CN113227233B - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
- Publication number
- CN113227233B CN113227233B CN201980085792.8A CN201980085792A CN113227233B CN 113227233 B CN113227233 B CN 113227233B CN 201980085792 A CN201980085792 A CN 201980085792A CN 113227233 B CN113227233 B CN 113227233B
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- acid
- conductive paste
- dispersant
- mass
- powder
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- 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
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- 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
- C08K3/24—Acids; Salts thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Spectroscopy & Molecular Physics (AREA)
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- Conductive Materials (AREA)
- Ceramic Capacitors (AREA)
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a conductive paste with excellent dispersibility. The conductive paste of the present invention contains a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant contains a first acid-based dispersant having an average molecular weight of more than 500 and not more than 2000 and having one or more branched chains composed of hydrocarbon groups with respect to the main chain, and a second acid-based dispersant which is a dispersant other than the first acid-based dispersant and has a carboxyl group, 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 laminated ceramic capacitor.
Background
With miniaturization and higher performance of electronic devices such as mobile phones and digital devices, miniaturization and higher capacity are also desired 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 laminated, and the dielectric layers and the internal electrode layers are thinned, thereby achieving miniaturization and high capacity.
For example, a laminated ceramic capacitor can be manufactured as follows. First, barium titanate (BaTiO) 3 ) A conductive paste for internal electrodes is printed (coated) on the surface of a dielectric green sheet of dielectric powder and binder resin in a predetermined electrode pattern, and dried to form a dry film. Next, the dried film and the dielectric green sheet are stacked alternately, and heat-press bonded to integrate them to form a press-bonded body. The pressure-bonded body is cut, subjected to an organic binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip (laminate). Next, external electrode paste is applied to both end portions of the fired chip (laminate), and after firing, nickel plating or the like is applied to the external electrode surface, thereby obtaining a laminated ceramic capacitor.
As a printing method used for printing the conductive paste on the dielectric green sheet, a screen printing method has been generally used in the past, but in view of the demands for miniaturization, thinning, and improvement in productivity of electronic devices, it is demanded to print finer electrode patterns with higher productivity.
As one of printing methods of the conductive paste, a gravure printing method is proposed as a continuous printing method in which a conductive paste is filled in a recess provided in a plate making process, and the plate making process is pressed against a surface to be printed to transfer the conductive paste from the plate making process. The gravure printing method is high in printing speed and excellent in productivity. In the case of using the gravure printing method, it is necessary to appropriately select a binder resin, a dispersant, a solvent, and the like in the conductive paste, and adjust the characteristics of viscosity and the like to a range suitable for gravure printing.
For example, patent document 1 describes a conductive paste for forming an internal conductor film by gravure printing, which is an internal conductor film in a laminated ceramic electronic component including a plurality of ceramic layers and an internal conductor film extending along a specific interface between the ceramic layers, the conductive paste including 30 to 70% by weight of a solid component containing a metal powder, 1 to 10% by weight of an ethylcellulose resin component having an ethoxy content of 49.6% or more, 0.05 to 5% by weight of a dispersant, and the balance of a solvent component, the conductive paste having a shear rate of 0.1 (s -1 ) Viscosity η at time 0.1 Is 1 Pa.s or more and has a shear rate of 0.02 (s -1 ) Viscosity η at time 0.02 Thixotropic fluids satisfying the conditions expressed by specific formulas.
Patent document 2 describes a conductive paste for forming an internal conductor film by gravure printing, which contains 30 to 70 wt% of a solid component containing a metal powder, 1 to 10 wt% of a resin component, 0.05 to 5 wt% of a dispersant, and the balance of a solvent component, and has a shear rate of 0.1(s) -1 ) Thixotropic fluids having a viscosity of 1 Pa.s or more at a shear rate of 0.1 (s -1 ) When the viscosity at the time was used as a reference, the shear rate was 10 (s -1 ) The viscosity change rate at the time of the preparation is 50% or more.
According to patent documents 1 and 2, the conductive paste has a shear rate of 0.1 (s -1 ) A thixotropic fluid having a viscosity of 1 Pa.s or more can provide stable continuous printability at high speed in gravure printing, and can produce a laminated ceramic electronic component such as a laminated ceramic capacitor with good production efficiency.
Patent document 3 describes a conductive paste for internal electrodes of multilayer ceramic capacitors, which contains a conductive powder (a), an organic resin (B) composed of polyvinyl butyral having a polymerization degree of 10000 to 50000 and ethylcellulose having a weight average molecular weight of 10000 to 100000, an organic solvent (C) 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, an additive (D) 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 uniformity and stability of the paste and has good drying property.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2003-187638
Patent document 2: japanese patent laid-open publication No. 2003-242835
Patent document 3: japanese patent application laid-open No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
With the recent thinning of the internal electrode layers, 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 increases, so that the surface activity of the conductive powder (metal powder) increases, and the dispersibility of the conductive paste may decrease, and a conductive paste having higher dispersibility is demanded.
In addition, in the case of printing a conductive paste by a gravure printing method, since a lower paste viscosity is required than in a screen printing method, it is considered that a conductive powder having a large specific gravity is settled and the dispersibility of the paste is lowered. In addition, in the conductive paste described in patent documents 1 and 2, although dispersibility of the paste is improved by removing the lumps in the conductive paste by using a filter, a step of removing the lumps is required, and thus the manufacturing process is easily complicated.
In view of such a situation, an object of the present invention is to provide a conductive paste which is excellent in dispersibility and productivity of the paste and has a paste viscosity suitable for gravure printing.
Means for solving the problems
In a first aspect of the present invention, there is provided a conductive paste comprising a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant comprises a first acid-based dispersant having an average molecular weight of more than 500 and not more than 2000 and having one or more branched chains composed of hydrocarbon groups with respect to a main chain, the second acid-based dispersant being a dispersant other than the first acid-based dispersant and having a carboxyl group, the binder resin comprises an acetal resin, and the organic solvent comprises a glycol ether solvent.
The first acid-based dispersant is preferably an acid-based dispersant having a carboxyl group, and more preferably a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain. 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. Further, it is preferable that the conductive powder contains 0.2 to 2 parts by mass of the first acid-based dispersant, and the conductive powder contains 0.01 to 2 parts by mass of the second acid-based dispersant. The conductive powder preferably contains at least one metal powder selected from Ni, pd, pt, au, ag, cu and an alloy thereof. The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less. 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 binder resin preferably contains a butyral based resin. The conductive paste is preferably used for the internal electrode of the laminated ceramic member. In addition, the conductive paste preferably has a shear rate of 100sec -1 The viscosity at the time of the reaction is 0.8 Pa.S or less, and the shear rate at the time of the reaction is 10000sec -1 Viscosity at the time of 0.18 Pa.SThe following is given.
In a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.
In a third aspect of the present invention, there is provided a multilayer ceramic capacitor comprising at least a laminate of a dielectric layer and an internal electrode layer, the internal electrode layer being formed using the above-described conductive paste.
Effects of the invention
The conductive paste of the present invention is excellent in dispersibility and productivity. In addition, the conductive paste of the present invention has a viscosity suitable for gravure printing. The electrode pattern of an electronic component such as a multilayer ceramic capacitor formed using the electroconductive paste of the present invention is excellent in printability and has a uniform thickness even when a thin-film electrode is formed.
Drawings
A in fig. 1 is a perspective view showing a multilayer ceramic capacitor according to an embodiment, and B in fig. 1 is a cross-sectional view thereof.
Detailed Description
[ conductive paste ]
The conductive paste of the present embodiment contains a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent. The components are described in detail below.
(conductive powder)
The conductive powder is not particularly limited, and a metal powder may be used, and for example, one or more kinds of powder selected from Ni, pd, pt, au, ag, cu and an alloy thereof may be used. Among them, from the viewpoints of conductivity, corrosion resistance, and cost, a powder of Ni or an alloy thereof (hereinafter, sometimes referred to as "Ni powder") is preferably used. As the Ni alloy, for example, an alloy of Ni and at least one or more elements selected from the group consisting of Mn, cr, co, al, fe, cu, zn, ag, au, pt and Pd can be used. The Ni content in the Ni alloy is, for example, 50 mass% or more, and preferably 80 mass% or more. In addition, the Ni powder may contain the element S in the order of several hundred ppm in order to suppress severe gas generation due to thermal decomposition of a portion of the binder resin at the time of binder removal treatment.
The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. When the average particle diameter of the conductive powder is within the above range, the conductive powder can be suitably used as a paste for internal electrodes of a laminated ceramic capacitor (laminated ceramic component) which is thinned, and for example, the smoothness and dry film density of the dry film can be improved. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is a number average value obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 10,000.
The content of the conductive powder is preferably 30 mass% or more and less than 70 mass%, more preferably 40 mass% or more and 60 mass% or less, relative to the total amount of the conductive paste. When the content of the conductive powder is within the above range, the conductive property and dispersibility are excellent.
(ceramic powder)
The ceramic powder is not particularly limited, and for example, in the case of being a conductive paste for the internal electrode of a multilayer ceramic capacitor, a known ceramic powder may be appropriately selected according to the type of the multilayer ceramic capacitor to be used. Examples of the ceramic powder include perovskite oxides containing Ba and Ti, and barium titanate (BaTiO 3 )。
As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. The oxide may be one or more oxides selected from Mn, cr, si, ca, ba, mg, V, W, ta, nb and rare earth elements.
As the ceramic powder, for example, barium titanate (BaTiO 3 ) The Ba atoms and Ti atoms of the ceramic powder are replaced with other atoms such as Sn, pb, zr, etc.
When used as a conductive paste for internal electrodes, ceramic powder can be used as a material for forming a multilayer ceramic capacitor (electronic componentComponent) dielectric green sheet, and the dielectric ceramic powder of the dielectric green sheet. Thereby, occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering process can be suppressed. Examples of such ceramic powders include ZnO, ferrite, and PZT, baO, al, in addition to the above-mentioned perovskite oxides containing Ba and Ti 2 O 3 、Bi 2 O 3 R (rare earth element) 2 O 3 、TiO 2 、Nd 2 O 3 And the like. In addition, one kind of ceramic powder may be used, or two or more kinds may be used.
The average particle diameter of the ceramic powder is, for example, in the range of 0.01 μm to 0.5 μm, preferably 0.01 μm to 0.3 μm. When the average particle diameter of the ceramic powder is within the above range, a sufficiently thin and uniform internal electrode can be formed when the ceramic powder is used as a slurry for internal electrodes. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is a number average value obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 50,000.
The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the conductive powder.
The content of the ceramic powder is preferably 1 mass% or more and 20 mass% or less, more preferably 3 mass% or more and 20 mass% or less, relative to the total amount of the conductive paste.
(adhesive resin)
The binder resin contains an acetal resin. The acetal resin is preferably a butyral resin such as polyvinyl butyral. When the binder resin contains an acetal resin, the viscosity can be adjusted to be suitable for gravure printing, and the adhesive strength with the green sheet can be further improved. The binder resin may contain, for example, 20 mass% or more of an acetal resin with respect to the entire binder resin, 30 mass% or more, or may be composed of only an acetal resin. In addition, even if the content of the acetal resin is less than 40 mass% relative to the entire binder resin, the slurry viscosity can be low and the adhesive strength can be sufficiently high.
The content of the acetal resin is preferably 1 part by mass or more and 10 parts by mass or less, 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 binder resin may contain a resin other 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 viewpoints of solubility in a solvent, and combustion degradability. 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, 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% or more and 10 mass% or less, more preferably 0.5 mass% or more and 6 mass% or less, with respect to the total amount of the 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 a glycol ether solvent.
Examples of the glycol ether solvents include (di) glycol ethers such as diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, 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 (PNB) is more preferable. When the organic solvent contains a glycol ether solvent, the compatibility with the binder resin is excellent and the drying property is excellent.
The organic solvent may contain, for example, 25 mass% or more of the glycol ether solvent, 50 mass% or more of the entire organic solvent, or may be composed of only the glycol ether solvent. The glycol ether solvents may be used singly or in combination of two or more.
The organic solvent may further contain an acetate solvent. Examples of the acetate 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 solvent, for example, at least one acetate 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 contained in an amount of 0 to 80 mass%, preferably 10 to 60 mass%, and more preferably 20 to 40 mass%, based on the entire organic solvent.
In the case where the organic solvent contains an acetate solvent, for example, the above-mentioned acetate solvent (a) and at least one acetate 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 solvent (a) and the acetate solvent (B), the organic solvent preferably contains 50 mass% to 90 mass% of the acetate solvent (a), more preferably 60 mass% to 80 mass%, with respect to the entire acetate solvent. In the case of the above-mentioned mixed solution, the content of the acetate-based solvent (B) is preferably 10 to 50 mass%, more preferably 20 to 40 mass%, based on 100 mass% of the entire acetate-based solvent.
The organic solvent may contain an organic solvent other than the glycol ether solvent and the acetate solvent. The other organic solvents are not particularly limited, and known organic solvents capable of dissolving the binder resin can be used. Examples of the other organic solvents 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 the aliphatic hydrocarbon solvents. Further, one kind of the other organic solvents may be used, or two or more kinds 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 to 50 parts by mass, more preferably 40 to 50 parts by mass, based on 100 parts by mass of the conductive powder, and the aliphatic hydrocarbon solvent is preferably contained in an amount of 20 to 80 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the conductive powder. In addition, even when the conductive powder contains 25 parts by mass or more of an aliphatic hydrocarbon solvent, the conductive paste is excellent in dispersibility, 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, 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%, with respect to the total amount of the conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(dispersant)
As a result of the studies of various dispersants for the dispersants used in the conductive paste, the inventors of the present invention have found that the use of a dispersant comprising a first acid-based dispersant having an average molecular weight of more than 500 and not more than 2000 and having one or more branches composed of a hydrocarbon group with respect to the main chain and a second acid-based dispersant having a carboxyl group other than the first acid-based dispersant makes the dispersibility of the powder material (conductive powder, ceramic powder) contained in the conductive paste excellent and the smoothness of the dried film surface excellent.
Although the reason for this effect is not clear, it is considered that the first acid-based dispersant has a branched chain composed of a hydrocarbon group, whereby a steric hindrance is effectively formed to suppress aggregation of the powder material, and the second acid-based dispersant has a carboxyl group, whereby the first acid-based dispersant can be dispersed more effectively. Further, by setting the molecular weight of the first acid-based dispersant to a specific value, it is possible to maintain a proper viscosity according to the use of the conductive paste. The present invention is not limited by the above theory (reason). The dispersant according to the present embodiment will be described in further detail below.
The first acid-based dispersant has one or more branched chains each comprising a hydrocarbon group, preferably a plurality of branched chains each comprising a hydrocarbon group, with respect to the main chain. The first acid-based dispersant preferably has a carboxyl group, and more preferably is a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain. In addition, the polycarboxylic acid preferably has an ester structure. In addition, the hydrocarbon group preferably has a chain structure. In addition, the hydrocarbyl group may be an alkyl group. The alkyl group may be composed of only carbon and hydrogen, and a part of the hydrogen constituting the alkyl group may be substituted with a substituent.
The molecular weight of the first acid-based dispersant is more than 500 and not more than 2000, or may be 1000 or more and not more than 2000. When the molecular weight is within the above range, the dispersibility of the conductive powder or the ceramic powder is excellent, and the density and smoothness of the dried film surface are excellent. In addition, in this specification, in the case where the molecular weight of the dispersant has a distribution to some extent, the molecular weight of the dispersant means a weight average molecular weight.
The first acid-based dispersant may be used by selecting an acid-based dispersant satisfying the above characteristics from commercially available products, for example. The first acid-based dispersant may be produced by a conventionally known production method so as to satisfy the above-described characteristics.
The first acid-based dispersant is preferably contained in an amount of 0.2 to 2 parts by mass based on 100 parts by mass of the conductive powder. When the content of the first acid-based dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the dried electrode surface after coating are excellent, and the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and peeling failure of the green sheet can be suppressed. In addition, in the conductive paste according to the present embodiment, even if the content of the first acid-based dispersant is 1 part by mass or less, high dispersibility can be obtained.
The second acid-based dispersant is an acid-based dispersant having a carboxyl group. The second acid-based dispersant preferably has a molecular weight of 5000 or less, more preferably has a molecular weight of 1000 or less, and still more preferably has a molecular weight of 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. In the case where the second acid-based dispersant has the above-described structure, the effect obtained by adding the first acid-based dispersant can be further improved, and the dispersibility in forming the conductive paste can be further improved.
Examples of the second acid-based dispersant include higher fatty acids, amino acids, and other acid-based dispersants. In addition, the second acid-based 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 examples thereof include surfactants selected from the following surfactants: among them, the ethyleneoxide-added diamine is preferably selected from the group consisting of an alkyl monoamine type represented by monoalkylamine salts, an alkyl diamine type represented by N-alkyl (C14-C18) propylenediamine dioleate, an alkyl trimethyl ammonium salt type represented by alkyl trimethyl ammonium chloride, an alkyl dimethylbenzyl ammonium salt type represented by palmityl dimethylbenzyl ammonium chloride, a quaternary ammonium salt type represented by alkyl/polyoxyethylene methyl ammonium chloride, an alkylpyridinium salt type, a tertiary amine type represented by dimethyl stearylamine, a polyoxyethylene alkylamine type represented by polyoxypropylene/polyoxyethylene alkylamine, and a diamine represented by N, N ', N' -tris (2-hydroxyethyl) -N-alkyl (C14-18) 1, 3-diaminopropane.
The alkyl monoamine salt type is preferably oleoyl sarcosine, lauroyl sarcosine, stearic acid amide or the like.
The second 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. 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 and the ceramic powder in the conductive paste is more excellent, the smoothness of the dried electrode surface after coating is more excellent, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and peeling failure of the green sheet can be suppressed. In the conductive paste according to the present embodiment, the content of the second acid-based dispersant may be 1 part by mass or less, 0.1 part by mass or less, or 0.05 part by mass or less.
The second acid-based dispersant may be contained in an amount of, for example, 1 to 500 parts by mass, preferably 50 to 300 parts by mass, more preferably 50 to 200 parts by mass, and still more preferably 50 to 150 parts by mass, based on 100 parts by mass of the first acid-based dispersant. When the second acid-based dispersant is contained in the above range, the dry film density and the surface roughness tend to be good.
The conductive paste may contain only the first acid-based dispersant and the second acid-based dispersant as dispersants, or may contain dispersants other than the above-described acid-based dispersants within a range that does not hinder the effects of the present invention. Examples of the dispersant other than the above include an acid-based dispersant containing a higher fatty acid, a polymer surfactant, etc., an alkali-based dispersant, an amphoteric surfactant, a polymer dispersant, etc., and more preferably an alkali-based dispersant. In addition, one or a combination of two or more of these dispersants may be used.
The content (total content) of the entire dispersant including the first acid-based dispersant and the second acid-based dispersant is preferably 0.01 part by mass or more and 3 parts by mass or less, more preferably 0.23 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the conductive powder. In the conductive paste according to the present embodiment, the content (total content) of the entire dispersant may be 2 parts by mass or less or 1 part by mass or less. Even if the content of the entire dispersant is within the above range, high dispersibility can be obtained.
The total content of the acid-based dispersant is preferably 3 mass% or less relative to the total amount of the conductive paste. The upper limit of the total content of the dispersant is preferably 2 mass% or less, more preferably 1 mass% or less. The lower limit of the total content of the dispersant is not particularly limited, and is, for example, 0.01 mass% or more, preferably 0.05 mass% or more. When the total content of the dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and peeling failure of the green sheet can be suppressed.
(other Components)
The conductive paste of the present embodiment may contain other components than the above components as necessary. As the other component, for example, conventionally known additives such as an antifoaming agent, a plasticizer, and a thickener can be used.
(conductive paste)
The method for producing the conductive paste of the present embodiment is not particularly limited, and a conventionally known method can be used. For example, the above-described components may be stirred and kneaded by a three-roll mill, a ball mill, a mixer, or the like to produce a conductive paste. In this case, if the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is not aggregated, and the dispersant can be sufficiently dispersed over the surface, so that a uniform conductive paste can be easily obtained. The conductive paste may be prepared by dissolving the binder resin in a part of the organic solvent in advance, adding the conductive powder, the ceramic powder, the dispersant, and the organic carrier to the organic solvent for paste adjustment after preparing the organic carrier, and stirring and kneading the mixture.
The conductive paste had a shear rate of 100sec -1 The viscosity at the time of the reaction is preferably 0.8pa·s or less, and may be 0.5pa·s or less, or may be 0.4pa·s or less, or may be 0.3pa·s or less, or may be 0.25pa·s or less. At a shear rate of 100sec -1 When the viscosity is within the above range, the conductive paste can be suitably used 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. The conductive paste of the present embodiment has a shear rate of 100sec -1 The lower limit of the viscosity is not particularly limited, and is, for example, 0.1pa·s or more.
In addition, the conductive paste had a shear rate of 10000sec -1 The viscosity at the time is preferably 0.18pa·s or less, and may be less than 0.14pa·s. 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. When the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. For a shear rate of 10000sec -1 The lower limit of the viscosity is not particularly limited, and is, for example, 0.05pa·s or more.
In addition, after printing the conductive paste, the Dry Film Density (DFD) of the dry film obtained by drying is preferably more than 5.0g/cm 3 Can be 5.2g/cm 3 Above, it may be more than 5.2g/cm 3 May also be 5.3g/cm 3 The above. There is no upper limit on the dry film densityIs specifically limited to 9.8g/cm of the true density of metallic nickel 3 For example, it may be 6.5g/cm 3 The following is given.
The arithmetic average roughness Sa when a dried film having a thickness of 1 to 3 μm and a square 20mm is produced by printing a conductive paste and drying it in the atmosphere at 120 ℃ for 1 hour is preferably 0.2 μm or less, and may be 0.16 μm or less. On the other hand, the lower limit of the arithmetic average roughness Sa is not particularly limited, and the surface is preferably flat, and a value exceeding 0 is more preferable as the value becomes smaller. Further, the arithmetic average roughness Sa is measured based on the standard of ISO 25178.
The conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors. The multilayer ceramic capacitor has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
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 manufactured by 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 ]
Hereinafter, embodiments of an electronic component and the like according to the present invention will be described with reference to the drawings. In the drawings, the drawings may be schematically represented or may be represented by changing the scale. The position, direction, and the like of the member will be described with reference to an XYZ orthogonal coordinate system shown in fig. 1 and the like, as appropriate. In the XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is vertical direction (vertical direction).
A in fig. 1 and B in fig. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 has a laminate 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20.
Hereinafter, a method for manufacturing a multilayer ceramic capacitor using the above conductive paste will be described. First, a conductive paste is printed on a dielectric green sheet and dried to form a dried film, and a plurality of dielectric green sheets each having the dried film on the upper surface thereof are laminated by pressure bonding, and then fired to integrate the dielectric green sheets, thereby producing a multilayer ceramic fired body (multilayer body 10) which is a ceramic capacitor body. Thereafter, a pair of external electrodes 20 are formed at both end portions of the laminate 10 to produce the laminated ceramic capacitor 1. Hereinafter, the present invention will be described 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 slurry for a dielectric layer, which is obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate, onto a support film such as a PET film, and drying the support film to remove the solvent. The thickness of the dielectric layer formed of the 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 1.
Next, a plurality of sheets are prepared, each of which is formed with a dry film by printing and coating the conductive paste on one surface of the dielectric green sheet by gravure printing and drying. In view of the requirement for thinning the internal electrode layer 11, the thickness of the printed conductive paste (dry film) is preferably 1 μm or less after drying.
Next, the dielectric green sheet is peeled from the support film, laminated so that the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet are alternately arranged, and then heated and pressed to obtain a laminate (pressure bonded body). The protective dielectric green sheet to which the conductive paste is not applied may be further disposed on both surfaces of the laminate.
Next, the laminate is cut into a predetermined size to form green chips, and the green chips are subjected to binder removal treatment and fired in a reducing atmosphere to produce laminated ceramicsCeramic fired body (laminate 10). The atmosphere in the binder removal treatment is preferably the atmosphere or N 2 A gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature at the time of the binder removal treatment is preferably 0.5 hours to 24 hours. In addition, 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 which the laminate 10 is fired is, for example, 1000 ℃ to 1350 ℃, and the holding time of the temperature at which the firing is performed is, for example, 0.5 hours to 8 hours.
The firing of the green chip completely removes the organic binder in the dielectric green sheet, and fires the ceramic raw material powder to form the ceramic dielectric layer 12. The organic carrier in the dried film is removed, and the internal electrode layers 11 are formed by sintering or melting and integrating nickel powder or alloy powder containing nickel as a main component, thereby forming a multilayer ceramic fired body (multilayer body 10) in which a plurality of dielectric layers 12 and a plurality of internal electrode layers 11 are alternately stacked. In addition, from the viewpoints of improving reliability by introducing oxygen into the dielectric layer 12 and suppressing reoxidation of the internal electrode layers 11, the fired laminated ceramic fired body (laminate 10) may be subjected to an annealing treatment.
Then, the laminated ceramic capacitor 1 is manufactured by providing the produced laminated ceramic fired body (laminated 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 layer 21 is electrically connected to the internal electrode layer 11. Further, as a material of the external electrode 20, copper, nickel, or an alloy thereof, for example, can be preferably used. In addition, electronic components other than the multilayer ceramic capacitor can be used as the electronic components.
[ example ]
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the examples.
[ evaluation method ]
(viscosity of conductive paste)
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).
(Density of dried film)
The prepared conductive paste was placed on a PET film and extended to a length of about 100mm by an applicator having a width of 50mm and a gap of 125. Mu.m. The obtained PET film was dried at 120 ℃ for 40 minutes to form a dried film, and then the dried film was cut into four squares of 2.54cm (1 inch), and the thickness and weight of each of the four dried films were measured to calculate the dried film density (average value) after peeling the PET film.
(surface roughness)
The prepared conductive paste was printed on heat-resistant tempered glass having a square diameter of 2.54cm (1 inch), and dried at 120℃for 1 hour in the atmosphere, thereby producing a dried film having a square diameter of 20mm and a film thickness of 1 to 3. Mu.m. The surface roughness Sa (arithmetic average roughness) of the produced dried film was measured using a device for measurement based on the standard of ISO 25178. The arithmetic average roughness Sa is a parameter obtained by expanding the arithmetic average roughness Ra (arithmetic average height of a line) to a plane.
[ use of materials ]
(conductive powder)
As the conductive powder, ni powder (SEM average particle diameter of 0.3 μm) was used.
(ceramic powder)
As the ceramic powder, barium titanate (BaTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the SEM average particle size was 0.10. Mu.m).
(adhesive resin)
As the binder resin, polyvinyl butyral resin (PVB) and Ethylcellulose (EC) were used.
(dispersant)
(1) As the first acid-based dispersant (a), an acid-based dispersant having an average molecular weight of 1500 and being a hydrocarbon-based graft copolymer (having a branched chain composed of a hydrocarbon) having a polycarboxylic acid as a main chain was used.
(2) As the second acid-based dispersant (B), oleoyl creatinine was usedAcid (C) 21 H 39 NO 3 )。
(3) For comparison, a phosphoric acid-based dispersant (C) (molecular weight: 1400, without a branched chain composed of hydrocarbon) used in a conventional conductive paste 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 ceramic powder, 0.2 part by mass of the first acid-based dispersant (a) as a dispersant, 1.0 part by mass of the second acid-based dispersant (B), 2 parts by mass of PVB as a binder resin, and 4 parts by mass of EC, 41 parts by mass of PNB as an organic solvent, and 27 parts by mass of MA with respect to 100 parts by mass of Ni powder as a conductive powder. The viscosity of the prepared conductive paste was evaluated by the above method, and the dry film density and surface roughness of the paste were evaluated. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Example 2
A conductive paste was prepared and evaluated in the same manner as in example 1, except that the content of the first acid-based dispersant (a) was 0.74 parts by mass. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Example 3
A conductive paste was prepared and evaluated in the same manner as in example 1, except that the content of the first acid-based dispersant (a) was 2.0 parts by mass. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Example 4
A conductive paste was prepared and evaluated in the same manner as in example 2, except that the content of the second acid-based dispersant (B) was 0.01 parts by mass. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Example 5
A conductive paste was prepared and evaluated in the same manner as in example 2, except that the content of the second acid-based dispersant (B) was 2.0 parts by mass. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Example 6
A conductive paste was prepared and evaluated in the same manner as in example 1, except that the content of the first acid-based dispersant (a) was 0.6 part by mass and the content of the second acid-based dispersant (B) was 1.2 parts by mass. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness 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 parts by mass of a phosphoric acid-based dispersant was used as the dispersant. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Comparative example 2
A conductive paste was prepared and evaluated in the same manner as in example 2, except that 68 parts by mass of TPO was used as the main solvent and no auxiliary solvent was used. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Comparative example 3
A conductive paste was prepared and evaluated in the same manner as in example 2, except that 6 parts by mass of EC was used as the binder resin and PVB was not used. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Reference example 1
A conductive paste was prepared and evaluated in the same manner as in example 2, except that the second acid-based dispersant (B) was not used as the dispersant. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
Reference example 2
A conductive paste was prepared and evaluated in the same manner as in example 2, except that the first acid-based dispersant (a) was not used and 0.8 parts by mass of the second acid-based dispersant (B) was used as the dispersant. The contents of the dispersing agent and the like of the conductive paste are shown in table 1, and the evaluation results of the viscosity of the conductive paste, the density of the dried film, and the surface roughness are shown in table 2.
TABLE 2
(evaluation results)
The conductive paste of the example had a shear rate of 100sec -1 The viscosity at the time is 0.20 to 0.23 Pa.s, and the shear rate is 10000sec -1 The viscosity at the time was 0.11 to 0.14 Pa.s, and the film was stably displayed as a low value at any shear rate, indicating that the film had a viscosity suitable for gravure printing. Further, it was confirmed that the dry film density of the conductive paste of examples was 5.1 to 5.4g/cm 3 The surface roughness of the dried film is 0.13 to 0.16 mu m, and the dispersibility is excellent.
In addition, when the conductive pastes of examples 1 to 3 were compared, it was found that the dry film density increased and the surface roughness was smoother as the content of the first acid-based dispersant (a) increased. Among them, the dry film density and surface roughness values of example 3 were almost saturated values. As is clear from examples 2, 4 and 5, the dry film density and surface roughness can be improved by increasing the content of the second acid-based dispersant. Further, as is clear from a comparison of the conductive pastes and the like of examples 1 and 4 and example 6, the dry film density and the surface roughness tend to be good when the mixing ratio is relatively close, as compared with the case where there is a large difference in the mixing ratio of the first acid-based dispersant (a) and the second acid-based dispersant (B).
In contrast, when the conductive paste of comparative example 1, which does not contain the first acid-based dispersant but uses the phosphoric acid-based dispersant, was produced under the same conditions, the viscosity was higher than that of examples, and the dry film density was not sufficiently improved, and the surface roughness was also higher than that of examples.
In addition, the conductive paste of comparative example 2 using TPO as a main solvent, which is generally used in most cases, has extremely high viscosity, is unsuitable for gravure printing, and has higher surface roughness than the examples. In addition, the conductive paste of comparative example 3, which does not contain an acetal resin in the binder resin, has a high viscosity, and the dry film density is not sufficiently improved.
In addition, it was revealed that in the conductive paste of reference example 1 containing the first acid-based dispersant (a) alone or the conductive paste of reference example 2 containing the second acid-based dispersant (B) alone as the dispersant, the dry film density was higher, the surface roughness was also lower, and the dispersibility was improved as compared with comparative example 1 using the phosphoric acid-based dispersant.
As is clear from the above, when the conductive paste of the embodiment of the present invention containing both the first acid-based dispersant (a) and the second acid-based dispersant (B) is compared with the conductive paste of the comparative example and the reference example, the dry film density is higher, the surface roughness is lower, and the dispersibility of the conductive paste is further improved. Further, it is found that the conductive paste of the embodiment of the present invention containing both dispersants is lower in viscosity than the conductive paste of the comparative example and the reference example, and is more suitable for gravure printing.
The technical scope of the present invention is not limited to the embodiments described in the above embodiments and the like. One or more of the elements described in the above embodiments and the like may be omitted. The elements described in the above embodiments and the like may be appropriately combined. The disclosures of all documents cited in the above embodiments and the like are incorporated by reference as part of the description herein, as permitted by law.
Industrial applicability
The conductive paste of the present invention has a viscosity suitable for gravure printing, and the dried film after coating has a high density, and the dried film has excellent surface smoothness and excellent dispersibility. Therefore, the conductive paste of the present invention is particularly suitable as a raw material for internal electrodes of laminated ceramic capacitors used as chip parts of electronic devices such as mobile phones and digital devices which are increasingly miniaturized, and particularly suitable as a conductive paste for gravure printing.
The technical scope of the present invention is not limited to the embodiments described in the above embodiments and the like. One or more of the elements described in the above embodiments and the like may be omitted. The elements described in the above embodiments and the like may be appropriately combined. In addition, the contents of all documents cited in Japanese patent application publication No. 2018-241705 and the present specification are incorporated by reference as if allowed by law.
Description of the reference numerals
1. Multilayer ceramic capacitor
10. Ceramic laminate
11. Internal electrode layer
12. Dielectric layer
20. External electrode
21. External electrode layer
22. Electroplated layer
Claims (11)
1. A conductive paste containing conductive powder, ceramic powder, a dispersant, a binder resin and an organic solvent, wherein,
The dispersant comprises a first acid-based dispersant and a second acid-based dispersant,
the first acid dispersant has an average molecular weight of more than 500 and not more than 2000 and has at least one branched chain composed of a hydrocarbon group with respect to a main chain,
the second acid-based dispersant is a dispersant other than the first acid-based dispersant and has a carboxyl group,
the binder resin comprises an acetal-based resin,
the organic solvent comprises a glycol ether solvent,
the first acid-based dispersant is a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain,
the first acid-based dispersing agent is contained in an amount of 0.2 to 2 parts by mass based on 100 parts by mass of the conductive powder, and the second acid-based dispersing agent is contained in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the conductive powder.
2. The conductive paste according to claim 1, wherein 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.
3. The conductive paste according to claim 1 or 2, wherein the conductive powder contains a metal powder selected from at least one of Ni, pd, pt, au, ag, cu and an alloy thereof.
4. 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.
5. The electroconductive paste according to claim 1 or 2, wherein the ceramic powder contains perovskite-type oxides.
6. The electroconductive paste according to claim 1 or 2, wherein the ceramic powder has an average particle diameter of 0.01 μm or more and 0.5 μm or less.
7. The conductive paste according to claim 1 or 2, wherein the binder resin contains a butyral based resin.
8. The conductive paste according to claim 1 or 2, wherein the conductive paste has a shear rate of 100sec -1 The viscosity at the time of the reaction is 0.8 Pa.S or less, and the shear rate at the time of the reaction is 10000sec -1 The viscosity at the time is 0.18 Pa.S or less.
9. The electroconductive paste according to claim 1 or 2, wherein the electroconductive paste is used for internal electrodes of a laminated ceramic part.
10. An electronic component formed using the electroconductive paste according to any one of claims 1 to 8.
11. A multilayer ceramic capacitor comprising a laminate of at least a dielectric layer and an internal electrode formed by using the electroconductive paste according to claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018241705 | 2018-12-25 | ||
| JP2018-241705 | 2018-12-25 | ||
| PCT/JP2019/045824 WO2020137289A1 (en) | 2018-12-25 | 2019-11-22 | Conductive paste, electronic component, and laminated ceramic capacitor |
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| Publication Number | Publication Date |
|---|---|
| CN113227233A CN113227233A (en) | 2021-08-06 |
| CN113227233B true CN113227233B (en) | 2023-12-12 |
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| CN201980085792.8A Active CN113227233B (en) | 2018-12-25 | 2019-11-22 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| JP (1) | JP7405098B2 (en) |
| KR (1) | KR20210110285A (en) |
| CN (1) | CN113227233B (en) |
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| WO (1) | WO2020137289A1 (en) |
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| CN112322099A (en) * | 2020-10-21 | 2021-02-05 | 河北银隆新能源有限公司 | Primer slurry, battery pole piece, preparation method of battery pole piece and battery |
| JP7544157B2 (en) * | 2021-02-02 | 2024-09-03 | 株式会社村田製作所 | Inorganic particle-containing paste, inorganic particle-containing film, and laminate |
| WO2024062857A1 (en) * | 2022-09-21 | 2024-03-28 | 住友金属鉱山株式会社 | Electrically conductive paste, electronic component, and multilayer ceramic capacitor |
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- 2019-11-22 WO PCT/JP2019/045824 patent/WO2020137289A1/en active Application Filing
- 2019-11-22 JP JP2020562938A patent/JP7405098B2/en active Active
- 2019-11-22 KR KR1020217012061A patent/KR20210110285A/en not_active Application Discontinuation
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| WO2020137289A1 (en) | 2020-07-02 |
| JPWO2020137289A1 (en) | 2021-11-04 |
| TW202034353A (en) | 2020-09-16 |
| CN113227233A (en) | 2021-08-06 |
| KR20210110285A (en) | 2021-09-07 |
| JP7405098B2 (en) | 2023-12-26 |
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