CN111052263B - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents

Conductive paste, electronic component, and multilayer ceramic capacitor Download PDF

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CN111052263B
CN111052263B CN201880056646.8A CN201880056646A CN111052263B CN 111052263 B CN111052263 B CN 111052263B CN 201880056646 A CN201880056646 A CN 201880056646A CN 111052263 B CN111052263 B CN 111052263B
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conductive paste
mass
dispersant
parts
powder
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CN111052263A (en
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川岛刚
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Sumitomo Metal Mining Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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 an amino acid-based dispersant having a molecular weight of 5000 or less, the binder resin contains an acetal-based resin, and the organic solvent contains a glycol ether-based solvent.

Description

Conductive paste, electronic component, and multilayer ceramic capacitor
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 added 3 ) The dielectric green sheets containing dielectric powder and binder resin are printed with a paste for internal electrodes (conductive paste) containing conductive powder, binder resin, organic solvent and the like in a predetermined electrode pattern on the surfaces thereof, and the dielectric green sheets printed with the paste for internal electrodes are stacked in a plurality of layers, thereby obtaining a multilayer body in which the internal electrodes and the dielectric green sheets are stacked in a plurality of layers. Then, the laminate is subjected toThe resultant is heated and pressure bonded to form a pressure bonded body. The pressure bonded 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, 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 η of 0.1 1 pas or more and a shear rate of 0.02(s) -1 ) Viscosity η of 0.02 A thixotropic fluid satisfying the conditions expressed by a specific formula.
Patent document 2 describes a conductive paste, and the conductive paste is used for the purpose of passing through the conductive paste as in patent document 1A 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 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 ) When the viscosity of the resulting polymer is regarded as a reference, the shear rate is 10(s) -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 literature
Patent document 1: japanese patent laid-open publication No. 2003-187638
Patent document 2: japanese patent laid-open No. 2003-242835
Patent document 3: japanese patent laid-open No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
With the recent reduction in the thickness of internal electrode layers, the conductive powder also 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 production process is easily complicated because a process for removing the lumps is required.
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 paste dispersibility and productivity.
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 an amino acid-based dispersant having a molecular weight of 5000 or less, the binder resin contains an acetal-based resin, and the organic solvent contains a glycol ether-based solvent.
The amino acid-based dispersant is preferably an amino acid-based dispersant represented by the following general formula (1).
[ CHEM 1]
Figure BDA0002395659950000031
(wherein, in the general formula (1), R 1 Represents a straight-chain alkyl group having 10 to 20 carbon atoms or a straight-chain alkenyl group having 10 to 20 carbon atoms。)
The amino acid-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 glycol ether solvent is preferably contained in an amount of 30 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the conductive powder. The dispersant may further contain an alkali-based dispersant. The 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-type 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 -1 The viscosity at that time is 0.8Pa · S or less, and the shear rate is 10000sec -1 The viscosity is 0.18Pa · 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 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.
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.
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. The average particle diameter is a value determined by observation with a Scanning Electron Microscope (SEM), and refers to a number average value (sum of particle diameters measured as individual particles/number of particles observed) determined by SEM observation.
The content of the conductive powder is preferably 30 mass% to 70 mass% with respect to the entire conductive paste, and more preferably 40 mass% to 65 mass%. 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 may be used, for example, in the internal circuit of a multilayer ceramic capacitorIn the case of the electrode slurry, a known ceramic powder can be appropriately selected according to 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 oxides composed of at least one element 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 cited 3 ) 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 the dielectric ceramic powder constituting the 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 Al 2 O 3 、Bi 2 O 3 R (rare earth element) 2 O 3 、TiO 2 、Nd 2 O 3 And 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 diameter is a value determined by observation with a Scanning Electron Microscope (SEM), and refers to a number average value (sum of particle diameters measured as individual particles/number of particles observed) determined by SEM observation.
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.
As described later, when the conductive paste contains an alkali dispersant as a dispersant, the paste viscosity can be made low even if the acetal resin content is less than 40 mass%.
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 these, 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, at least one acetate-based solvent (a) selected from the group consisting of dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate may be contained. 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.
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 organic solvent preferably contains the acetate-based solvent (a) in an amount of 50 to 90 mass%, more preferably 60 to 80 mass%, based on the entire organic solvent. In the case of the mixed solution, the organic solvent contains the acetate-based solvent (B) in an amount of 10 mass% to 50 mass%, more preferably 20 mass% to 40 mass%, based on 100 mass% of the entire organic 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, aliphatic hydrocarbon solvents are 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 contained preferably 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 preferably in an amount of 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. Further, even when the aliphatic hydrocarbon solvent is contained by 25 parts by mass or more based on 100 parts by mass of the conductive powder, the dispersibility of the conductive paste can be made excellent.
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 contains an amino acid-based dispersant. 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 formation of lumps can be greatly suppressed when forming the internal electrodes by including the amino acid-based dispersant together with the binder resin and the organic solvent, and the dispersibility of the paste can be improved.
The amino acid-based dispersant has a carboxyl group and an amide bond. Although details thereof are not clear, it is presumed that the amino acid-based dispersant has a carboxyl group, and the carboxyl group is adsorbed on the surface of the conductive powder or the like to neutralize the surface potential or deactivate the hydrogen bond site, and the specific steric structure of the site other than the carboxyl group effectively suppresses aggregation of the conductive powder or the like, thereby further improving the dispersibility of the slurry.
The molecular weight of the amino acid-based dispersant is 5000 or less, preferably 1000 or less, and more preferably 500 or less. On the other hand, the lower limit of the molecular weight is preferably 100 or more, more preferably 200 or more. One or two or more kinds of the amino acid-based dispersants may be used.
The amino acid-based dispersant is preferably an amino acid-based dispersant represented by the following general formula (1).
[ CHEM 2]
Figure BDA0002395659950000091
In the above general formula (1), R 1 Represents a straight-chain alkyl group having 10 to 20 carbon atoms or a straight-chain alkenyl group having 10 to 20 carbon atoms. R 1 The number of carbon atoms is preferably 15 to 20, and more preferably 17. In addition, R 1 The alkenyl group may be a straight-chain alkenyl group or a straight-chain alkenyl group having a carbon double bond, and is preferably a straight-chain alkenyl group.
The amino acid-based dispersant is preferably contained in an amount of 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and still more preferably 0.05 to 1.0 part by mass, based on 100 parts by mass of the conductive powder. When the content of the amino acid-based dispersant is within the above range, the dispersibility of the conductive powder in the conductive paste is excellent. In addition, although the viscosity of the conductive paste tends to be lowered by increasing the content of the amino acid-based dispersant within the above range to improve the printability, the drying property of the conductive paste tends to be lowered to cause sheet corrosion and to make it impossible to maintain the print shape. Therefore, in actual use, the content composition of the combination to be an appropriate balance may be selected according to the requirements of the electronic component using the conductive paste.
The conductive paste contains, for example, 3 mass% or less of an amino acid-based dispersant with respect to the entire conductive paste. The upper limit of the content of the amino 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 amino acid-based dispersant is not particularly limited, and is, for example, 0.01 mass% or more, preferably 0.05 mass% or more.
When the organic solvent is used in combination with a binder resin, sheet corrosion and green sheet peeling failure may occur, but by containing an amino acid-based dispersant in a specific amount, the occurrence of these problems can be suppressed. In addition, in the case where an acetal resin is contained in the binder resin and a glycol ether solvent is contained in the organic solvent, a lump may be generated when a phosphoric acid dispersant or the like is used as another acid dispersant instead of an amino acid dispersant, but the generation of the lump can be greatly suppressed when the conductive paste of the present embodiment is used.
The amino acid-based dispersant can be selected from commercially available products, for example, and used while satisfying the above-described characteristics. The amino acid-based dispersant may be produced by a conventionally known production method so as to satisfy the above-described characteristics.
The conductive paste may contain an acid-based dispersant other than the amino acid-based dispersant. Examples of the other acid-based dispersant include higher fatty acids and polymeric surfactants. These dispersants 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 other acid-based dispersant is not particularly limited, and may be a surfactant selected from the following surfactants: the addition molding of ethylene oxide to diamines represented by monoalkylamine salts, alkyldiamine salts represented by N-alkyl (C14-C18) propylenediamine dioleate, alkyltrimethylammonium salts represented by alkyltrimethylammonium chlorides, alkyldimethylbenzylammonium salts represented by palmityldimethylbenzylammonium chlorides, quaternary ammonium salts represented by alkyl/polyoxyethylenemethylammonium chlorides, alkylpyridinium salts, tertiary amines represented by dimethylstearylamine, polyoxyethylenealkylamines represented by polyoxypropylene/polyoxyethylenealkylamines, and diamines represented by N, N ', N' -tris (2-hydroxyethyl) -N-alkyl (C14-18) 1,3-diaminopropane.
The dispersant may contain a dispersant other than the acid-based dispersant. Examples of the dispersant other than the acid-based dispersant include an alkali-based dispersant, a nonionic dispersant, and an amphoteric dispersant. These dispersants may be used singly or in combination.
Examples of the alkali-based dispersant include aliphatic amines such as laurylamine, macrogollaurylamine, abietylamine, hexadecylamine, tetradecylamine, stearylamine, and oleylamine. When the conductive paste further contains an alkali dispersant together with the amino acid dispersant, viscosity stability over time and paste dispersibility can be both achieved at a very high level.
For example, the alkali-based dispersant may be contained in an amount of 0.01 parts by mass or more and less than 2 parts by mass, preferably 0.02 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the conductive powder. For example, the alkali-based dispersant may be contained by about 10 parts by mass or more and about 300 parts by mass or less based on 100 parts by mass of the amino acid-based dispersant.
The content of the alkali-based dispersant in the conductive paste may be less than that of the amino acid-based dispersant, and may be 80 parts by mass or less, or may be 50 parts by mass or less, or may be 30 parts by mass or less, based on 100 parts by mass of the amino acid-based dispersant. When the alkali dispersant is contained in the above range together with the binder resin, the organic solvent, and the amino acid dispersant, the viscosity of the conductive paste can be further reduced.
For example, the alkali-based dispersant is contained in an amount of 0 mass% to 2.5 mass%, preferably 0 mass% to 1.0 mass%, more preferably 0.1 mass% to 1.0 mass%, and further preferably 0.1 mass% to 0.8 mass% with respect to the entire conductive paste. The alkali-based dispersant may be 0.3% by mass or less with respect to the entire conductive paste. When the alkali dispersant is contained in the above range, the viscosity stability of the slurry with time is further excellent.
The content of the dispersant (the whole) containing the amino acid-based dispersant in the conductive paste is, for example, preferably 0.2 parts by mass or more and 2 parts by mass or less, and may be 1 part by mass or less, based on 100 parts by mass of the conductive powder. If the content of the dispersant (all) 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 -1 The viscosity is preferably 0.8Pa · S or less. When the shear rate is 100sec -1 When 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 -1 The lower limit of the viscosity in the case of (d) 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 is preferably 0.18Pa · S or less. When the shear rate is 10000sec -1 When 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 -1 The 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. The laminated ceramic device produced using the conductive paste of the present embodiment can suppress sheet erosion and peeling failure of the green sheet even when the thickness of the dielectric green sheet is, for example, 3 μm or less.
[ electronic component ]
Embodiments of the electronic component 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 multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20.
A method for manufacturing a multilayer ceramic capacitor using the conductive paste will be described below. First, a conductive paste is printed on the dielectric green sheets, dried to form a dry film, and a plurality of dielectric green sheets having the dry film on the upper surface thereof are laminated by pressure bonding and then fired to be integrated, thereby preparing a multilayer ceramic fired body (laminate 10) as a ceramic capacitor body. Then, the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes 20 on both ends of the multilayer body 10. Hereinafter, the description will be made in more detail.
First, a dielectric green sheet (ceramic 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 raw material powder such as barium titanate onto a support film such as a PET film in a sheet form, and drying the sheet 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 the multilayer ceramic capacitor 1.
Next, a plurality of sheets on which the conductive paste was print-applied by a gravure printing method on one surface of the dielectric green sheet and dried to form a dry film were prepared. The thickness of the conductive paste (dried film) after printing 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 is peeled from the support film, and after the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet are stacked so as to be alternately arranged, a laminate (pressure-bonded body) is obtained by heating and pressing. In addition, a dielectric green sheet for protection, which is not coated with a conductive paste, may be further disposed on both surfaces of the laminate.
Next, the multilayer body is cut into a predetermined size to form green chips, and then the green chips are subjected to binder removal treatment and fired in a reducing atmosphere to prepare a multilayer ceramic fired body (multilayer body 10). Further, the atmosphere in the binder removal treatment is preferably the atmosphere orN 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 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 in the internal electrode layer 11, and the temperature at the time of firing the laminate 10 is, for example, 1000 ℃ to 1350 ℃, and the holding time at the time of firing is, for example, 0.5 hour to 8 hours.
The green chip is fired to completely remove the organic binder in the dielectric green sheet, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. Further, the organic vehicle in the dried film is removed, and an alloy powder containing nickel powder or nickel as a main component is sintered or melted and integrated to form the internal electrode layer 11, and further, a multilayer ceramic fired body (laminate 10) in which a plurality of dielectric layers 12 and internal electrode layers 11 are alternately laminated is formed. In addition, from the viewpoint of bringing oxygen into the dielectric layers 12 to improve reliability and suppressing reoxidation of the internal electrode layers 11, the fired multilayer ceramic body (multilayer body 10) after firing may be subjected to annealing treatment.
Then, the multilayer ceramic capacitor 1 is manufactured by providing the prepared multilayer ceramic fired body (multilayer body 10) 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 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 -1 The 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.
On a glass substrate (2 inch), a sample (GAP thickness =5 μm) was printed and dried. The drying is carried out in a belt furnace at a maximum temperature of 120 to 150 ℃ in an atmospheric atmosphere. The dried film (2 cm. Times.2 cm, thickness: 3 μm) obtained after drying was observed at X100 (eyepiece, objective lens; each 10 times) using an optical microscope while irradiating light (backlight) from the back surface of the glass substrate, and the presence or absence of the cake was confirmed. When no lumps were observed, the dispersibility of the conductive paste was judged to be good, and when one or more lumps were observed, the dispersibility of the conductive paste was judged to be poor.
[ 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 used 3 (ii) a The average particle diameter was 0.06. Mu.m).
(Binder resin)
As the binder resin, polyvinyl butyral resin (PVB) and Ethyl Cellulose (EC) are used.
(dispersing agent)
(1) As the amino acid-based dispersant having a molecular weight of 5000 or less, in the above general formula (1), R is used 1 ＝C 17 H 33 The acid dispersants (A) and (R) are 1 ＝C 11 H 23 The acid dispersant (B) is described.
[ CHEM 3]
Figure BDA0002395659950000151
(2) As the alkali-based dispersant, rosin amine (C), polyethylene glycol laurylamine (D), and oleylamine (E) were used.
(3) As the phosphoric acid-based dispersant, phosphoric acid polyester (F) was used.
(organic solvent)
As the organic solvent, propylene glycol monobutyl ether (PNB), mineral spirits (MA), terpineol (TPO) were used.
[ example 1]
A conductive paste was prepared by mixing 25 parts by mass of a ceramic powder, 2 parts by mass of an amino acid-based dispersant (a) as a dispersant, 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 1.5 parts by mass of the amino 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 0.8 part by mass of the amino 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 0.05 parts by mass of the amino 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 5]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.01 part by mass of the amino 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 6]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 part by mass of the amino acid-based dispersant (a) and 0.2 part by mass of the rosin amine (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.
[ example 7]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 parts by mass of the amino acid-based dispersant (a) and 0.2 parts by mass of the polyethylene glycol laurylamine (D) were 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 8]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 part by mass of the amino acid-based dispersant (a) and 0.2 part by mass of the oleylamine (E) 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.
[ example 9]
Conductive paste was prepared and evaluated in the same manner as in example 3, 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 10]
A conductive paste was prepared and evaluated in the same manner as in example 3, except that 50 parts by mass of PNB and 18 parts by mass of MA 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.
[ example 11]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 part by mass of the amino 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 12]
A conductive paste was prepared and evaluated in the same manner as in example 1, except that 0.8 parts by mass of the amino acid-based dispersant (B) and 0.2 parts by mass of the rosin amine (C) were 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.
Comparative example 1
A 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) 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.
Comparative example 2
A 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) 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 3
A conductive paste was prepared and evaluated in the same manner as in example 1, except that only 0.8 part by mass of the alkali-based dispersant (C) 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.
Comparative example 4
A conductive paste was prepared and evaluated in the same manner as in example 3, except that Terpineol (TPO) alone 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 5
A conductive paste was prepared and evaluated in the same manner as in example 3, 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 6
A conductive paste was prepared and evaluated in the same manner as in example 3, except that only EC was used as a binder resin and only Terpineol (TPO) 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.
Figure BDA0002395659950000181
TABLE 2
Figure BDA0002395659950000191
(evaluation results)
The conductive paste of the example was cut at a shear rate of 100sec -1 The viscosity at that time is 0.44 to 0.79Pa · S, and the shear rate is 10000sec -1 The viscosity at that time is 0.13 to 0.18Pa · S, and is a viscosity 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 pastes of comparative examples 1 and 2, in which the phosphoric acid-based dispersant was contained instead of the amino acid-based dispersant, 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 3 in which the dispersant does not contain an acid-based dispersant but is composed of only an alkali-based dispersant, comparative example 4 in which an organic solvent is out of the range of the present invention, comparative example 5 in which a binder resin is out of the range of the present invention, and comparative example 6 in which an organic solvent and a binder resin are out of the range of the present invention, a viscosity suitable for gravure printing cannot be obtained. Therefore, the surface appearance after printing was rough and not sufficiently smooth, and therefore, the observation of lumps was not performed.
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.
Description of the reference numerals
1. Laminated ceramic capacitor
10. Laminate
11. Internal electrode layer
12. Dielectric layer
20. External electrode
21. External electrode layer
22. Electroplated coating

Claims (14)

1. A conductive paste for gravure printing, comprising a conductive powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant comprises an amino acid-based dispersant having a molecular weight of 5000 or less, and an alkali-based dispersant, the binder resin comprises an acetal-based resin, the organic solvent comprises a glycol ether-based solvent,
the content of the alkali dispersant is 80 parts by mass or less based on 100 parts by mass of the amino acid dispersant,
the conductive paste has a shear rate of 10000sec -1 The viscosity is 0.14Pa · S or less.
2. The conductive paste according to claim 1, wherein the amino acid-based dispersant is an amino acid-based dispersant represented by the following general formula (1),
[ CHEM 1]
Figure FDA0003801741190000011
Wherein, in the general formula (1), R 1 Represents a straight-chain alkyl group having 10 to 20 carbon atoms or a straight-chain alkenyl group having 10 to 20 carbon atoms.
3. The conductive paste according to claim 1 or 2, wherein the amino acid-based dispersant is contained in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the conductive powder.
4. The conductive paste according to claim 1 or 2, wherein the glycol ether solvent is contained in an amount of 30 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the conductive powder.
5. The conductive paste according to claim 1 or 2, wherein the dispersant is contained in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the conductive powder.
6. The electroconductive paste according to claim 1 or 2, wherein said electroconductive powder contains at least one metal powder selected from the group consisting of Ni, pd, pt, au, ag, cu, and alloys thereof.
7. The conductive paste according to claim 1 or 2, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
8. The electroconductive paste according to claim 1 or 2, which contains a ceramic powder.
9. The conductive paste according to claim 8, wherein the ceramic powder contains a perovskite oxide.
10. The conductive paste according to claim 8, wherein the average particle size of the ceramic powder is 0.01 μm or more and 0.5 μm or less.
11. The conductive paste according to claim 1 or 2, which is used for an internal electrode of a laminated ceramic part.
12. The electroconductive paste according to claim 1 or 2, which is 100sec in shear rate -1 The viscosity is 0.8Pa · S or less.
13. An electronic component formed using the conductive paste according to any one of claims 1 to 12.
14. 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 12.
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