CN112786309B - Paste for external electrode - Google Patents
Paste for external electrode Download PDFInfo
- Publication number
- CN112786309B CN112786309B CN202011219717.7A CN202011219717A CN112786309B CN 112786309 B CN112786309 B CN 112786309B CN 202011219717 A CN202011219717 A CN 202011219717A CN 112786309 B CN112786309 B CN 112786309B
- Authority
- CN
- China
- Prior art keywords
- paste
- external electrode
- resin
- solvent
- electrode paste
- 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.)
- Active
Links
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 60
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 32
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 32
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 239000002003 electrode paste Substances 0.000 claims description 59
- 239000000919 ceramic Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 7
- -1 ester alcohols Chemical class 0.000 claims description 3
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 2
- 238000005520 cutting process Methods 0.000 description 17
- 239000003985 ceramic capacitor Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/26—Cellulose ethers
- C09J101/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
-
- 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
- C08K2003/085—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Provided is a paste for external electrodes, which can suppress expansion of the central portion compared with the end portions when applied. The paste for external electrodes comprises: a resin comprising at least a portion of a copolymerized ethylcellulose-based resin and an acrylic resin; a Cu filler; and a solvent, wherein an interfacial tension generated between the resin and the solvent is 15mN/m or more.
Description
Technical Field
The present invention relates to an external electrode paste used for forming an external electrode of an electronic component.
Background
Conventionally, a method of forming external electrodes of electronic components such as a multilayer ceramic capacitor using external electrode paste has been known. Such external electrode paste generally contains a resin as a binder, a metal filler, and a solvent.
Patent document 1 describes an adhesive composition containing Ethylcellulose (ethylcellosose) and an acrylic polymer, and describes the use of such an adhesive composition for the production of laminated ceramic capacitors and the like. The adhesive composition is a composition in which ethylcellulose and an acrylic polymer are simply mixed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-71986
When a conventional external electrode paste such as the external electrode paste containing the adhesive composition described in patent document 1 is applied to a ceramic body, the central portion expands compared with the end portions due to the influence of surface tension or the like. Therefore, the formed external electrode has a convex shape with a thick central portion and thin end portions, and thus, miniaturization of the electronic component becomes difficult.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an external electrode paste which can suppress expansion of the central portion compared with the end portions when the paste is applied.
Means for solving the problems
The paste for external electrodes of the present invention is characterized by comprising: a resin comprising at least a portion of a copolymerized ethylcellulose (Ethocel) based resin and an acrylic based resin; a Cu filler; and a solvent, wherein an interfacial tension generated between the resin and the solvent is 15mN/m or more.
Effects of the invention
According to the external electrode paste of the present invention, the expansion of the central portion compared to the end portions can be suppressed when the paste is applied. Therefore, the electronic component manufactured using the paste for external electrodes of the present invention can be miniaturized.
Drawings
Fig. 1 is a diagram schematically showing the structure of a resin including at least a part of a copolymerized ethylcellulose-based resin and an acrylic resin.
Fig. 2 is a graph showing a relationship between the weight% of the ethylcellulose-based resin in the resin and the interfacial tension generated between the resin and the solvent.
Fig. 3 is a diagram for explaining a process of applying the external electrode paste to the ceramic body, in which fig. 3 (a) shows a state in which the ceramic body is immersed in the external electrode paste, fig. 3 (b) shows a state in which the ceramic body is lifted, fig. 3 (c) shows a state in which an outward flow of the external electrode paste from the center portion to the end portion is generated, and fig. 3 (d) shows a state in which the external electrode paste is dried.
Fig. 4 is a diagram showing the external shape and cutting position of a ceramic body used when investigating the flatness of the external electrode paste.
Fig. 5 (a) is a schematic cross-sectional view of a laminated ceramic capacitor in which external electrodes are formed using the external electrode paste of the present invention, and fig. 5 (b) is a schematic cross-sectional view of a laminated ceramic capacitor in which external electrodes are formed using a conventional external electrode paste.
Description of the reference numerals
10: ethylcellulose
11: vinyl group
20: acrylic resin
31: paste for external electrode
31a: paste for external electrode adhered to ceramic body
32: ceramic body
40: ceramic body
41: end face
42: internal electrode
50a, 50b: laminated ceramic capacitor
51a, 51b: ceramic body
52a, 52b: an external electrode.
Detailed Description
The following shows embodiments of the present invention, and specifically describes features of the present invention.
The paste for external electrodes in one embodiment comprises: a resin comprising at least a portion of a copolymerized ethylcellulose-based resin and an acrylic resin; a Cu filler; and a solvent, wherein an interfacial tension generated between the resin and the solvent is 15mN/m or more.
The ethylcellulose-based resin is, for example, at least 1 kind of ethylcellulose, methylcellulose, hydroxypropyl cellulose, tritylcellulose, acetylcellulose, carboxymethyl cellulose, and nitrocellulose.
The acrylic resin is, for example, at least 1 of isobutyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate.
The Cu filler is a particle containing at least one of Cu and a Cu alloy.
The solvent comprises, for example, terpineol, dihydroterpineol acetate, propylene glycol phenyl ether, benzyl alcohol,At least 1 of the ester alcohols and butyl carbitol acetate. The solvent species can be separated by measuring the generated gas by gas chromatography mass spectrometryAnd (5) separating. Gas chromatography mass spectrometry can be performed, for example, using a mass spectrometer 7890A/5975C (500 ℃ C. Heating) manufactured by Agilent technologies (Agilent Technology) Inc.
As described above, at least a part of the ethylcellulose-based resin and the acrylic resin is copolymerized. As an example, the OH group of the ethylcellulose resin is replaced with a vinyl group, and the ethylcellulose resin and the acrylic resin are bonded via the replaced vinyl group.
Fig. 1 is a diagram schematically showing the structure of a resin including at least a part of a copolymerized ethylcellulose-based resin and an acrylic resin. Fig. 1 is a schematic diagram showing a case where the ethylcellulose-based resin is ethylcellulose 10. As shown in fig. 1, a part of ethyl cellulose 10 and a part of acrylic resin 20 are copolymerized. As described above, the OH group of the ethylcellulose 10 may be replaced with the vinyl group 11, and the ethylcellulose 10 and the acrylic resin 20 may be bonded via the replaced vinyl group 11. In addition, at least a portion of ethylcellulose 10 is hydrogen bonded.
Fig. 2 is a graph showing a relationship between the weight% of the ethylcellulose-based resin in the resin and the interfacial tension generated between the resin and the solvent. In the paste for external electrodes of the present embodiment, the interfacial tension generated between the resin and the solvent is 15mN/m or more. Since the interfacial tension between the resin and the solvent is 15mN/m or more, the force of the outward flow due to the interfacial tension difference due to the Coffee Ring Effect (Coffee-Ring Effect) becomes larger, and thus the fluidity is improved as compared with the conventional paste for external electrodes, and the expansion of the central portion at the time of application can be suppressed from being formed as compared with the end portions.
When the ratio of the ethylcellulose-based resin in the resin is 20% by weight or more and 50% by weight or less, the interfacial tension generated between the resin and the solvent becomes 40mN/m or more and less than 56mN/m, and the swelling of the central portion compared with the end portions when the external electrode paste is applied can be more effectively suppressed. Therefore, the interfacial tension generated between the resin and the solvent is preferably 40mN/m or more and less than 56mN/m.
In addition, when forming an external electrode using a paste for an external electrode containing a Cu filler, it is necessary to burn the electrode by lowering the oxygen partial pressure in order to suppress occurrence of bubble defects and suppress oxidation of Cu. That is, a resin which is decomposed even if oxygen is small is preferably used as the binder, and a resin containing a large amount of an acrylic resin is preferably used as such a resin.
Here, the interfacial tension generated between the resin and the solvent can be obtained by the following method. First, a resin contained in a paste for external electrodes is coated on a glass substrate and dried, thereby obtaining a resin film. Next, the contact angles of pure water, diiodomethane, ethylene glycol with respect to the resin film were measured using a contact angle meter, and the surface free energy of the resin was calculated from the measured values. For example, a full-automatic contact angle meter "DMo-701" of the company, interfacial science co.ltd can be used as the contact angle meter.
Next, the contact angle of the solvent with respect to the resin film was measured. Finally, the interfacial tension is calculated by substituting the calculated surface free energy of the resin and the measured contact angle of the solvent into Dupre (dupray) formula and Young-Dupre formula.
In the case of using an external electrode paste that does not contain an ethylcellulose resin and an acrylic resin in a simple manner, the dried coating film becomes fragile. Therefore, in the sheet-type electronic component coated with such external electrode paste, defects and peeling of the dry coating film may occur during the transportation process. This is thought to be caused by the following reason.
The dry coating film obtained by coating the external electrode paste containing the ethylcellulose-based resin and at least a part of the acrylic resin copolymerized resin has flexibility derived from the acrylic resin and rigidity derived from the ethylcellulose-based resin, and has sufficient strength as the dry coating film.
In contrast, in the paste for external electrodes containing the unpolymerized ethylcellulose resin and acrylic resin, phase separation of the acrylic resin and ethylcellulose resin is promoted in the kneading step with the Cu filler in the production process, and thus glass frit segregation occurs in the paste for external electrodes. It is considered that if an external force is applied to a dry coating film obtained by applying the external electrode paste, cracks tend to develop from a weak portion such as the interface between the glass segregated portion and Cu, which causes chipping or peeling. Further, chipping and peeling of the external electrode of the chip electronic component can be detected by observing the appearance with an optical microscope.
Fig. 3 is a diagram for explaining a process of applying the external electrode paste 31 in the present embodiment to the ceramic body 32.
First, the region of the ceramic body 32 where the external electrode is formed is immersed in the external electrode paste 31 (see fig. 3 a), and then lifted up (see fig. 3 b). The regions where the external electrodes are formed are, for example, both end surfaces of the ceramic body 32. Here, the external electrode paste adhered to the ceramic body 32 will be described with reference numeral 31 a. If the ceramic body 32 is lifted up, marangoni (Marangoni) convection occurs as indicated by an arrow in fig. 3 (b) due to a temperature difference between the central portion and the end portion of the external electrode paste 31a adhering to the ceramic body 32 and a concentration difference of the solute. The solute is a Cu filler and a resin contained in the paste for external electrodes.
The amount of paste applied to the external electrode at the end portions is smaller than that at the central portion, and thus drying of the end portions is easier to advance. Therefore, the proportion of the resin in the paste for external electrodes is greater at the end than at the center, and the paste for external electrodes is unstable in energy, and thus an outward flow of the paste for external electrodes from the center to the end is generated (see fig. 3 (c)). The outward flow is generated during a period when the resin concentration at the end portion is higher than that at the center portion. Further, it is considered that if drying proceeds, the interface between the solute and the solvent increases, and the interfacial tension at this time becomes more unstable in energy and the outward flow becomes stronger.
Here, since the ethylcellulose-based resin has high rigidity and high heat storage property, the ethylcellulose-based resin plays a role of suppressing solidification of the external electrode paste during the flow in the drying step, and promoting the outward flow. Since the external electrode paste flows from the center portion to the end portion by generating a strong outward flow, the external electrode paste can be prevented from expanding outward at the center portion (see fig. 3 d).
That is, in the paste for external electrodes of the present embodiment, since the interfacial tension generated between the resin and the solvent is 15mN/m or more, the force of the outward flow becomes greater, and thus the fluidity is improved as compared with the conventional paste for external electrodes, and the paste can be suppressed from having a shape in which the central portion swells as compared with the end portions. Therefore, the electronic component manufactured using the paste for external electrodes in the present embodiment can be miniaturized.
Fig. 5 (a) is a schematic diagram showing a cross section of a laminated ceramic capacitor 50a in which an external electrode 52a is formed on a ceramic body 51a using the external electrode paste according to the present embodiment. Fig. 5 (b) is a schematic diagram showing a cross section of a laminated ceramic capacitor 50b in which an external electrode 52b is formed on a ceramic body 51b using a conventional external electrode paste.
As shown in fig. 5 (b), the external electrode 52b formed using the conventional external electrode paste has a convex shape with a thick central portion and thin end portions. In contrast, the external electrode 52a formed using the external electrode paste according to the present embodiment has a flat shape, and can be suppressed from having the convex shape described above. Therefore, the multilayer ceramic capacitor in which the external electrode is formed using the external electrode paste according to the present embodiment can be miniaturized. In addition, when the comparison is made with the same size, the external electrode can be thinned and the internal element can be enlarged, and thus the capacitance can be increased.
The method of applying the paste for external electrodes in the present embodiment to the ceramic body is not limited to the above-described impregnation of the paste for external electrodes.
Table 1 shows the results of examining the flatness of the external electrode paste when the ratio of the average particle diameter D50 of the Cu filler included in the external electrode paste and the nonvolatile components other than the solvent included in the external electrode paste were changed.
[ Table 1 ]
The average particle diameter D50 of the Cu filler contained in the external electrode paste is changed within a range of 0.3 μm or more and 8.0 μm or less. The average particle diameter D50 of the glass contained in the paste for external electrodes was 1.0. Mu.m. The proportion of the non-volatile component other than the solvent contained in the external electrode paste is changed in the range of 5vol% or more and 40vol% or less. The PVC (Pigment Volume Concentration ) of the paste for external electrodes was 56%. The ratio of the ethylcellulose-based resin and the acrylic resin contained in the external electrode paste was set to 5:5 by weight.
The flatness of the paste for external electrodes was examined by the following method. First, as shown in fig. 4, a ceramic body 40 having a length L of 1.0mm, a width W of 0.5mm, and a thickness T of 0.5mm was prepared. The ceramic body 40 is a ceramic body constituting a laminated ceramic capacitor after formation of external electrodes, and is a ceramic body obtained by firing a laminate of a plurality of ceramic green sheets coated with internal electrode paste. The internal electrode 42 is exposed at the end face 41 of the ceramic body 40 and the end face located opposite to the end face 41 in the longitudinal direction L.
The prepared end face 41 of the ceramic body 40 is immersed in the external electrode paste, and then the applied external electrode paste is dried. Then, the difference in film thickness of the external electrode paste when the ceramic body 40 was cut along the A-A cutting line and the B-B cutting line shown in fig. 4 was examined. More specifically, the difference between the thickness of the thickest part of the external electrode paste at the position where the ceramic body 40 is cut along the A-A cutting line and the thickness of the thinnest part of the external electrode paste at the position where the ceramic body 40 is cut along the B-B cutting line was examined. The thickness of the thickest part of the external electrode paste at the position cut along the A-A cutting line is the thickness at the position of the center part in the thickness direction T. The thickness of the thinnest part of the external electrode paste at the position cut along the B-B cutting line is the thickness at the end in the thickness direction T.
Here, the A-A cutting line is a cutting line at the center in the width direction W of the ceramic body 40 when cutting along a plane defined by the longitudinal direction L and the thickness direction T. The B-B cutting line is a line parallel to the A-A cutting line, and is a cutting line at a position of an end portion of the internal electrode 42 in the width direction W of the ceramic body 40. The position of the B-B cutting line is, for example, a position 30 μm inward in the width direction W from the end in the width direction of the ceramic body 40.
Here, when the thickness of the thinnest part of the external electrode paste at the position cut along the B-B cutting line is 0.5 μm or more, the difference between the above-mentioned thicknesses is 16 μm or less, and a region where the external electrode paste is not applied does not exist on the end face of the ceramic body 40, the other part is judged as good (o), and the other part is judged as defective (x).
As shown in table 1, when the proportion of the non-volatile components other than the solvent contained in the external electrode paste was 15vol% or more and 32vol% or less, a desired good product coated with the external electrode paste was obtained regardless of the average particle diameter D50 of the Cu filler. Therefore, the proportion of the non-volatile component other than the solvent contained in the external electrode paste is preferably 15vol% or more and 32vol% or less. The average particle diameter D50 of the Cu filler is preferably in the range shown in table 1, that is, 0.3 μm or more and 8.0 μm or less.
As shown in table 1, when the proportion of the non-volatile components other than the solvent contained in the external electrode paste is 10vol%, the average particle diameter D50 of the Cu filler is preferably 0.3 μm or more and 2.0 μm or less. In the case where the proportion of the nonvolatile components other than the solvent contained in the external electrode paste is 35vol%, the average particle diameter D50 of the Cu filler is preferably 5.0 μm or more and 8.0 μm or less.
Here, C is preferably polymerized on the surface of the Cu filler for the purpose of oxidation prevention, improvement of dispersibility, and the like. In the external electrode paste of the present embodiment, C was polymerized on the surface of the Cu filler, and the results of examining the flatness of the external electrode paste when the amount of polymerized C was changed are shown in table 2.
[ Table 2 ]
The average particle diameter D50 of the Cu filler is 0.05-1.0 μm, and the amount of C polymerized on the surface of the Cu filler is changed within a range of 0.03-1.33 wt%. The average particle diameter D50 of the glass contained in the paste for external electrodes was 0.5. Mu.m. The proportion of the non-volatile component other than the solvent contained in the external electrode paste was 20vol%, and the proportion of the solvent was 80vol%. The ratio of the ethylcellulose-based resin and the acrylic resin contained in the paste for external electrodes was set to 5:5 by weight.
The flatness of the paste for external electrodes was examined by using the method described with reference to fig. 4. Here, the difference in film thickness, that is, the difference in film thickness of the external electrode paste when the ceramic body 40 is cut along the A-A cutting line and the B-B cutting line is 16 μm or less was judged as good (good), and the case of 14 μm or less was judged as good (good).
As shown in table 2, the flatness of the paste for external electrodes can be ensured as long as the amount of C polymerized on the surface of the Cu filler is in the range of at least 0.03 wt% to 1.33 wt%. Therefore, the amount of C polymerized on the surface of the Cu filler is preferably 0.03 wt% or more and 1.33 wt% or less. Further, when the amount of C polymerized on the surface of the Cu filler is 0.11 wt% or more and 0.98 wt% or less, the flatness of the external electrode paste is further improved. Therefore, the amount of C polymerized on the surface of the Cu filler is more preferably 0.11 wt% or more and 0.98 wt% or less.
The present invention is not limited to the above-described embodiments, and various applications and modifications can be made within the scope of the present invention.
Claims (5)
1. An external electrode paste for forming an external electrode of a laminated ceramic electronic component, comprising:
a resin comprising at least a portion of a copolymerized ethylcellulose-based resin and an acrylic resin;
a Cu filler;
a solvent; and
the glass powder is prepared from the glass powder,
the interfacial tension generated between the resin and the solvent is 15mN/m or more.
2. The paste for external electrodes according to claim 1, wherein,
the interfacial tension generated between the resin and the solvent is 40mN/m or more and less than 56mN/m.
3. The paste for external electrodes according to claim 1 or 2, wherein,
the Cu filler is particles containing at least one of Cu and a Cu alloy, and has an average particle diameter D50 of 8 [ mu ] m or less.
4. The paste for external electrodes according to claim 1 or 2, wherein,
the proportion of the non-volatile component other than the solvent contained in the external electrode paste is 15vol% or more and 32vol% or less.
5. The paste for external electrodes according to claim 1 or 2, wherein,
the solvent comprises terpineol, dihydroterpineol acetate, propylene glycol phenyl ether, benzyl alcohol,At least 1 of the ester alcohols and butyl carbitol acetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-202445 | 2019-11-07 | ||
| JP2019202445A JP7192743B2 (en) | 2019-11-07 | 2019-11-07 | External electrode paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112786309A CN112786309A (en) | 2021-05-11 |
| CN112786309B true CN112786309B (en) | 2023-07-28 |
Family
ID=75750309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011219717.7A Active CN112786309B (en) | 2019-11-07 | 2020-11-04 | Paste for external electrode |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7192743B2 (en) |
| KR (1) | KR102366442B1 (en) |
| CN (1) | CN112786309B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024214399A1 (en) * | 2023-04-14 | 2024-10-17 | 株式会社村田製作所 | Conductive paste and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017190404A (en) * | 2016-04-14 | 2017-10-19 | 新中村化学工業株式会社 | Burned paste composition and manufacturing method of copolymer |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2370568B (en) * | 1999-12-13 | 2003-01-22 | Murata Manufacturing Co | Monolithic ceramic electronic component and production process therefor |
| JP2004264031A (en) | 2003-01-23 | 2004-09-24 | Matsushita Electric Ind Co Ltd | Method for measuring conductive particle |
| US7158364B2 (en) * | 2005-03-01 | 2007-01-02 | Tdk Corporation | Multilayer ceramic capacitor and method of producing the same |
| JP2008050594A (en) | 2006-07-26 | 2008-03-06 | Sekisui Chem Co Ltd | Binder resin composition |
| JP4442596B2 (en) * | 2006-09-08 | 2010-03-31 | Ｔｄｋ株式会社 | Conductive paste, multilayer ceramic electronic component and manufacturing method thereof |
| JP4359607B2 (en) * | 2006-09-19 | 2009-11-04 | Ｔｄｋ株式会社 | Electrode step absorbing printing paste and method for producing multilayer ceramic electronic component |
| TW200824076A (en) * | 2006-11-16 | 2008-06-01 | Chipmos Technologies Inc | Carrier film having leads with improved strength and semiconductor package utilizing the film |
| JP5633285B2 (en) * | 2010-01-25 | 2014-12-03 | 日立化成株式会社 | Electrode paste composition and solar cell |
| JP5683202B2 (en) | 2010-10-13 | 2015-03-11 | ナミックス株式会社 | Thermosetting conductive paste |
| JP5715535B2 (en) | 2011-09-27 | 2015-05-07 | 互応化学工業株式会社 | Binder composition for firing |
| CN104620325B (en) * | 2012-06-15 | 2016-09-21 | 株式会社村田制作所 | Conductive paste and laminated ceramic electronic part and its manufacture method |
| KR20160060925A (en) * | 2014-11-21 | 2016-05-31 | 한국에너지기술연구원 | Paste composition containing metal particle for rear electrode of solar cell and its manufacturing method |
| JP2016213355A (en) * | 2015-05-11 | 2016-12-15 | ニチバン株式会社 | Adhesive composition for electronic component fixing and adhesive tape |
-
2019
- 2019-11-07 JP JP2019202445A patent/JP7192743B2/en active Active
-
2020
- 2020-10-27 KR KR1020200139895A patent/KR102366442B1/en active IP Right Grant
- 2020-11-04 CN CN202011219717.7A patent/CN112786309B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017190404A (en) * | 2016-04-14 | 2017-10-19 | 新中村化学工業株式会社 | Burned paste composition and manufacturing method of copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021077750A (en) | 2021-05-20 |
| CN112786309A (en) | 2021-05-11 |
| KR102366442B1 (en) | 2022-02-23 |
| JP7192743B2 (en) | 2022-12-20 |
| KR20210055596A (en) | 2021-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10529486B2 (en) | Conductive paste for external electrode and method for manufacturing electronic component including the conductive paste for external electrode | |
| JP6001977B2 (en) | Porous aluminum body, aluminum electrolytic capacitor, and method for producing porous aluminum body | |
| JP5278709B2 (en) | Conductive resin composition and chip-type electronic component | |
| JP5440309B2 (en) | Manufacturing method of multilayer ceramic electronic component | |
| CN112786309B (en) | Paste for external electrode | |
| CN104620325B (en) | Conductive paste and laminated ceramic electronic part and its manufacture method | |
| CN107871543B (en) | Conductive paste | |
| KR102426098B1 (en) | Chip-type ceramic electronic component | |
| JP7338665B2 (en) | Multilayer ceramic capacitor | |
| US9978521B2 (en) | Multilayer electronic component | |
| US9001492B2 (en) | Electrode sintered body, multilayer electronic device, internal electrode paste, a manufacturing method of electrode sintered body and a manufacturing method of multilayer electronic device | |
| TW200525564A (en) | Electrode paste, ceramic electronic component and method for producing same | |
| JP2002110444A (en) | Conductive paste and laminated ceramic electronic part | |
| CN116344213A (en) | Laminated ceramic capacitor | |
| CN116344215A (en) | Laminated ceramic capacitor | |
| JP5780035B2 (en) | Ceramic electronic components | |
| TW202242910A (en) | Joint structure | |
| JP2023093064A (en) | Multilayer ceramic capacitor | |
| JP2021010034A (en) | Chip type ceramic electronic component | |
| US9474193B2 (en) | Bonded compact and method of producing green bonded compact | |
| JP4788753B2 (en) | Manufacturing method of multilayer ceramic electronic component | |
| CN113571230B (en) | Conductive silver paste, electrode structure and laminated common mode filter | |
| WO2022234739A1 (en) | Paste for external electrode | |
| JP5887919B2 (en) | Electrode sintered body and laminated electronic component | |
| JP2011134943A (en) | Method of manufacturing internal electrode of electronic component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |