CN113227233A - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
- Publication number
- CN113227233A CN113227233A CN201980085792.8A CN201980085792A CN113227233A CN 113227233 A CN113227233 A CN 113227233A CN 201980085792 A CN201980085792 A CN 201980085792A CN 113227233 A CN113227233 A CN 113227233A
- Authority
- CN
- China
- Prior art keywords
- conductive paste
- acid
- mass
- dispersant
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003985 ceramic capacitor Substances 0.000 title claims description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 146
- 239000000843 powder Substances 0.000 claims abstract description 100
- 239000002253 acid Substances 0.000 claims abstract description 91
- 239000000919 ceramic Substances 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011354 acetal resin Substances 0.000 claims abstract description 13
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- 239000004210 ether based solvent Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
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- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims 1
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- 230000003746 surface roughness Effects 0.000 description 23
- 238000007646 gravure printing Methods 0.000 description 21
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- 238000000034 method Methods 0.000 description 14
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- 238000011156 evaluation Methods 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
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- 239000001856 Ethyl cellulose Substances 0.000 description 7
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- 239000012298 atmosphere Substances 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 6
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- 238000007747 plating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRKIAJBQOUBNSE-GYSYKLTISA-N Isobornyl isobutyrate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(C)C)C[C@@H]1C2(C)C KRKIAJBQOUBNSE-GYSYKLTISA-N 0.000 description 2
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- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- FAFMZORPAAGQFV-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] propanoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)CC)C[C@@H]1C2(C)C FAFMZORPAAGQFV-BREBYQMCSA-N 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- DIICMQCJAQLQPI-UHFFFAOYSA-N isobornyl propionate Natural products CCC(=O)C1CC2CCC1(C)C2(C)C DIICMQCJAQLQPI-UHFFFAOYSA-N 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
-
- 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
-
- 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
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Abstract
The invention provides a conductive paste with excellent dispersibility and the like. 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 includes a first acid-based dispersant and a second acid-based dispersant, the first acid-based dispersant has an average molecular weight of more than 500 and 2000 or less and has one or more branched chains 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 includes an acetal resin, and the organic solvent includes a glycol ether-based solvent.
Description
Technical Field
The invention relates to a conductive paste, an electronic component and a multilayer ceramic capacitor.
Background
With the miniaturization and high performance of electronic devices such as mobile phones and digital devices, miniaturization and high capacity are also demanded for electronic components including multilayer ceramic capacitors and the like. The multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and can be reduced in size and increased in capacity by making the dielectric layers and the internal electrode layers thin.
For example, a laminated ceramic capacitor can be manufactured as follows. Firstly, barium titanate (BaTiO) is added3) The conductive paste for internal electrodes is printed (applied) on the surfaces of the dielectric green sheets of the dielectric powder and the binder resin in a predetermined electrode pattern, and dried to form a dry film. Then, the dry film and the dielectric green sheet are alternately stacked, and are heated and pressed to be bondedIntegrated to form a crimp body. The pressure-bonded body is cut, subjected to a binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip (laminate). Next, an external electrode paste is applied to both ends of the fired chip (laminate), 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 of0.11 pas or more and a shear rate of 0.02(s)-1) Viscosity η of0.02A thixotropic fluid that satisfies the conditions expressed by a specific formula.
Patent document 2 describes a conductive paste for the purpose of passing through the conductive paste, as in patent document 1An electroconductive paste for forming an internal conductor film by gravure printing, which comprises 30 to 70 wt% of a solid component containing a metal powder, 1 to 10 wt% of a resin component, 0.05 to 5 wt% of a dispersant, and the balance being a solvent component, and has a shear rate of 0.1(s)-1) A thixotropic fluid having a viscosity of 1Pa s or more at a shear rate of 0.1(s)-1) The shear rate was 10(s) based on the viscosity-1) The viscosity change rate is 50% or more.
According to the above patent documents 1 and 2, the shear rate of the conductive paste is 0.1(s)-1) A thixotropic fluid having a viscosity of 1 pas or more, and can provide stable continuous printability at high speed in gravure printing, and can produce a multilayer ceramic electronic component such as a multilayer ceramic capacitor with good production efficiency.
Patent document 3 describes a conductive paste for an internal electrode of a multilayer ceramic capacitor, which contains a conductive powder (a), an organic resin (B), an organic solvent (C), an additive (D), and a dielectric powder (E), wherein the organic resin (B) is composed of polyvinyl butyral having a polymerization degree of 10000 or more and 50000 or less and ethyl cellulose having a weight average molecular weight of 10000 or more and 100000 or less, the organic solvent (C) is composed of propylene glycol monobutyl ether, or a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, or a mixed solvent of propylene glycol monobutyl ether and mineral spirits, the additive (D) is composed of a separation inhibitor and a dispersant, and the separation inhibitor is composed of a composition containing a polycarboxylic acid polymer or a polycarboxylate. According to patent document 3, the conductive paste has a viscosity suitable for gravure printing, and can improve the uniformity and stability of the paste, and has good drying properties.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-187638
Patent document 2: japanese patent laid-open publication No. 2003 and No. 242835
Patent document 3: japanese laid-open patent publication No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
With the recent reduction in the thickness of the internal electrode layer, the conductive powder tends to have a smaller particle size. When the particle diameter of the conductive powder is small, the specific surface area of the particle surface thereof becomes large, and therefore the surface activity of the conductive powder (metal powder) becomes high, and the dispersibility of the conductive paste may decrease, and a conductive paste having a higher dispersibility is required.
In addition, when printing the conductive paste by the gravure printing method, since a paste viscosity lower than that of the screen printing method is required, it is considered that the conductive powder having a large specific gravity is precipitated to lower the dispersibility of the paste. In the conductive pastes described in patent documents 1 and 2, the dispersibility of the paste is improved by removing the lumps in the conductive paste using a filter, but the process of removing the lumps is required, and the production process is therefore easily complicated.
In view of such circumstances, an object of the present invention is to provide a conductive paste 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 2000 or less and having one or more branches composed of a hydrocarbon group with respect to a 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 comprises an acetal resin, and the organic solvent comprises a glycol ether-based 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 atomsOr an alkenyl group having 10 to 20 carbon atoms. Preferably, the first acid-based dispersant is contained in an amount of 0.2 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the conductive powder, and the second acid-based dispersant is contained in an amount of 0.01 parts by mass or more and 2 parts by mass or less with respect to 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. 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 size of the ceramic powder is preferably 0.01 μm or more and 0.5 μm or less. The binder resin preferably contains a butyral resin. The conductive paste is preferably used for internal electrodes of a multilayer ceramic component. In addition, preferably, the conductive paste has a shear rate of 100sec-1The viscosity at that time is 0.8Pa · S or less, and the shear rate is 10000sec-1The viscosity is 0.18Pa · S or less.
In a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.
In a third aspect of the present invention, there is provided a multilayer ceramic capacitor including at least a multilayer body in which dielectric layers and internal electrode layers are laminated, the internal electrode layers being formed using the conductive paste.
Effects of the invention
The conductive paste of the present invention is excellent in dispersibility and productivity of the paste. In addition, the conductive paste of the present invention has a viscosity suitable for gravure printing. 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 a is a perspective view showing a multilayer ceramic capacitor according to the embodiment, and fig. 1B 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. Hereinafter, each component will be described in detail.
(conductive powder)
The conductive powder is not particularly limited, and a metal powder may be used, and for example, at least one powder selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof may be used. Among them, from the viewpoint of conductivity, corrosion resistance and cost, it is preferable to use a powder of Ni or an alloy thereof (hereinafter, sometimes referred to as "Ni powder"). 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, the Ni powder may contain the element S in an amount of several hundred ppm 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 average particle diameter of the conductive powder is preferably 0.05 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. 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 (laminated ceramic member) 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 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 observed at a magnification of 10,000 times by SEM.
The content of the conductive powder is preferably 30 mass% or more and less than 70 mass%, and more preferably 40 mass% or more and 60 mass% or less with respect to the total amount of the conductive paste. When the content of the conductive powder is within the above range, the conductivity and dispersibility are excellent.
(ceramic powder)
The ceramic powder is not particularly limited, and may be used in a multilayer ceramic capacitorIn the case of the conductive paste for the partial electrode, a known ceramic powder can be appropriately selected according to the type of the 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)。
As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. Examples of the oxide include at least one oxide selected from the group consisting of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and rare earth elements.
Further, as the ceramic powder, for example, barium titanate (BaTiO) can be used3) 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.
When used as a conductive paste for internal electrodes, the ceramic powder may have the same composition as that of the dielectric ceramic powder constituting the dielectric green sheets of a multilayer ceramic capacitor (electronic device). This can suppress the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the firing step. Examples of such ceramic powders include, in addition to the perovskite-type oxides containing Ba and Ti, ZnO, ferrite, PZT, BaO, and Al2O3、Bi2O3R (rare earth element)2O3、TiO2、Nd2O3And the like. One kind of the ceramic powder may be used, or two or more kinds may be used.
The average particle size of the ceramic powder is, for example, in the range of 0.01 to 0.5. mu.m, preferably in the range of 0.01 to 0.3. mu.m. 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 observed at a magnification of 50,000 times by SEM.
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 total amount of the conductive paste.
(Binder 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 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 of an acetal resin, or only the acetal resin. In addition, even if the content of the acetal resin is less than 40 mass% with respect to the entire binder resin, the adhesive composition can have a low paste viscosity and a sufficient adhesive strength.
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 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 solvent include (di) glycol ethers such as diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, and ethylene glycol monohexyl ether, and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether (PNB). Among them, propylene glycol monoalkyl ethers are preferable, and propylene glycol monobutyl ether (PNB) is more preferable. When the organic solvent contains a glycol ether solvent, the organic solvent is excellent in compatibility with the binder resin and excellent in drying property.
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.
The organic solvent may further contain an acetate-based solvent. Examples of the acetate-based solvent include glycol ether acetates such as dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxypropyl-2-acetate.
When the organic solvent contains an acetate-based solvent, for example, the acetate-based solvent (a) may contain at least one selected from the group consisting of dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. Among them, isobornyl acetate is more preferable. The acetate-based solvent is contained in an amount of 0 to 80% by mass, preferably 10 to 60% by mass, and more preferably 20 to 40% by mass, based on the total 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 acetate-based solvent. In the case of the mixed solution, the acetate-based solvent (B) is preferably contained in an amount of 10 mass% to 50 mass%, more preferably 20 mass% to 40 mass%, based on 100 mass% of the entire acetate-based solvent.
The organic solvent may contain other organic solvents besides the glycol ether solvent and the acetate solvent. The other organic solvent is not particularly limited, and a known organic solvent capable of dissolving the binder resin can be used. Examples of the other organic solvent include acetate solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, terpene solvents such as terpineol and dihydroterpineol, and aliphatic hydrocarbon solvents such as tridecane, nonane, and cyclohexane. Among them, an aliphatic hydrocarbon solvent is preferable, and mineral spirits are more preferable among aliphatic hydrocarbon solvents. One or two or more of the other organic solvents may be used.
The organic solvent may contain, for example, a glycol ether solvent as a main solvent and an aliphatic hydrocarbon solvent as a sub-solvent. In this case, the glycol ether solvent is preferably contained in an amount of 30 parts by mass or more and 50 parts by mass or less, more preferably 40 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the conductive powder, and the aliphatic hydrocarbon solvent is preferably contained 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 conductive powder contains 25 parts by mass or more of the aliphatic hydrocarbon solvent based on 100 parts by mass of the conductive powder, the conductive paste has excellent dispersibility.
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%, 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.
(dispersing agent)
The inventors of the present invention have studied various dispersants with respect to a dispersant used in a conductive paste, and as a result, have found that by using a dispersant containing a first acid-based dispersant having an average molecular weight of more than 500 and 2000 or less and having one or more branched chains composed of a hydrocarbon group with respect to a main chain and a second acid-based dispersant having a carboxyl group other than the first acid-based dispersant, the dispersibility of a powder material (conductive powder, ceramic powder) contained in the conductive paste is excellent, and the smoothness of a dried film surface is excellent.
Although the reason why the effect is obtained is not clearly understood, it is considered that the steric hindrance is effectively formed and the aggregation of the powder material is suppressed by providing the first acid-based dispersant with a branch chain made of a hydrocarbon group, and the carboxyl group is provided in the second acid-based dispersant, whereby the first acid-based dispersant can be more effectively dispersed. Further, by setting the molecular weight of the first acid-based dispersant to a specific size, it is possible to maintain a viscosity suitable for 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 preferably has at least one branch chain made of a hydrocarbon group, preferably a plurality of branch chains made of 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. 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 hydrogen constituting the alkyl group may be substituted with a substituent.
The molecular weight of the first acid-based dispersant is greater than 500 and 2000 or less, and may be 1000 or more and 2000 or less. When the molecular weight is in the above range, the dispersibility of the conductive powder or ceramic powder is excellent, and the density and smoothness of the surface of the dried film are excellent. In the present specification, the molecular weight of the dispersant means a weight average molecular weight when the molecular weight of the dispersant has a certain degree of distribution.
The first acid-based dispersant may be selected from commercially available products, for example, and used so as to satisfy the above-described characteristics. The 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 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the conductive powder. When the content of the acid-based dispersant is in the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the surface of the dried electrode after coating are 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, even if the content of the acid-based dispersant is 1 part by mass or less, the conductive paste can have high dispersibility.
The second acid-based dispersant is an acid-based dispersant having a carboxyl group. The molecular weight of the second acid-based dispersant is preferably 5000 or less, more preferably 1000 or less, and still more preferably 500 or less. The second acid-based dispersant is, for example, an acid-based dispersant having a hydrocarbon group. The hydrocarbon group preferably contains an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. When the second acid-based dispersant has the above-described structure, the effect of 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 acid-based dispersants such as higher fatty acids and amino acids. Further, the second dispersant may be used singly or in combination.
The higher fatty acid may be an unsaturated carboxylic acid or a saturated carboxylic acid, and examples thereof include, but are not particularly limited to, higher fatty acids having 11 or more carbon atoms such as stearic acid, oleic acid, behenic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid. Among them, oleic acid or stearic acid is preferable.
The second acid-based dispersant other than the higher fatty acid is not particularly limited, and examples thereof include surfactants selected from the following: the preferred examples of the antioxidant include those of the monoamine type represented by monoalkylamine salts, those of the diaminoalkyl type represented by N-alkyl (C14-C18) propylenediamine dioleate, those of the trimethylalkyl ammonium represented by alkyltrimethylammonium chloride, those of the dimethylbenzyl alkyl ammonium represented by palmityldimethylbenzylammonium chloride, those of the quaternary ammonium represented by alkyl/polyoxyethylenemethylammonium chloride, those of the alkylpyridinium, those of the tertiary amine represented by dimethylstearylamine, those of the polyoxyethylenealkylamine represented by polyoxypropylene/polyoxyethylenealkylamine, and those of the diamine represented by N, N ', N' -tris (2-hydroxyethyl) -N-alkyl (C14-18) 1, 3-diaminopropane, and among these, the monoamine type is preferably the alkylmonoamine salt.
The alkyl monoamine salt type is preferably oleoylsarcosine, lauroylsarcosine, or stearic acid amide.
The second acid-based dispersant is 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 surface smoothness of the dried electrode 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, may be 0.1 part by mass or less, and may be 0.05 part by mass or less.
The second acid-based dispersant may be contained by, for example, about 1 part by mass or more and about 500 parts by mass or less, preferably about 50 parts by mass or more and about 300 parts by mass or less, more preferably about 50 parts by mass or more and about 200 parts by mass or less, and still more preferably about 50 parts by mass or more and about 150 parts by mass or less, 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 the dispersants, or may contain a dispersant other than the above-described acid-based dispersant within a range not to impair 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, and the like, an alkali-based dispersant, an amphoteric surfactant, a polymer-based dispersant, and the like, and an alkali-based dispersant is more preferably contained. These dispersants may be used singly or in combination.
The content (total content) of the entire dispersant including the first acid-based dispersant and the second acid-based dispersant is preferably 0.01 to 3 parts by mass, more preferably 0.23 to 3 parts by mass, 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 may be 1 part by mass or less. Even if the content of the whole dispersant is within the above range, the dispersant can have high dispersibility.
The total content of the acid-based dispersant is preferably 3% by mass or less based on the total amount of the conductive paste. The upper limit of the total content of the dispersant is preferably 2% by mass or less, and more preferably 1% by 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 corrosion 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 components, 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 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 spreads over the surface, thereby facilitating the production of a uniform conductive paste. Alternatively, the conductive paste may be prepared by dissolving the binder resin in a part of the organic solvent in advance, preparing the organic vehicle, adding the conductive powder, the ceramic powder, the dispersant and the organic vehicle to the organic solvent for paste adjustment, and then stirring and kneading the mixture.
The conductive paste has a shear rate of 100sec-1The viscosity at the time of use is preferably 0.8Pa · S or less, may be 0.5Pa · S or less, may be 0.4Pa · S or less, may be 0.3Pa · S or less, and may be 0.25Pa · S or less. When the shear rate is 100sec-1When the viscosity is within the above range, the conductive paste can be suitably used as a conductive paste for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. The shear rate of the conductive paste of the present embodiment is 100sec-1The lower limit of the viscosity in the case of (3) is not particularly limited, and is, for example, 0.1Pa · S or more.
In addition, the conductive paste had a shear rate of 10000sec-1The viscosity at that time is preferably 0.18 pas or less, and may be less than 0.14 pas. When the shear rate is 10000sec-1When the viscosity is within the above range, the conductive paste can be suitably used as a conductive paste for gravure printing. If the viscosity exceeds the above range, the viscosity may be too high to be suitable for gravure printing. For shear rate of 10000sec-1The lower limit of the viscosity in the case of (3) is not particularly limited, and is, for example, 0.05Pa · S or more.
In addition, after printing the conductive paste, the dry film obtained by drying preferably has a Dry Film Density (DFD) of more than 5.0g/cm3And may be 5.2g/cm3Above, it may be more than 5.2g/cm3And may be 5.3g/cm3The above. The upper limit of the dry film density is not particularly limited, and is not more than 9.8g/cm of the true density of metallic nickel3For example, it may be 6.5g/cm3The following.
The arithmetic average roughness Sa when a dried film having a thickness of 1 to 3 μm and a square width of 20mm is produced by printing a conductive paste and drying the paste at 120 ℃ for 1 hour in the air 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, but the surface is preferably flat, and a value exceeding 0 and a smaller value are more preferable. 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 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 multilayer ceramic device manufactured 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 electronic components and the like according to the present invention will be described below with reference to the drawings. In the drawings, the drawings are schematically illustrated and the scale may be changed as appropriate. The position, direction, and the like of the member will be described with reference to the XYZ rectangular coordinate system shown in fig. 1 and the like as appropriate. In the XYZ rectangular coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (vertical direction).
Fig. 1 a and 1B are views showing a multilayer ceramic capacitor 1 as an example of an electronic component according to an 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 and dried to form a dried film, and a plurality of dielectric green sheets having the dried film on the upper surface thereof are laminated by pressure bonding and then fired to be integrated, thereby preparing a multilayer ceramic fired body (multilayer body 10) as a ceramic capacitor main 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. In addition, from the viewpoint of the requirement for making the internal electrode layer 11 thinner, the thickness of the conductive paste (dry film) after printing is preferably 1 μm or less after drying.
Next, the dielectric green sheet was peeled off from the support film, and laminated so that the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet were alternately arranged, followed by heating and pressing to obtain a laminate (pressure-bonded body). In addition, a dielectric green sheet for protection, 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 a binder removal treatment and fired in a reducing atmosphere to produce a multilayer ceramic fired body (multilayer body 10). Further, the atmosphere in the binder removal treatment is preferably air or N2A gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature when the binder removal treatment is performed is preferably 0.5 hours or more and 24 hours or less. The firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used 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 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 pair of external electrodes 20 to the multilayer ceramic fired body (multilayer body 10) thus manufactured. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layers 21 are electrically connected to the internal electrode layers 11. Further, as the material of the external electrode 20, for example, copper, nickel, or an alloy thereof can be preferably used. In addition, electronic components other than the multilayer ceramic capacitor may be used.
[ examples ] A method for producing a compound
The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to the examples at all.
[ evaluation method ]
(viscosity of electroconductive paste)
Using a rheometer at a shear rate of 100sec-1、10000sec-1The viscosity of the conductive paste after production was measured under the conditions of (1).
(Dry film Density)
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 μm. The obtained PET film was dried at 120 ℃ for 40 minutes to form a dried film, and 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 after the PET film was peeled off, and the dried film density (average value) was calculated.
(surface roughness)
The prepared conductive paste was printed on a 2.54cm (1 inch) square heat-resistant tempered glass, and dried at 120 ℃ for 1 hour in the air to prepare a dried film having a thickness of 1 to 3 μm and a square thickness of 20 mm. The surface roughness Sa (arithmetic average roughness) of the produced dried film was measured using an apparatus 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 (the arithmetic average height of the line) into a plane.
[ materials used ]
(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) was used3(ii) a SEM average particle diameter of 0.10 μm).
(Binder resin)
As the binder resin, polyvinyl butyral resin (PVB) and Ethyl Cellulose (EC) are used.
(dispersing agent)
(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 branch chain composed of a hydrocarbon) having a polycarboxylic acid as a main chain was used.
(2) Oleoylsarcosine (C) was used as the second acid-based dispersant (B)21H39NO3)。
(3) For comparison, a phosphoric acid-based dispersant (C) (molecular weight: 1400, no 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]
With respect to 100 parts by mass of Ni powder as conductive powder, 25 parts by mass of ceramic powder, 0.2 parts 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 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 were mixed to prepare conductive paste. The viscosity of the prepared conductive paste, the dry film density of the paste, and the surface roughness were evaluated by the methods described above. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste are shown in table 2.
[ example 2]
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 dispersant and the like in the conductive paste are shown in Table 1, and the conductivity is shown in 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 changed to 2.0 parts by mass. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness 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 2, except that the content of the second acid-based dispersant (B) was 0.01 part by mass. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness 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 2, except that the content of the second acid-based dispersant (B) was 2.0 parts by mass. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness 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 the content of the first acid-based dispersant (a) was 0.6 parts by mass and the content of the second acid-based dispersant (B) was 1.2 parts by mass. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness 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 parts by mass of a phosphoric acid-based dispersant 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, the dry film density, and the surface roughness of the conductive paste are shown in table 2.
Comparative example 2
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 sub-solvent was used. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste are shown in table 2.
Comparative example 3
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 a binder resin and PVB was not used. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste 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 a 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, the dry film density, and the surface roughness of the conductive paste 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 part by mass of the second acid-based dispersant (B) was used as the dispersant. The contents of the dispersant and the like in the conductive paste are shown in table 1, and the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste are shown in table 2.
TABLE 2
(evaluation results)
The conductive paste of the example was cut at a shear rate of 100sec-1The viscosity at that time is 0.20 to 0.23 pas and the shear rate is 10000sec-1The viscosity of the ink composition is 0.11 to 0.14 pas, and the ink composition shows a low value stably at any shear rate, indicating that the ink composition has a viscosity suitable for gravure printing. In addition, it was confirmed that the dry film density of the conductive paste of the examples was 5.1 to 5.4g/cm3The surface roughness of the dried film is 0.13 to 0.16 μm, and the dispersibility is excellent.
In addition, in the case of comparing the conductive pastes of examples 1 to 3, it is understood that the dry film density is increased and the surface roughness becomes smoother as the content of the first acid-based dispersant (a) is increased. In example 3, the dry film density and surface roughness were almost saturated values. As is clear from examples 2, 4 and 5, the dry film density and the surface roughness can be improved by increasing the content of the second acid-based dispersant. Further, as is clear from comparison of the conductive pastes of examples 1 and 4 and example 6, when the mixing ratios are close to each other, the dry film density and the surface roughness tend to be good as compared with the case where the mixing ratios of the first acid-based dispersant (a) and the second acid-based dispersant (B) are greatly different.
On the other hand, when the conductive paste of comparative example 1, which did not contain the first acid-based dispersant but used the phosphoric acid-based dispersant, was produced under the same conditions, the viscosity was higher than that of the example, the dry film density could not be sufficiently increased, and the surface roughness was higher than that of the example.
In addition, the conductive paste of comparative example 2, which uses TPO generally used as a main solvent, has a very high viscosity and is not suitable for gravure paste, and the surface roughness is higher than that of the examples. In addition, the conductive paste of comparative example 3, which contained no acetal resin in the binder resin, had a high viscosity and failed to sufficiently increase the dry film density.
It is also shown that 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 has a higher dry film density, a lower surface roughness, and improved dispersibility as compared with comparative example 1 using a phosphoric acid-based dispersant.
As is clear from the above, when the conductive paste of the example of the present invention containing both the first acid-based dispersant (a) and the second acid-based dispersant (B) was compared with the conductive pastes of the comparative examples and the reference examples, the dry film density was higher, the surface roughness was lower, and the dispersibility of the conductive paste was further improved. In addition, it is found that the conductive paste of the example of the present invention containing both dispersants is also lower in viscosity than the conductive pastes of the comparative examples and the reference examples, 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-described embodiments and the like may be omitted. In addition, the elements described in the above embodiments and the like can be combined as appropriate. The disclosures of all documents cited in the above-described embodiments and the like are incorporated by reference as part of the description herein, as far as permitted by law.
Industrial applicability
The conductive paste of the present invention has a viscosity suitable for gravure printing, and has a high density of a dried film after coating, excellent surface smoothness of the dried film, and excellent dispersibility. 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 which are becoming smaller in size, such as mobile phones and digital devices, 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-described embodiments and the like may be omitted. In addition, the elements described in the above embodiments and the like can be combined as appropriate. In addition, the contents of japanese patent application No. 2018-.
Description of the reference numerals
1 laminated ceramic capacitor
10 ceramic laminate
11 internal electrode layers
12 dielectric layer
20 external electrode
21 external electrode layer
22 plating layer
Claims (14)
1. 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 and a second acid-based dispersant,
the first acid-based dispersant has an average molecular weight of more than 500 and 2000 or less and has one or more branches 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 resin and a binder resin,
the organic solvent includes a glycol ether-based solvent.
2. The conductive paste according to claim 1, wherein the first acid-based dispersant has a carboxyl group.
3. The conductive paste according to claim 1 or 2, wherein the first acid-based dispersant is a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain.
4. The conductive paste according to any one of claims 1 to 3, 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.
5. The conductive paste according to any one of claims 1 to 4, wherein the first acid-based dispersant is contained in an amount of 0.2 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the conductive powder, and the second acid-based dispersant is contained in an amount of 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the conductive powder.
6. The conductive paste according to any one of claims 1 to 5, wherein the conductive powder contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof.
7. The conductive paste according to any one of claims 1 to 6, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
8. The conductive paste according to any one of claims 1 to 7, wherein the ceramic powder contains a perovskite oxide.
9. The conductive paste according to any one of claims 1 to 8, wherein the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less.
10. The electroconductive paste according to any one of claims 1 to 9, wherein the binder resin contains a butyral based resin.
11. The electroconductive paste according to any one of claims 1 to 10, wherein the electroconductive paste has a shear rate of 100sec-1The viscosity at that time is 0.8Pa · S or less, and the shear rate is 10000sec-1The viscosity is 0.18Pa · S or less.
12. The conductive paste according to any one of claims 1 to 11, wherein the conductive paste is used for an internal electrode of a laminated ceramic member.
13. An electronic component, wherein the conductive paste according to any one of claims 1 to 11 is used to form the electronic component.
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 claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| 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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| CN113227233A true CN113227233A (en) | 2021-08-06 |
| CN113227233B CN113227233B (en) | 2023-12-12 |
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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 |
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| KR20230128323A (en) * | 2021-02-02 | 2023-09-04 | 가부시키가이샤 무라타 세이사쿠쇼 | 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
- 2019-11-22 WO PCT/JP2019/045824 patent/WO2020137289A1/en active Application Filing
- 2019-11-22 CN CN201980085792.8A patent/CN113227233B/en active Active
- 2019-11-22 JP JP2020562938A patent/JP7405098B2/en active Active
- 2019-11-22 KR KR1020217012061A patent/KR20210110285A/en not_active Application Discontinuation
- 2019-11-28 TW TW108143497A patent/TW202034353A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| WO2013161976A1 (en) * | 2012-04-27 | 2013-10-31 | 富士フイルム株式会社 | Radiation sensitive composition, light-blocking film and solid-state imaging element |
| CN105981111A (en) * | 2013-12-10 | 2016-09-28 | 同和电子科技有限公司 | Conductive paste and method for manufacturing conductive film using same |
| JP2015149121A (en) * | 2014-02-04 | 2015-08-20 | 大日本印刷株式会社 | Copper particle dispersion paste and manufacturing method of conductive substrate |
| CN105860054A (en) * | 2015-02-06 | 2016-08-17 | 日油株式会社 | Nonaqueous dispersant and nonaqueous dispersion composition |
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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 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210110285A (en) | 2021-09-07 |
| TW202034353A (en) | 2020-09-16 |
| JP7405098B2 (en) | 2023-12-26 |
| CN113227233B (en) | 2023-12-12 |
| JPWO2020137289A1 (en) | 2021-11-04 |
| WO2020137289A1 (en) | 2020-07-02 |
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