CN111373491A - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
- Publication number
- CN111373491A CN111373491A CN201880075253.1A CN201880075253A CN111373491A CN 111373491 A CN111373491 A CN 111373491A CN 201880075253 A CN201880075253 A CN 201880075253A CN 111373491 A CN111373491 A CN 111373491A
- Authority
- CN
- China
- Prior art keywords
- conductive paste
- mass
- acid
- dispersant
- conductive
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a conductive paste which has viscosity suitable for gravure printing and excellent dispersibility of the paste. Disclosed is a conductive paste which contains a conductive powder, a dispersant, a binder resin and an organic solvent, wherein the dispersant contains a first acid-based dispersant and a second acid-based dispersant, wherein the first acid-based dispersant is an alkyl phosphate compound, the second acid-based dispersant is an acid-based dispersant having a carboxyl group other than the first acid-based dispersant, the binder resin contains an acetal resin, and the organic solvent contains a glycol ether-based solvent.
Description
Technical Field
The invention relates to a conductive paste, an electronic component and a multilayer ceramic capacitor.
Background
With the miniaturization and high performance of electronic devices such as mobile phones and digital devices, miniaturization and high capacity are also demanded for electronic components including multilayer ceramic capacitors and the like. The multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately stacked, and can be reduced in size and increased in capacity by making the dielectric layers and the internal electrode layers thin.
For example, a laminated ceramic capacitor can be manufactured as follows. Firstly, barium titanate (BaTiO) is added3) The dielectric green sheet is formed by printing an internal electrode paste (conductive paste) containing a conductive powder, a binder resin, an organic solvent, and the like on the surface of the dielectric green sheet containing the dielectric powder and the binder resin in a predetermined electrode pattern, and drying the paste to form a dry film. Next, the dry film and the dielectric green sheet are stacked alternately in a multilayer, and then heated and pressure bonded to be integrated, thereby forming a pressure bonded body. The pressure-bonded body is cut, subjected to a binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, nickel plating or the like is applied to the surface of the external electrode, thereby obtaining a multilayer ceramic capacitor.
As a printing method used when printing the conductive paste on the dielectric green sheet, a screen printing method has been generally used, but from the demands for downsizing, thinning, and improvement in productivity of electronic devices, printing of a finer electrode pattern with high productivity is required.
As one of the printing methods of the conductive paste, a gravure printing method has been proposed as a continuous printing method in which a concave portion provided in a plate is filled with the conductive paste, the plate is pressed against a surface to be printed, and the conductive paste is transferred from the plate. The gravure printing method has a high printing speed and excellent 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 properties 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, the internal conductor film being an internal conductor film in a multilayer 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 wt% of a solid component containing a metal powder, 1 to 10 wt% of an ethyl cellulose resin component having an ethoxy content of 49.6% or more, 0.05 to 5 wt% of a dispersant, and the balance being a solvent component, the conductive paste having a shear rate of 0.1 (s/s)-1) Viscosity of η0.11 pas or more and a shear rate of 0.02(s)-1) Viscosity of η0.02A thixotropic fluid that satisfies the conditions expressed by a specific formula.
Patent document 2 describes a conductive paste for forming an internal conductor film by gravure printing, which is similar to the conductive paste described in patent document 1, and 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 being a solvent component, and has a shear rate of 0.1(s)-1) A thixotropic fluid having a viscosity of 1Pa s or more at a shear rate of 0.1(s)-1) The shear rate was 10(s) based on the viscosity-1) The viscosity change rate is 50% or more.
According to the above patent documents 1 and 2, the shear rate of the conductive paste is 0.1(s)-1) A thixotropic fluid having a viscosity of 1 pas or more, and 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 an internal electrode of a multilayer ceramic capacitor, which contains a conductive powder (a), an organic resin (B), an organic solvent (C), an additive (D), and a dielectric powder (E), wherein the organic resin (B) is composed of polyvinyl butyral having a polymerization degree of 10000 or more and 50000 or less and ethyl cellulose having a weight average molecular weight of 10000 or more and 100000 or less, the organic solvent (C) is composed of propylene glycol monobutyl ether, or a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, or a mixed solvent of propylene glycol monobutyl ether and mineral spirits, the additive (D) is composed of a separation inhibitor and a dispersant, and the separation inhibitor is composed of a composition containing a polycarboxylic acid polymer or a polycarboxylate. According to patent document 3, the conductive paste has a viscosity suitable for gravure printing, and can improve the uniformity and stability of the paste, and has good drying properties.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-187638
Patent document 2: japanese patent laid-open publication No. 2003 and No. 242835
Patent document 3: japanese laid-open patent publication No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
With the recent reduction in the thickness of the internal electrode layer, the conductive powder tends to have a smaller particle size. When the particle diameter of the conductive powder is small, the specific surface area of the particle surface thereof becomes large, and therefore the surface activity of the conductive powder (metal powder) becomes high, and the dispersibility of the conductive paste may decrease, and a conductive paste having a higher dispersibility is required.
In addition, when printing the conductive paste by the gravure printing method, since a paste viscosity lower than that of the screen printing method is required, it is considered that the conductive powder having a large specific gravity is precipitated to lower the dispersibility of the paste. In the conductive pastes described in patent documents 1 and 2, the dispersibility of the paste is improved by removing the lumps in the conductive paste using a filter, but the process of removing the lumps is required, and the production process is therefore easily complicated.
In view of such circumstances, an object of the present invention is to provide a conductive paste having a paste viscosity suitable for gravure printing and excellent in dispersibility and productivity of the paste.
Means for solving the problems
A first aspect of the present invention provides a conductive paste containing a conductive powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant contains a first acid-based dispersant and a second acid-based dispersant, the first acid-based dispersant is an alkyl phosphate compound, the second acid-based dispersant is an acid-based dispersant having a carboxyl group other than the first acid-based dispersant, the binder resin contains an acetal resin, and the organic solvent contains a glycol ether-based solvent.
The first acid-based dispersant is preferably an alkylpolyoxyalkylene phosphate compound.
Preferably, the second acid-based dispersant has a molecular weight of 5000 or less and contains an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. The dispersant preferably further contains an alkali-based dispersant.
The first acid-based dispersant is preferably contained in an amount of 0.2 to 1 part by mass based on 100 parts by mass of the conductive powder, and the second acid-based dispersant is preferably contained in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the conductive powder. The dispersant may further contain an alkali-based dispersant. The alkali-based dispersant is preferably contained in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the conductive powder.
The conductive powder preferably contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. In addition, the conductive paste preferably contains a ceramic powder. The ceramic powder preferably contains a perovskite oxide. The average particle diameter of the ceramic powder is preferably 0.01 μm or more and 0.5 μm or less. The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less. The conductive paste is preferably used for internal electrodes of the multilayer ceramic component. In addition, it is preferable that the conductive paste has a shear rate of 100sec-1Viscosity at shear rate of 0.8Pa · S or lessThe rate is 10000sec-1The viscosity is 0.19Pa · S or less.
A second aspect of the present invention provides an electronic component formed using the conductive paste.
A third aspect of the present invention provides a multilayer ceramic capacitor including at least a multilayer body in which dielectric layers and internal electrodes are laminated, wherein the internal electrodes are formed using the conductive paste.
Effects of the invention
The conductive paste of the present invention has a viscosity suitable for gravure printing, and is excellent in dispersibility and productivity of the paste. In addition, the electrode pattern of an electronic device such as a multilayer ceramic capacitor formed using the conductive paste of the present invention is excellent in printability of the conductive paste and has a uniform thickness when forming a thin electrode.
Drawings
Fig. 1 is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.
Description of the reference numerals
1 laminated ceramic capacitor
10 ceramic laminate
11 internal electrode layers
12 dielectric layer
20 external electrode
21 external electrode layer
22 plating layer
Detailed Description
[ conductive paste ]
The conductive paste of the present embodiment contains a conductive powder, a dispersant, a binder resin, and an organic solvent. Hereinafter, each component will be described in detail.
(conductive powder)
The conductive powder is not particularly limited, and for example, one or more kinds of powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among them, Ni or an alloy thereof is preferably used as the powder in terms of conductivity, corrosion resistance, and cost. As the Ni alloy, for example, an alloy of Ni and at least one element 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, preferably 80 mass% or more. In addition, in order to suppress the generation of a violent gas due to the thermal decomposition of the binder resin portion during the binder removal treatment, the Ni powder may contain S in the order of several hundred ppm.
The average particle diameter of the conductive powder is preferably 0.05 μm to 1.0 μm, more preferably 0.1 μm to 0.5. mu.m. When the average particle diameter of the conductive powder is within the above range, the conductive powder can be suitably used as a slurry for internal electrodes of a laminated ceramic capacitor to be made thin, and for example, the smoothness and density of a dried film can be improved. In the present specification, unless otherwise specified, the average particle diameter of the conductive powder refers to a particle diameter calculated from a specific surface area obtained by a BET method. For example, the calculation formula of the average particle diameter of the nickel powder is shown below.
Average particle size 6/s.a × ρ … (formula)
(ρ ═ 8.9 (true density of nickel), s.a ═ BET specific surface area of nickel powder)
The content of the conductive powder is preferably 30 mass% to 70 mass%, more preferably 40 mass% to 65 mass% of the entire conductive paste. When the content of the conductive powder is within the above range, the conductivity and dispersibility are excellent.
(ceramic powder)
The conductive paste may contain a ceramic powder. The ceramic powder is not particularly limited, and for example, in the case of a slurry for internal electrodes of a multilayer ceramic capacitor, a known ceramic powder can be appropriately selected depending on the type of multilayer ceramic capacitor to be used. The ceramic powder includes, for example, a perovskite-type oxide containing Ba and Ti, preferably barium titanate (BaTiO)3). One kind of the ceramic powder may be used, or two or more kinds may be used.
As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. Examples of the oxide include at least one oxide selected from the group consisting of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and rare earth elements.
Further, as the ceramic powder, for example, barium titanate (BaTiO) can be cited3) The ceramic powder of a perovskite oxide ferroelectric material in which Ba atoms and Ti atoms are substituted with other atoms such as Sn, Pb, and Zr.
As the ceramic powder in the internal electrode slurry, a powder having the same composition as that of the dielectric ceramic powder constituting the dielectric green sheets of the multilayer ceramic capacitor can be used. This can suppress the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the firing step. Examples of such ceramic powders include, in addition to the perovskite-type oxides containing Ba and Ti, ZnO, ferrite, PZT, BaO, and Al2O3、Bi2O3R (rare earth element)2O3、TiO2、Nd2O3And the like.
The average particle size of the ceramic powder is, for example, 0.01 to 0.5. mu.m, preferably 0.01 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 size of the ceramic powder is a particle size calculated from a specific surface area obtained by a BET method in the same manner as the conductive powder.
The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, and 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.
The content of the ceramic powder is preferably 1 mass% to 20 mass%, more preferably 3 mass% to 20 mass%, with respect to the entire conductive paste.
(Binder resin)
The binder resin contains an acetal resin. As the acetal resin, a butyral resin such as polyvinyl butyral is preferable. When the binder resin contains an acetal resin, the viscosity can be adjusted to a viscosity suitable for gravure printing, and the adhesion strength with the green sheet can be further improved. The binder resin may contain, for example, 20 mass% or more of an acetal resin, 30 mass% or more, 60 mass% or more of the acetal resin, or only the acetal resin, based on the whole binder resin.
The content of the acetal resin is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the conductive powder.
In addition, the binder resin may contain other resins than the acetal resin. The other resin is not particularly limited, and a known resin can be used. Examples of the other resin include cellulose resins such as methyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, and acrylic resins, and among them, ethyl cellulose is preferable from the viewpoint of solubility in a solvent, and combustion decomposition properties. The molecular weight of the binder resin is, for example, about 20000 to 200000.
The content of the binder resin is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the conductive powder.
The content of the binder resin is preferably 0.5 mass% to 10 mass%, more preferably 0.5 mass% to 6 mass%, with respect to the entire conductive paste. When the content of the binder resin is within the above range, the electrical conductivity and dispersibility are excellent.
(organic solvent)
The organic solvent contains at least one of a glycol ether solvent and an acetate solvent, and preferably contains a glycol ether solvent.
Examples of the glycol ether solvent include (di) glycol ethers such as diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, and ethylene glycol monohexyl ether, 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). Among them, propylene glycol monoalkyl ethers are preferable, and propylene glycol monobutyl ether is more preferable. When the organic solvent contains a glycol ether solvent, the binder resin has excellent compatibility with the binder resin and excellent drying properties.
The organic solvent may contain, for example, 25 mass% or more of the glycol ether solvent based on the whole organic solvent, 50 mass% or more of the organic solvent, or only the glycol ether solvent. The glycol ether solvent may be used alone or in combination of two or more.
Examples of the acetate-based solvent include glycol ether acetates such as dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxypropyl-2-acetate.
When the organic solvent contains an acetate-based solvent, for example, the acetate-based solvent (a) may contain at least one selected from the group consisting of dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. Among them, isobornyl acetate is more preferable. The acetate-based solvent is preferably contained in an amount of 90 to 100 mass%, more preferably 100 mass%, based on the entire organic solvent excluding the glycol ether-based solvent.
In addition, when the organic solvent contains an acetate-based solvent, for example, the acetate-based solvent (a) and at least one acetate-based solvent (B) selected from ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate may be contained. When such a mixed solvent is used, the viscosity of the conductive paste can be easily adjusted, and the drying rate of the conductive paste can be increased.
In the case of a mixed solution containing the acetate-based solvent (a) and the acetate-based solvent (B), the acetate-based solvent (a) is preferably contained in an amount of 50 to 90 mass%, more preferably 60 to 80 mass%, based on the entire acetate-based solvent. In the case of the mixed solution, the acetate-based solvent (B) is contained in an amount of 10 mass% to 50 mass%, more preferably 20 mass% to 40 mass%, based on 100 mass% of the entire acetate-based solvent.
The organic solvent may contain other organic solvents besides the glycol ether solvent and the acetate solvent. The other organic solvent is not particularly limited, and a known organic solvent capable of dissolving the binder resin can be used. Examples of the other organic solvent include acetate solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, terpene solvents such as terpineol and dihydroterpineol, and aliphatic hydrocarbon solvents such as tridecane, nonane, and cyclohexane. Among them, an aliphatic hydrocarbon solvent is preferable, and mineral spirits are more preferable among aliphatic hydrocarbon solvents. One or two or more of the other organic solvents may be used.
The organic solvent may contain, for example, a glycol ether solvent as a main solvent and an aliphatic hydrocarbon solvent as a sub-solvent. In this case, the glycol ether solvent is preferably contained in an amount of 30 parts by mass or more and 50 parts by mass or less, more preferably 40 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the conductive powder, and the aliphatic hydrocarbon solvent is contained in an amount of, for example, 15 parts by mass or more and 80 parts by mass or less, preferably 20 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the conductive powder.
The content of the organic solvent is preferably 50 parts by mass or more and 130 parts by mass or less, and 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.
The content of the organic solvent is preferably 20 mass% to 50 mass%, more preferably 25 mass% to 45 mass%, based on the entire conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(dispersing agent)
The conductive paste of the present embodiment preferably contains an acid-based dispersant containing phosphorus as the acid-based dispersant, and particularly preferably contains a first acid-based dispersant composed of an alkyl phosphate compound. The inventors of the present invention have studied various dispersants for the dispersant used in the conductive paste, and as a result, although the reason for this is not clear, they have found that the inclusion of the first acid-based dispersant together with the binder resin and the organic solvent can greatly suppress the generation of lumps at the time of forming the internal electrode, and improve the dispersibility of the paste.
The first acid-based dispersant is a phosphate having an alkyl group. The alkyl phosphate compound preferably has a polyoxyalkylene structure, and an alkylpolyoxyalkylene phosphate compound is preferred.
The first acid-based dispersant may be a dispersant having a linear structure, or may be an acid-based dispersant having a complicated branched structure (for example, two or more branched chains), and is preferably a linear structure.
The first acid-based dispersant preferably contains a compound represented by the following general formula (1), for example.
[ CHEM 1]
In the general formula (1), X represents a linear alkyl group having 1 to 18 carbon atoms, and Y represents- (OCH)2CH2) n-is 1 to 18.
Although details thereof are not clear, it is presumed that by using an alkyl phosphate compound as the first acid-based dispersant, the phosphoric acid site is adsorbed on the surface of the conductive powder or the like to neutralize the surface potential or inactivate the hydrogen bond site, and the specific steric structure in which the site other than the phosphoric acid site contains an alkyl group can effectively suppress aggregation of the conductive powder or the like to further improve the stability of the slurry viscosity. The first acid-based dispersant is preferably a single dispersant, not a mixture with other phosphoric acid-based dispersants.
The conductive paste of the present embodiment may contain a phosphorus-containing acid-based dispersant (phosphoric acid-based dispersant) other than the first acid-based dispersant, but the phosphorus-containing acid-based dispersant in the conductive paste preferably contains only an alkyl phosphate compound, and more preferably contains only an alkylpolyoxyalkylene phosphate compound. The first acid-based dispersant may be a mixture, but is preferably a single compound.
The first acid-based dispersant may be contained, for example, in an amount of 0.2 to 2 parts by mass, or in an amount of 0.2 to 1 part by mass, and preferably in an amount of 0.2 to less than 1 part by mass, based on 100 parts by mass of the conductive powder. When the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder in the conductive paste is excellent.
The first acid-based dispersant is contained in an amount of, for example, 3 mass% or less based on the entire conductive paste. The upper limit of the content of the acid-based dispersant is preferably 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1% by mass or less. The lower limit of the content of the acid-based dispersant is not particularly limited, and is, for example, 0.1 mass% or more.
The first acid-based dispersant can be used by selecting a product satisfying the above-mentioned characteristics from commercially available products, for example. The dispersant may be produced by a conventionally known production method so as to satisfy the above characteristics.
The conductive paste contains a second acid-based dispersant in addition to the first acid-based dispersant. The second acid-based dispersant is an acid-based dispersant having a carboxyl group, and preferably an acid-based dispersant other than the phosphoric acid-based dispersant. Although details thereof are not clear, the conductive paste of the present embodiment is excellent in dispersibility and viscosity stability of the paste by using the second acid-based dispersant in combination with the first acid-based dispersant.
The molecular weight of the second acid-based dispersant is preferably 5000 or less, more preferably 1000 or less, and still more preferably 500 or less. The second acid-based dispersant is, for example, an acid-based dispersant having a hydrocarbon group. The hydrocarbon group preferably contains an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. The second acid-based dispersant has a carboxyl group. When the second acid-based dispersant has the above-described structure as in the first acid-based dispersant, the dispersibility of the slurry can be further improved while maintaining the effect of the addition of the first acid-based dispersant.
Examples of the second acid-based dispersant include acid-based dispersants such as higher fatty acids and amino acids. Further, the second dispersant may be used singly or in combination.
The higher fatty acid may be an unsaturated carboxylic acid or a saturated carboxylic acid, and examples thereof include, but are not particularly limited to, higher fatty acids having 11 or more carbon atoms such as stearic acid, oleic acid, behenic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid. Among them, oleic acid or stearic acid is preferable.
The second acid-based dispersant other than the higher fatty acid is not particularly limited, and may be a surfactant selected from the following surfactants: the preferred examples of the antioxidant include those of the monoamine type represented by monoalkylamine salts, those of the diaminoalkyl type represented by N-alkyl (C14-C18) propylenediamine dioleate, those of the trimethylalkyl ammonium represented by alkyltrimethylammonium chloride, those of the dimethylbenzyl alkyl ammonium represented by palmityldimethylbenzylammonium chloride, those of the quaternary ammonium represented by alkyl/polyoxyethylenemethylammonium chloride, those of the alkylpyridinium, those of the tertiary amine represented by dimethylstearylamine, those of the polyoxyethylenealkylamine represented by polyoxypropylene/polyoxyethylenealkylamine, and those of the diamine represented by N, N ', N' -tris (2-hydroxyethyl) -N-alkyl (C14-18) 1, 3-diaminopropane, and among these, the monoamine type is preferably the alkylmonoamine salt.
The alkyl monoamine salt type is preferably oleoylsarcosine, lauroylsarcosine, or stearic acid amide.
The second acid-based dispersant is contained, for example, in an amount of 0.01 to 2 parts by mass, preferably 0.01 to 1 part by mass, more preferably 0.01 to less than 1 part by mass, and further preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the conductive powder. When the second acid-based dispersant is contained in the above range together with the first acid-based dispersant, the dispersibility of the conductive powder in the conductive paste is particularly excellent.
The second acid-based dispersant is contained, for example, in an amount of 50 to 200 parts by mass, preferably 50 to 150 parts by mass, based on 100 parts by mass of the first acid-based dispersant.
The conductive paste may contain other dispersants in addition to the first acid-based dispersant and the second acid-based dispersant. Examples of the other dispersant include an alkali dispersant, a nonionic dispersant, and an amphoteric dispersant. The other dispersant may be used singly or in combination of two or more.
Examples of the alkali-based dispersant include aliphatic amines such as laurylamine, macrogollaurylamine, abietylamine, hexadecylamine, tetradecylamine, and stearylamine. When the conductive paste further contains an alkali dispersant together with the acid dispersant having a carboxyl group, viscosity stability with time and paste dispersibility can be both achieved at a very high level.
For example, the alkali-based dispersant may be contained by 0.01 parts by mass or more and less than 2 parts by mass, preferably 0.01 parts by mass or more and 1 part by mass or less, and more preferably 0.02 parts by mass or more and less than 1 part by mass, based on 100 parts by mass of the conductive powder. For example, the alkali dispersant may be contained in an amount of 10 to 300 parts by mass, preferably 50 to 150 parts by mass, based on 100 parts by mass of the first acid dispersant. When the alkali dispersant is contained within the above range, the viscosity stability of the slurry with time is further excellent.
For example, the alkali-based dispersant is contained in an amount of 0 mass% to 2.5 mass% with respect to the entire conductive paste, preferably 0 mass% to 1.5 mass%, more preferably 0 mass% to 1.0 mass%, further preferably 0.1 mass% to 1.0 mass%, and further preferably 0.1 mass% to 0.8 mass%. When the alkali dispersant is contained in the above range, the viscosity stability of the slurry with time is more excellent.
The content of the dispersant (the whole) containing the first acid-based dispersant and the second acid-based dispersant in the conductive paste is preferably 0.21 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the conductive powder, for example. If the content of the dispersant (as a whole) exceeds the above range, the drying property of the conductive paste may be deteriorated, sheet corrosion may occur, and the green sheet may not be peeled off from the PET film of the liner sheet.
(other Components)
The conductive paste of the present embodiment may contain other components than the above components as necessary. As the other components, for example, conventionally known additives such as a defoaming agent, a plasticizer, a surfactant, and a thickener can be used.
(conductive paste)
The method for producing the conductive paste of the present embodiment is not particularly limited, and conventionally known methods can be used. For example, the conductive paste can be produced by stirring and kneading the above components by a three-roll mill, a ball mill, a mixer, or the like. In this case, when the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is dispersed sufficiently without being aggregated, and the dispersant is distributed over the surface of the conductive powder, so that a uniform conductive paste can be easily obtained. Alternatively, the conductive paste may be prepared by dissolving the binder resin in a part of the organic solvent in advance, preparing the organic vehicle, adding the conductive powder, the ceramic powder, the dispersant and the organic vehicle to the organic solvent for paste adjustment, and then stirring and kneading the mixture.
The conductive paste has a shear rate of 100sec-1The viscosity is preferably 0.8Pa · S or less. When the shear rate is 100sec-1When the viscosity is within the above range, the conductive paste can be suitably used as a conductive paste for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing.For shear rate of 100sec-1The lower limit of the viscosity in the case of (3) is not particularly limited, and is, for example, 0.2Pa · S or more.
In addition, the conductive paste had a shear rate of 10000sec-1The viscosity at that time is preferably 0.19Pa · S or less, more preferably 0.18Pa · S or less. When the shear rate is 10000sec-1When the viscosity is within the above range, the conductive paste can be suitably used as a conductive paste for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. For shear rate of 10000sec-1The lower limit of the viscosity in the case of (3) 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 dielectric layers formed using the dielectric green sheets and internal electrode layers formed using a conductive paste.
In the multilayer ceramic capacitor, the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste are preferably powders having the same composition. Even when the thickness of the dielectric green sheet is, for example, 3 μm or less, the laminated ceramic device produced using the conductive paste of the present embodiment can suppress sheet erosion and peeling failure of the dielectric green sheet.
[ electronic component ]
Embodiments of electronic components and the like according to the present invention will be described below with reference to the drawings. In the drawings, the drawings are schematically illustrated and the scale may be changed as appropriate. The position, direction, and the like of the member will be described with reference to the XYZ rectangular coordinate system shown in fig. 1 and the like as appropriate. In the XYZ rectangular coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (vertical direction).
Fig. 1 a and 1B are views 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 and external electrodes 20 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated.
A method for manufacturing a multilayer ceramic capacitor using the conductive paste will be described below. First, a conductive paste is formed on a dielectric green sheet by a printing method, and a dry film is formed. The plurality of dielectric green sheets having the dried film on the upper surface thereof are laminated by pressure bonding, and then fired to be integrated, thereby producing a multilayer ceramic fired body (ceramic laminate 10) as a ceramic capacitor body. Then, a pair of external electrodes is formed on both end portions of the ceramic laminate 10, thereby manufacturing the multilayer ceramic capacitor 1. Hereinafter, the description will be made in more detail.
First, a dielectric green sheet as an unfired ceramic sheet is prepared. Examples of the dielectric green sheet include a dielectric green sheet formed by applying a dielectric layer slurry obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic powder such as barium titanate onto a support film such as a PET film in a sheet form, and drying the slurry to remove the solvent. The thickness of the dielectric layer formed of the dielectric green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of the demand for downsizing of the multilayer ceramic capacitor.
Next, a plurality of sheets in which the internal electrode layers 11 made of the conductive paste were formed by printing and applying the conductive paste on one surface of the dielectric green sheets by a gravure printing method were prepared. The thickness of the internal electrode layer 11 made of the conductive paste is preferably 1 μm or less after drying, from the viewpoint of the requirement for making the internal electrode layer 11 thinner.
Next, the dielectric green sheet was peeled off from the support film, and laminated so that the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet were alternately arranged, followed by heating and pressing to obtain a laminate (pressure-bonded body). In addition, a dielectric green sheet for protection to which no conductive paste is applied may be further disposed on both surfaces of the laminate (pressure-bonded body).
Then, the laminate is cut into predetermined piecesAfter the green chip is formed to have a certain size, the green chip is subjected to a binder removal treatment and fired in a reducing atmosphere to prepare a multilayer ceramic fired body (ceramic laminate 10). Further, the atmosphere in the binder removal treatment is preferably air or N2A gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature when the binder removal treatment is performed is preferably 0.5 hours or more and 24 hours or less. The firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used for the internal electrode layer, and the temperature at which the firing is performed for the laminate is, for example, 1000 ℃ to 1350 ℃ inclusive, and the holding time at which the firing is performed is, for example, 0.5 hour to 8 hours inclusive.
The green chip is fired to completely remove the organic binder in the green sheet, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. Further, the internal electrodes are formed by removing the organic vehicle in the internal electrode layers 11 and sintering or melting and integrating an alloy powder containing nickel powder or nickel as a main component, and the ceramic laminate 10 in which the dielectric layers 12 and the internal electrode layers 11 are alternately laminated in a plurality of layers is formed. In addition, the ceramic laminate 10 after firing may be subjected to annealing treatment in order to improve reliability by introducing oxygen into the dielectric layers and to suppress re-oxidation of the internal electrodes.
Then, the ceramic multilayer body 10 thus prepared was provided with a pair of external electrodes 20, thereby producing the multilayer ceramic capacitor 1. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layers 21 are electrically connected to the internal electrode layers 11. Further, as the material of the external electrode 20, for example, copper, nickel, or an alloy thereof can be preferably used. In addition, electronic components other than the multilayer ceramic capacitor may be used.
[ examples ] A method for producing a compound
The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to the examples at all.
[ evaluation method ]
(viscosity of electroconductive paste)
Using a rheometer at a shear rate of 100sec-1、10000sec-1The viscosity of the conductive paste after production was measured under the conditions of (1).
(dispersibility of conductive paste)
The dispersibility of the conductive paste was evaluated by the following method.
A sample (prepared conductive paste) (GAP thickness 5 μm) was printed on a glass substrate (2 inches), and the sample was dried, the drying was performed at a maximum temperature of 120 to 150 ℃ in a belt furnace under an atmospheric atmosphere, and dried films (2cm × 2cm, thickness 3 μm) obtained after the drying were observed with × 100 (eyepiece, objective lens; 10 times each) while light (backlight) was irradiated from the back surface of the glass substrate using an optical microscope (backlight was irradiated from the back surface of the glass substrate), and the presence or absence of lumps was confirmed.
[ materials used ]
(conductive powder)
As the conductive powder, Ni powder (average particle diameter 0.3 μm) was used.
(ceramic powder)
As the ceramic powder, barium titanate (BaTiO) was used3(ii) a The average particle diameter was 0.06. mu.m).
(Binder resin)
As the binder resin, polyvinyl butyral resin (PVB, acetal resin) and Ethyl Cellulose (EC) are used.
(dispersing agent)
(1) An alkylpolyoxyalkylene phosphate compound is used as the first acid-based dispersant (a).
(2) Using oleoyl sarcosine (C)21H39NO3) As the second acid-based dispersant (B).
(3) Rosin amine (C), polyethylene glycol laurylamine (D), oleylamine (E) were used as the alkali-based dispersants.
(4) As an acid-based dispersant (for comparative example) other than the above-mentioned acid-based dispersant (a), a phosphoric acid-based dispersant (F) containing a phosphoric acid polyester (polyester having a phosphoric acid group) as a main component and the balance of phosphoric acid was used.
(organic solvent)
As the organic solvent, propylene glycol monobutyl ether (PNB, glycol ether solvent), mineral spirits (MA), Terpineol (TPO) were used.
[ example 1]
A conductive paste was prepared by mixing 25 parts by mass of a ceramic powder, 0.3 parts by mass of a first acid-based dispersant (a) and 0.5 parts by mass of a second acid-based dispersant (B) as dispersants, 2 parts by mass of PVB and 4 parts by mass of EC as binder resins, 41 parts by mass of PNB and 27 parts by mass of MA as organic solvents, based on 100 parts by mass of Ni powder as a conductive powder. The viscosity of the prepared conductive paste and the dispersibility of the paste were evaluated by the above-described methods. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 2]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.5 part by mass of the first acid-based dispersant (a) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 3]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 1.0 part by mass of the first acid-based dispersant (a) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 4]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.2 part by mass of the second acid-based dispersant (B) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 5]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 1.0 part by mass of the second acid-based dispersant (B) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 6]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.3 part by mass of the first acid-based dispersant (a), 0.5 part by mass of the second acid-based dispersant (B), and 0.2 part by mass of the rosin amine (C) were mixed as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 7]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.3 part by mass of the first acid-based dispersant (a), 0.5 part by mass of the second acid-based dispersant (B), and 0.2 part by mass of the polyethylene glycol laurylamine (D) were mixed as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 8]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.3 part by mass of the first acid-based dispersant (a), 0.5 part by mass of the second acid-based dispersant (B), and 0.2 part by mass of the oleylamine (E) were mixed as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 9]
A conductive paste was prepared and evaluated in the same manner as in example 8, except that 0.4 part by mass of oleylamine (E) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 10]
A conductive paste was prepared and evaluated in the same manner as in example 8, except that 0.8 part by mass of oleylamine (E) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 11]
Conductive paste was prepared and evaluated in the same manner as in example 1, except that only 6 parts by mass of PVB was used as the binder resin. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
[ example 12]
Conductive paste was prepared and evaluated in the same manner as in example 1, except that 50 parts by mass of PNB and 18 parts by mass of MS were used as the organic solvent. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
Comparative example 1
Conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 part by mass of the phosphoric acid-based dispersant (F) containing a phosphoric acid polyester as a main component and 0.2 part by mass of the alkali-based dispersant (C) were used as the dispersants. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
Comparative example 2
A conductive paste was prepared and evaluated in the same manner as in example 1, except that only Terpineol (TPO) was used as the organic solvent. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
Comparative example 3
A conductive paste was prepared and evaluated in the same manner as in example 1, except that only EC was used as a binder resin. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
Comparative example 4
A conductive paste was prepared and evaluated in the same manner as in example 1, except that only EC was used as a binder resin and only terpineol was used as an organic solvent. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in table 2.
TABLE 2
(evaluation results)
The conductive paste of the example was cut at a shear rate of 100sec-1The viscosity at that time is 0.36 to 0.58 Pa.s, and the shear rate is 10000sec-1The viscosity is 0.12 to 0.17Pa · S, and is suitable for gravure printing. In addition, the conductive paste of this example showed excellent dispersibility of the paste, since no lumps were observed on the surface of the dried film after printing.
On the other hand, in the conductive paste of comparative example 1 using the phosphoric acid-based dispersant (F) other than the acid-based dispersant (a), lumps were observed on the surface of the dried film after printing, indicating that the dispersibility of the paste was poor. In addition, in the conductive pastes of comparative example 2 in which the organic solvent is out of the range of the present invention, comparative example 3 in which the binder resin is out of the range of the present invention, and comparative example 4 in which the organic solvent and the binder resin are out of the range of the present invention, a viscosity suitable for gravure printing cannot be obtained. Therefore, an appropriate dry film could not be obtained, and the dispersibility could not be evaluated.
Industrial applicability of the invention
The conductive paste has viscosity suitable for gravure printing, and the dispersibility of the paste is good. Therefore, the conductive paste of the present invention is particularly suitable as a raw material for internal electrodes of multilayer ceramic capacitors as chip components of electronic devices such as cellular phones and digital devices, and particularly suitable as a conductive paste for gravure printing.
Claims (15)
1. A conductive paste comprising a conductive powder, a dispersant, a binder resin and an organic solvent,
the dispersant comprises a first acid-based dispersant and a second acid-based dispersant,
the first acid-based dispersant is an alkyl phosphate compound,
the second acid-based dispersant is an acid-based dispersant having a carboxyl group other than the first acid-based dispersant,
the binder resin contains an acetal resin, and the binder resin contains an acetal resin,
the organic solvent contains a glycol ether solvent.
2. The conductive paste according to claim 1, wherein the first acid-based dispersant is an alkylpolyoxyalkylene phosphate compound.
3. The conductive paste according to claim 1 or 2, wherein the second acid-based dispersant has a molecular weight of 5000 or less and contains an alkyl group having 10 or more and 20 or less carbon atoms or an alkenyl group having 10 or more and 20 or less carbon atoms.
4. The conductive paste according to any one of claims 1 to 3, wherein the first acid-based dispersant is contained in an amount of 0.2 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the conductive powder, and the second acid-based dispersant is contained in an amount of 0.01 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the conductive powder.
5. The conductive paste according to any one of claims 1 to 4, wherein the dispersant further contains an alkali-based dispersant.
6. The conductive paste according to claim 5, wherein the alkali dispersant is contained in an amount of 0.02 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the conductive powder.
7. The conductive paste according to any one of claims 1 to 6, wherein the conductive powder contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof.
8. The conductive paste according to any one of claims 1 to 7, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
9. The conductive paste according to any one of claims 1 to 8, wherein the conductive paste contains a ceramic powder.
10. The electroconductive paste according to claim 9, wherein said ceramic powder contains a perovskite-type oxide.
11. The conductive paste according to claim 9 or 10, wherein the average particle size of the ceramic powder is 0.01 μm or more and 0.5 μm or less.
12. The conductive paste according to any one of claims 1 to 11, wherein the conductive paste is used for an internal electrode of a laminated ceramic member.
13. The electroconductive paste according to any one of claims 1 to 12, wherein the electroconductive paste has a shear rate of 100sec-1Viscosity of timeA degree of 0.8Pa · S or less and a shear rate of 10000sec-1The viscosity is 0.19Pa · S or less.
14. An electronic component formed using the conductive paste according to any one of claims 1 to 13.
15. A method for manufacturing a multilayer ceramic capacitor, comprising a multilayer body in which at least a dielectric layer and an internal electrode are laminated, wherein the internal electrode is formed using the conductive paste according to any one of claims 1 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-230981 | 2017-11-30 | ||
| JP2017230981 | 2017-11-30 | ||
| PCT/JP2018/044005 WO2019107501A1 (en) | 2017-11-30 | 2018-11-29 | Conductive paste, electronic component, and laminate ceramic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111373491A true CN111373491A (en) | 2020-07-03 |
| CN111373491B CN111373491B (en) | 2022-05-27 |
Family
ID=66664637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880075253.1A Active CN111373491B (en) | 2017-11-30 | 2018-11-29 | Conductive paste, electronic component, and multilayer ceramic capacitor |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7279643B2 (en) |
| KR (1) | KR102621947B1 (en) |
| CN (1) | CN111373491B (en) |
| TW (1) | TWI798302B (en) |
| WO (1) | WO2019107501A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220042052A (en) * | 2019-07-31 | 2022-04-04 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive paste for gravure printing, electronic components, and multilayer ceramic capacitors |
| TW202141532A (en) * | 2020-03-04 | 2021-11-01 | 日商住友金屬鑛山股份有限公司 | Electroconductive paste, electronic component, and laminated ceramic capacitor |
| KR20240016966A (en) * | 2021-06-02 | 2024-02-06 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive paste for gravure printing, electronic components, and multilayer ceramic capacitors |
| WO2023190613A1 (en) * | 2022-03-28 | 2023-10-05 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298792A (en) * | 2003-06-26 | 2005-10-27 | Sekisui Chem Co Ltd | Binder resin for conductive paste, and conductive paste |
| CN1896082A (en) * | 2005-07-15 | 2007-01-17 | 三星电机株式会社 | Phosphate dispersant, paste composition and dispersion method using the same |
| JP2007281306A (en) * | 2006-04-10 | 2007-10-25 | Sekisui Chem Co Ltd | Screen-print paste for multilayer ceramic electronic component |
| CN102160124A (en) * | 2008-08-29 | 2011-08-17 | Sscp株式会社 | Conductive paste composition |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| CN104755572A (en) * | 2012-10-31 | 2015-07-01 | 三之星机带株式会社 | Reactive polyolefin hot-melt adhesive with low adhesion to uncoated aluminium tools and use thereof as a laminating hot-melt |
| US20150321257A1 (en) * | 2012-12-14 | 2015-11-12 | Soloe Tech Co., Ltd. | Method for manufacturing silver nanowires using ionic liquid |
| CN105900196A (en) * | 2014-03-20 | 2016-08-24 | 积水化学工业株式会社 | Electroconductive paste |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3707941A1 (en) * | 1987-03-12 | 1988-09-22 | Henkel Kgaa | DISPERSING AGENTS AND THEIR USE IN AQUEOUS CARBON SUSPENSIONS |
| JPH1092226A (en) * | 1996-09-11 | 1998-04-10 | Murata Mfg Co Ltd | Conductive composition |
| 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 |
| JP2010118470A (en) * | 2008-11-12 | 2010-05-27 | Sekisui Chem Co Ltd | Conductive paste for laminated ceramic capacitor |
| KR101198004B1 (en) * | 2010-12-10 | 2012-11-05 | 삼성전기주식회사 | A ceramic paste composition for a multilayer ceramic capacitor, a multilayer ceramic capacitor and methods of manufacturing the same |
| CN104066534B (en) * | 2012-01-20 | 2016-05-11 | 同和电子科技有限公司 | Grafting material and use its joint method |
| JP6314728B2 (en) * | 2014-07-30 | 2018-04-25 | 住友金属鉱山株式会社 | Method for producing conductive paste and conductive paste obtained thereby |
| JP6836941B2 (en) * | 2016-03-22 | 2021-03-03 | 積水化学工業株式会社 | Conductive paste |
-
2018
- 2018-11-29 WO PCT/JP2018/044005 patent/WO2019107501A1/en active Application Filing
- 2018-11-29 JP JP2019557329A patent/JP7279643B2/en active Active
- 2018-11-29 CN CN201880075253.1A patent/CN111373491B/en active Active
- 2018-11-29 KR KR1020207014785A patent/KR102621947B1/en active IP Right Grant
- 2018-11-30 TW TW107143102A patent/TWI798302B/en active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298792A (en) * | 2003-06-26 | 2005-10-27 | Sekisui Chem Co Ltd | Binder resin for conductive paste, and conductive paste |
| CN1896082A (en) * | 2005-07-15 | 2007-01-17 | 三星电机株式会社 | Phosphate dispersant, paste composition and dispersion method using the same |
| JP2007281306A (en) * | 2006-04-10 | 2007-10-25 | Sekisui Chem Co Ltd | Screen-print paste for multilayer ceramic electronic component |
| CN102160124A (en) * | 2008-08-29 | 2011-08-17 | Sscp株式会社 | Conductive paste composition |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| CN104755572A (en) * | 2012-10-31 | 2015-07-01 | 三之星机带株式会社 | Reactive polyolefin hot-melt adhesive with low adhesion to uncoated aluminium tools and use thereof as a laminating hot-melt |
| US20150321257A1 (en) * | 2012-12-14 | 2015-11-12 | Soloe Tech Co., Ltd. | Method for manufacturing silver nanowires using ionic liquid |
| CN105900196A (en) * | 2014-03-20 | 2016-08-24 | 积水化学工业株式会社 | Electroconductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019107501A1 (en) | 2020-12-24 |
| JP7279643B2 (en) | 2023-05-23 |
| KR20200089267A (en) | 2020-07-24 |
| WO2019107501A1 (en) | 2019-06-06 |
| KR102621947B1 (en) | 2024-01-05 |
| TW201926365A (en) | 2019-07-01 |
| CN111373491B (en) | 2022-05-27 |
| TWI798302B (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111373491B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN113227246B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN111052263B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN112334995B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN113227233B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN111373490B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN111066098B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN111902882B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN111095439A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| TW201937511A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| WO2019043672A2 (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| WO2019043673A2 (en) | Conductive paste, electronic component, and multilayer ceramic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |