, for example, 0.2pa·s or more.
In addition, the conductive paste had a shear rate of 10000sec -1 The viscosity at the time is preferably 1 Pa.S or less. At a shear rate of 10000sec -1 When the viscosity is within the above range, the conductive paste can be suitably used for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. Shear rate of 10000sec -1 The lower limit of the viscosity is not particularly limited, and is, for example, 0.05pa·s or more.
The conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors. The multilayer ceramic capacitor has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
As a dry film obtained by gravure printing a conductive paste at a printing speed of 30m/min and a film thickness of 0.50 μm or more and 2 μm or less, the average height (Wc) of the waviness curve element when the cutoff value (λc=0.08 mm) is applied is preferably less than 0.5 μm, more preferably 0.47 μm or less, still more preferably 0.45 μm or less, still more preferably 0.4 μm or less, and still more preferably 0.35 μm or less.
The average height (Wc) of the waviness curve elements may be determined in accordance with JIS B0601: 2013. The average height (Wc) of the waviness curve elements represents the average value of the heights (Zti) of the waviness curve elements (contour curve elements) at the reference length. The contour curve element is an element in which adjacent peaks and valleys are set as a group, and the height of the contour curve element corresponds to the height difference between the adjacent peaks and valleys. The peaks (valleys) constituting the profile elements have a minimum height and a minimum length, and the peaks (valleys) having a height (depth) of 10% or less of the maximum height or a length of 1% or less of the length of the calculation section are regarded as noise as part of the valleys (peaks) continuing in the front-rear direction.
[ electronic component ]
Hereinafter, embodiments of an electronic component and the like according to the present invention will be described with reference to the drawings. In the drawings, the drawings may be schematically represented or may be represented by changing the scale. The position, direction, and the like of the member will be described with reference to an XYZ orthogonal coordinate system shown in fig. 1 and the like, as appropriate. In the XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is vertical direction (vertical direction).
A in fig. 1 and B in fig. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 includes a ceramic laminate 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20.
Hereinafter, a method for manufacturing a multilayer ceramic capacitor using the above conductive paste will be described. First, a ceramic laminate 10 is produced by printing a conductive paste on a ceramic green sheet, drying the paste to form a dried film, laminating a plurality of ceramic green sheets having the dried film on the upper surface by pressure bonding to obtain a laminate, and firing the laminate to integrate the laminate, thereby alternately laminating the internal electrode layers 11 and the dielectric layers 12. Thereafter, a pair of external electrodes are formed at both end portions of the ceramic laminate 10 to produce the laminated ceramic capacitor 1. Hereinafter, the present invention will be described in more detail.
First, a ceramic green sheet is prepared as an unfired ceramic sheet. Examples of the ceramic green sheet include a ceramic green sheet formed by applying a slurry for a dielectric layer, which is obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a raw material powder of a predetermined ceramic such as barium titanate, onto a support film such as a PET film, and drying the support film to remove the solvent. The thickness of the dielectric layer formed of the ceramic green sheet is not particularly limited, but is preferably 0.05 μm to 3 μm from the viewpoint of the demand for downsizing of the multilayer ceramic capacitor.
Next, a plurality of sheets are prepared, each of which is formed with a dry film on one surface of the ceramic green sheet by printing and applying the conductive paste on one surface of the ceramic green sheet by gravure printing and drying. From the viewpoint of the demand for thinner internal electrode layers 11, the thickness of the dried film formed from the conductive paste is preferably 1 μm or less after drying.
Then, the ceramic green sheet is peeled from the support film, laminated so that the ceramic green sheet and the dry film formed on one surface of the ceramic green sheet are alternately arranged, and then heated and pressed to obtain a laminate. The protective ceramic green sheet to which the conductive paste is not applied may be further disposed on both sides of the laminate.
Next, the laminate was cut into a predetermined size to form green chips, and then the green chips were subjected to binder removal treatment and fired in a reducing atmosphere to produce a laminate ceramic fired body (ceramic laminate 10). The atmosphere in the binder removal treatment is preferably the atmosphere or N 2 A gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature at the time of the binder removal treatment is preferably 0.5 hours or more and 24 hours or less. In addition, the firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used in the internal electrode layer, and the temperature at which the laminate is fired is, for example, 1000 ℃ or higher and 1350 ℃ Hereinafter, the holding time of the temperature at the time of firing is, for example, 0.5 to 8 hours.
The firing of the green chip completely removes the organic binder in the ceramic green sheet, and fires the raw material powder of the ceramic to form the ceramic dielectric layer 12. The internal electrode layers 11 are formed by removing the organic carrier in the dried film and sintering or melting and integrating nickel powder or alloy powder containing nickel as a main component, and a multilayer ceramic fired body is formed by alternately stacking a plurality of dielectric layers 12 and internal electrode layers 11. The laminate ceramic fired body after firing may be subjected to an annealing treatment from the viewpoints of introducing oxygen into the dielectric layer to improve reliability and suppressing reoxidation of the internal electrode.
Then, the laminated ceramic capacitor 1 is manufactured by providing the produced laminated ceramic fired body with a pair of external electrodes 20. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. As a material of the external electrode 20, copper, nickel, or an alloy thereof, for example, may be preferably used. The electronic component may be an electronic component other than a multilayer ceramic capacitor.
Examples
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the examples.
[ evaluation method ]
(viscosity of conductive paste)
The viscosity of the conductive paste after production was measured using a rheometer (rheometer MCR302, manufactured by Anton Paar Japan, inc.). The viscosity was measured using a conical plate having a cone angle of 1℃and a diameter of 25mm and a shear rate (shear rate) of 100sec -1 10000sec -1 The value in the case of measurement under the condition of (3).
(evaluation of dried film)
Guiding by a small gravure press (GP-10 TYPEII, manufactured by Kugaku Kagaku Co., ltd.)The electrical paste had a printing speed of 30m/min and a conductive powder (Ni powder) of 0.7mg/cm 2 After printing on a dielectric sheet, the coated film was dried in a box dryer at 80℃for 4 minutes, and taken out to obtain a dried film (width: 2.5 mm. Times.length: 5 mm) for evaluation. The film thickness of the dried film is 0.50 μm to 2 μm.
The waviness of the surface of the dried film was evaluated by using a laser microscope (VK-100, measurement objective x 20, measurement length: 2000 μm) and the average height (Wc) of waviness curve elements when a cutoff value (λc=0.08 mm) was applied. The average height (Wc) of the waviness curve elements was an average value obtained by evaluating a plurality of times.
[ use of materials ]
(conductive powder)
As the conductive powder, ni powder (SEM average particle diameter of 0.2 μm) was used.
(ceramic powder)
As the ceramic powder, barium titanate (BaTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the SEM average particle size was 0.10. Mu.m).
(adhesive resin)
As the binder resin, polyvinyl butyral resin and ethylcellulose were used.
(additive)
As an additive, a dicarboxylic acid is used.
(dispersant)
As the dispersant, an acid-based dispersant and a base-based dispersant are used. Further, as the acid-based dispersant, comb-type carboxylic acid and phosphoric acid-based dispersants are used, and as the alkali-based dispersant, oleylamine is used.
(organic solvent)
As the organic solvent, isobornyl acetate (IBA), methyl isobutyl ketone (MIBK), and diisobutyl ketone (DIBK), dihydroterpineol (DHT), propylene glycol monobutyl ether (PNB), diethylene glycol monobutyl ether acetate (BCA), propylene glycol monomethyl ether acetate (PMA), diethylene glycol monomethyl ether (DEGME), and mineral spirits (MA) were used.
Example 1
50 mass% of conductive powder, 12.5 mass% of ceramic powder, 0.5 mass% of dispersant (0.3 mass% of acid dispersant, 0.2 mass% of alkali dispersant), 0.2 mass% of dicarboxylic acid, 2.5 mass% of binder resin (polyvinyl butyral resin: ethylcellulose=1:2 (mass ratio)), 4.1 mass% of IBA as an organic solvent, 12.0 mass% of MA, and the balance DHT were added, and these materials were mixed to prepare a conductive paste so that the total amount is 100 mass%. Table 1 shows the evaluation results Wc of the average height of the waviness and the content of the additive and the like of the conductive paste.
Examples 2 to 18
In examples 2 to 18, conductive pastes were prepared and evaluated in the same manner as in example 1 except that the presence or absence of the addition of the additive, the type of the organic solvent, and the content ratio were changed as shown in table 1. Table 1 shows the evaluation results Wc of the average height of the waviness and the content of the additive and the like of the conductive paste.
Comparative examples 1 to 4
A conductive paste was prepared and evaluated in the same manner as in example 1, except that MA13.7 mass% and PNB (comparative example 1) as the remainder, MA13.7 mass% and DHT (comparative example 2) as the remainder, MA12 mass%, PMA5.9 mass% and DHT (comparative example 3) as the remainder, MA12 mass%, DEGME5.9 mass% and DHT (comparative example 4) as the remainder were used as the organic solvents. Table 1 shows the evaluation results Wc of the average height of the waviness and the content of the additive and the like of the conductive paste.
(evaluation results)
The conductive pastes of examples 1 to 18 were smaller in average height (Wc) of the waviness profile elements in the dried film than the conductive pastes of comparative examples 1 to 4 in which the first organic solvent (IBA, MIBK, DIBK) was not used.
In addition, atThe shear rate of the conductive pastes of all examples and comparative examples shown in Table 1 was 100sec -1 The viscosity at the time of the reaction is 3 Pa.S or less, and the shear rate is 10000sec -1 The viscosity at the time of gravure printing was 1 Pa.S or less, and it was confirmed that the gravure printing was suitable.
Industrial applicability
When the electroconductive paste of the present invention is used for forming the internal electrode of a multilayer ceramic capacitor, a highly reliable multilayer ceramic capacitor can be obtained with high productivity. Therefore, the conductive paste of the present invention can be used particularly suitably as a raw material for internal electrodes of multilayer ceramic capacitors used as chip components of electronic devices such as mobile phones and digital devices which are increasingly miniaturized, and can be used suitably as a conductive paste for gravure printing.
The technical scope of the present invention is not limited to the embodiments described in the above embodiments and the like. One or more elements described in the above embodiments and the like may be omitted. The elements described in the above embodiments and the like may be appropriately combined. The disclosures of all documents cited in the above embodiments and the like are incorporated by reference as part of the description herein, as long as they are allowed by law.
One or more elements described in the above embodiments and the like may be omitted. The elements described in the above embodiments and the like may be appropriately combined. Further, the contents of all documents cited in Japanese patent application Nos. 2020-179986, 2021-093300 and the present specification are incorporated by reference as part of the description herein, as long as they are allowed by law.
Description of the reference numerals
1: a laminated ceramic capacitor;
10: a ceramic laminate;
11: an internal electrode layer;
12: a dielectric layer;
20: an external electrode;
21: an external electrode layer;
22: plating layers.
Claims (15)
1. A conductive paste for gravure printing, which comprises a conductive powder, a ceramic powder, a dispersant, a binder resin and an organic solvent, characterized in that,
the organic solvent contains at least one selected from the group consisting of isobornyl acetate, methyl isobutyl ketone, and diisobutyl ketone.
2. The electroconductive paste for gravure printing according to claim 1, further comprising a dicarboxylic acid in an amount of 0.05 mass% or more and less than 3.0 mass% relative to the entire electroconductive paste.
3. The electroconductive paste for gravure printing according to claim 1 or 2, wherein,
the conductive paste for gravure printing contains 10 to 60 mass% of the organic solvent relative to the entire conductive paste.
4. The electroconductive paste for gravure printing according to any one of claim 1 to 3, wherein,
the conductive paste for gravure printing contains 0.01 to 3.0 mass% of the dispersant relative to the entire conductive paste.
5. The electroconductive paste for gravure printing according to any one of claims 1 to 4, wherein the dispersant comprises an acid-based dispersant.
6. The electroconductive paste for gravure printing according to any one of claims 1 to 5, wherein,
the conductive powder includes at least one metal powder selected from the group consisting of Ni, pd, pt, au, ag, cu and alloys thereof.
7. The electroconductive paste for gravure printing according to any one of claims 1 to 4, wherein the electroconductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
8. The electroconductive paste for gravure printing according to any one of claims 1 to 7, wherein the ceramic powder contains barium titanate.
9. The electroconductive paste for gravure printing according to any one of claims 1 to 8, wherein the ceramic powder has an average particle diameter of 0.01 μm or more and 0.5 μm or less.
10. The electroconductive paste for gravure printing according to any one of claims 1 to 9, wherein the electroconductive paste for gravure printing contains the ceramic powder in an amount of 1 mass% to 20 mass% inclusive with respect to the entire electroconductive paste.
11. The electroconductive paste for gravure printing according to any one of claims 1 to 10, wherein the binder resin comprises a cellulose-based resin.
12. The electroconductive paste for gravure printing according to any one of claims 1 to 11, wherein the electroconductive paste for gravure printing has a shear rate of 100sec -1 The viscosity at the time of the reaction is 3 Pa.S or less, and the shear rate at the time of the reaction is 10000sec -1 The viscosity at the time is 1 Pa.S or less.
13. The electroconductive paste for gravure printing according to any one of claims 1 to 12, wherein an average height of waviness curve elements of a dry film obtained by gravure printing the electroconductive paste for gravure printing at a printing speed of 30m/min and a film thickness of 0.50 μm or more and 2 μm or less is 0.5 μm or less.
14. An electronic component formed using the electroconductive paste for gravure printing according to any one of claims 1 to 13.
15. A multilayer ceramic capacitor comprising at least a laminate of dielectric layers and internal electrode layers,
the internal electrode layer is formed using the electroconductive paste for gravure printing according to any one of claims 1 to 13.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020179986 | 2020-10-27 | ||
| JP2020-179986 | 2020-10-27 | ||
| JP2021-093300 | 2021-06-02 | ||
| JP2021093300A JP2022070803A (en) | 2020-10-27 | 2021-06-02 | Conductive paste for gravure printing, electronic component, and laminate ceramic capacitor |
| PCT/JP2021/039371 WO2022092045A1 (en) | 2020-10-27 | 2021-10-25 | Conductive paste for gravure printing, electronic component, and laminate ceramic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116113671A true CN116113671A (en) | 2023-05-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180062800.4A Pending CN116113671A (en) | 2020-10-27 | 2021-10-25 | Conductive paste for gravure printing, electronic component, and multilayer ceramic capacitor |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20230093418A (en) |
| CN (1) | CN116113671A (en) |
| TW (1) | TW202229471A (en) |
| WO (1) | WO2022092045A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220380A (en) * | 2004-02-03 | 2005-08-18 | Dowa Mining Co Ltd | Silver powder and manufacturing method therefor |
| CN1741212A (en) * | 2004-08-10 | 2006-03-01 | Tdk株式会社 | Release layer paste and method of production of multilayer type electronic device |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| WO2020067363A1 (en) * | 2018-09-27 | 2020-04-02 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN111201578A (en) * | 2017-10-10 | 2020-05-26 | 株式会社则武 | Conductive paste |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4389431B2 (en) | 2001-12-13 | 2009-12-24 | 株式会社村田製作所 | Conductive paste for gravure printing, method for producing the same, and multilayer ceramic electronic component |
| JP2003187638A (en) | 2001-12-20 | 2003-07-04 | Murata Mfg Co Ltd | Conductive paste for gravure printing and its manufacturing method as well as laminated ceramic electronic component |
| JP6546309B1 (en) * | 2018-03-19 | 2019-07-17 | 株式会社ノリタケカンパニーリミテド | Conductive paste with stable viscosity over time |
-
2021
- 2021-10-25 WO PCT/JP2021/039371 patent/WO2022092045A1/en active Application Filing
- 2021-10-25 CN CN202180062800.4A patent/CN116113671A/en active Pending
- 2021-10-25 KR KR1020237008617A patent/KR20230093418A/en unknown
- 2021-10-27 TW TW110139896A patent/TW202229471A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220380A (en) * | 2004-02-03 | 2005-08-18 | Dowa Mining Co Ltd | Silver powder and manufacturing method therefor |
| CN1741212A (en) * | 2004-08-10 | 2006-03-01 | Tdk株式会社 | Release layer paste and method of production of multilayer type electronic device |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| CN111201578A (en) * | 2017-10-10 | 2020-05-26 | 株式会社则武 | Conductive paste |
| WO2020067363A1 (en) * | 2018-09-27 | 2020-04-02 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022092045A1 (en) | 2022-05-05 |
| KR20230093418A (en) | 2023-06-27 |
| TW202229471A (en) | 2022-08-01 |
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