WO2004061880A1 - 積層型電子部品の製造方法 - Google Patents
積層型電子部品の製造方法 Download PDFInfo
- Publication number
- WO2004061880A1 WO2004061880A1 PCT/JP2003/017011 JP0317011W WO2004061880A1 WO 2004061880 A1 WO2004061880 A1 WO 2004061880A1 JP 0317011 W JP0317011 W JP 0317011W WO 2004061880 A1 WO2004061880 A1 WO 2004061880A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- green sheet
- electrode layer
- layer
- adhesive layer
- electronic component
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 36
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- 238000003825 pressing Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 74
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- 239000004014 plasticizer Substances 0.000 claims description 33
- 238000012546 transfer Methods 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 20
- 239000002216 antistatic agent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- -1 phthalic acid ester Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 125000002636 imidazolinyl group Chemical group 0.000 claims 1
- 239000002003 electrode paste Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000003985 ceramic capacitor Substances 0.000 description 15
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- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 241001654684 Pinda Species 0.000 description 8
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
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- 229920002799 BoPET Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
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- 229920001249 ethyl cellulose Polymers 0.000 description 3
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003313 weakening effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JGXVFEZQAWZMGK-UHFFFAOYSA-N bis(2-butyloctyl) benzene-1,2-dicarboxylate Chemical compound CCCCCCC(CCCC)COC(=O)C1=CC=CC=C1C(=O)OCC(CCCC)CCCCCC JGXVFEZQAWZMGK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 239000000839 emulsion Substances 0.000 description 2
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- 150000002334 glycols Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
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- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01G4/005—Electrodes
- H01G4/012—Form of non-self-supporting electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- 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
-
- 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
- H01G4/308—Stacked capacitors made by transfer techniques
Definitions
- the present invention relates to a method for manufacturing a multilayer electronic component such as a multilayer ceramic capacitor.
- a ceramic paint consisting of ceramic powder, piner (acrylic resin, petital resin, etc.), plasticizer and organic solvent (toluene, alcohol, MEK, etc.) is prepared. I do. Next, the ceramic paint is applied on a carrier sheet such as PET using a doctor blade method or the like, and is heated and dried to produce the ceramic paint.
- a specific description of a method of manufacturing a multilayer ceramic capacitor using the above-described ceramic green sheet is as follows.
- a conductive paste for an internal electrode including a metal powder and a binder is printed in a predetermined pattern on the ceramic green sheet and dried. Then, an internal electrode pattern is formed.
- the carrier sheet is peeled off from the ceramic green sheet, and a laminate of a plurality of these sheets is cut into a chip to obtain a green chip.
- an external electrode is formed and manufactured.
- an adhesive layer may be formed on the surface of the electrode layer or the green sheet.
- the adhesive layer is formed directly on the surface of the electrode layer or the green sheet by a coating method or the like, the components of the adhesive layer permeate the electrode layer or the green sheet. Therefore, it is difficult to perform the function as the adhesive layer, and may adversely affect the formation of the electrode layer or the green sheet.
- Japanese Patent Application Laid-Open No. 2000-23853 discloses a manufacturing method in which laminated blocks are laminated via an adhesive layer (adhesive layer).
- the method described in this document is not suitable as an adhesive layer for transferring an electrode layer to an extremely thin green sheet, since the thickness of the adhesive layer is as thick as about 0.5 to 5 ⁇ .
- the present invention has been made in view of such a situation, and even if the green sheet is extremely thin, the dry type electrode layer can be easily and easily formed on the surface of the green sheet without breaking or deforming the green sheet. It is an object of the present invention to provide a method of manufacturing a laminated electronic component at a low cost which can be transferred with high accuracy.
- Another object of the present invention is to prevent the components of the adhesive layer from permeating into the electrode layer or the green sheet, and to easily peel off the support sheet, and to easily and accurately form a dry-type electrode layer on the surface of the green sheet.
- An object of the present invention is to provide a method of manufacturing a laminated electronic component capable of transferring with high accuracy. [0 0 1 6]
- the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the object of the present invention can be achieved by forming an adhesive layer having a predetermined thickness on a surface of an electrode layer or a Darline sheet in a dry manner.
- the present invention has been completed.
- the method for manufacturing a multilayer electronic component according to the first aspect of the present invention includes the steps of: pressing an electrode layer against a surface of a green sheet, and bonding the electrode layer to a surface of the green sheet.
- the surface of the electrode layer or the surface of the green sheet Before pressing the electrode layer against the surface of the green sheet, the surface of the electrode layer or the surface of the green sheet may have a thickness of 0.2 to 0.3 ⁇ , preferably 0.1 to 0.2 / i. It is characterized in that an adhesive layer having a thickness of Hi is formed.
- an adhesive layer having a thickness smaller than the average particle diameter of the dielectric particles included in the daline sheet is formed on the surface of the electrode layer or the surface of the green sheet. It is characterized by doing.
- pressing the electrode layer against the surface of the green sheet has the same meaning as “pressing the green sheet against the surface of the electrode”. [0 0 2 0]
- an adhesive layer is formed on a surface of an electrode layer or a green sheet, and the electrode layer is formed via the adhesive layer. Adhere to the surface of the green sheet.
- the formation of the adhesive layer eliminates the need for high pressure and heat when bonding and transferring the electrode layer to the surface of the green sheet, and enables lower pressure and lower temperature bonding. Therefore, even when the green sheet is extremely thin, the green sheet is not destroyed, the green sheet with the internal electrode can be laminated well, and short-circuit failure does not occur.
- the thickness of the adhesive layer becomes smaller than the convexity of the green sheet surface, and the adhesiveness tends to be significantly reduced. Also, if the thickness of the adhesive layer is too thick, a gap is easily formed inside the element body after sintering depending on the thickness of the adhesive layer, and the capacitance corresponding to the volume tends to be significantly reduced. Also, if an adhesive layer thicker than the average particle diameter of the dielectric particles contained in the green sheet is formed, a gap is easily formed inside the element body after sintering depending on the thickness of the adhesive layer. The capacitance tends to decrease significantly.
- the thickness of the green sheet is 3 ⁇ or less, and the thickness of the adhesive layer is 1 Z5 or less of the thickness of the green sheet.
- the present invention is particularly effective when the thickness of the green sheet is 3 ⁇ m or less.
- the green sheet includes dielectric particles containing barium titanate as a main component, and the dielectric particles have an average particle diameter of 0.4 ⁇ or less. If the average particle size of the dielectric particles is too large, it tends to be difficult to form a thin green sheet.
- the green sheet contains, as a pinda, an acrylic resin and a ⁇ or butyral resin.
- a binder can be used to form a thin green sheet having sufficient strength.
- the adhesive layer contains substantially the same organic polymer material as the binder contained in the green sheet. This is because when depinning the green chip, the pinda is removed from the chip by depinning under the same conditions.
- the adhesive layer includes a plasticizer
- the plasticizer is at least one of glycol phthalate, adipic acid, and phosphate.
- the adhesive layer includes an antistatic agent
- the antistatic agent includes one of imidazoline-based surfactants
- the amount of the antistatic agent based on weight is based on the amount of the organic polymer material. It is not more than the weight-based addition amount.
- the adhesive layer includes dielectric particles, the dielectric particles having an average particle diameter equal to or smaller than the average particle diameter of the dielectric particles included in the green sheet, and a dielectric composition included in the Darine sheet. It may contain substantially the same type of dielectric composition. Since the adhesive layer becomes a part of the element body after firing, it is preferable that the adhesive layer contains substantially the same type of dielectric particles as the dielectric particles contained in the green sheet.
- the average particle diameter of the dielectric particles is preferably equal or smaller.
- the weight-based addition ratio of the dielectric particles included in the adhesive layer is smaller than the weight-based addition ratio of the dielectric particles included in the green sheet. This is for maintaining good adhesiveness of the adhesive layer.
- a step of bonding the electrode layer to the surface of the green sheet and bonding another green sheet to the surface of the green sheet on which the electrode layer is formed is repeated.
- a plurality of the green sheets are laminated via the electrode layer to form a laminated yoke,
- a plurality of the laminated blocks are laminated via the adhesive layer to form the green chip.
- a green chip in which green sheets are laminated in, for example, 500 or more layers can be easily manufactured.
- the electrode layer when forming the laminated block, is bonded to the surface of the green sheet without using an adhesive layer, and another green sheet is bonded to the surface of the green sheet on which the electrode layer is formed. May be repeated to form a laminated block. Then, a plurality of laminated blocks may be laminated via an adhesive layer of 0.02 to 0.3 ⁇ to form a green chip.
- the adhesive layer may be formed by a normal coating method or the like, but is preferably formed by a transfer method.
- the adhesive layer is first formed releasably on the surface of the support sheet, and is transferred by being pressed against the surface of the green sheet or the surface of the electrode layer.
- the adhesive layer By forming the adhesive layer on the surface of the electrode layer or the green sheet by the transfer method instead of forming it directly by the coating method, etc., the components of the adhesive layer do not seep into the electrode layer or the green sheet, and extremely A thin adhesive layer can be formed.
- the thickness of the adhesive layer can be reduced to about 0.2 to 0.3 m. Even if the thickness of the adhesive layer is small, the adhesive strength is sufficient because the components of the adhesive layer do not penetrate into the electrode layer or the green sheet, and there is no possibility that the composition of the electrode layer or the green sheet is adversely affected. .
- the electrode layer is formed on the surface of the support sheet with a predetermined pattern via a release layer, and the surface of the release layer where the electrode layer is not formed is substantially in contact with the electrode layer.
- a blank pattern layer of the same thickness is formed,
- the green sheet is made of substantially the same material.
- the blank pattern layer By forming the blank pattern layer, a step on the surface due to the electrode layer of a predetermined pattern is eliminated. Therefore, even if pressure is applied before firing after laminating a large number of green sheets, the outer surface of the laminate is kept flat, the electrode layers do not shift in the planar direction, and the green sheets are broken through and short-circuits occur. There is no cause.
- the release layer includes a dielectric composition substantially the same as the dielectric composition constituting the green sheet.
- the remaining release layer does not pose a problem. The reason is that the remaining release layer is sufficiently thinner than the green sheet and contains the same dielectric as the dielectric constituting the green sheet. Is also a part of the dielectric layer, like the green sheet.
- the adhesive strength of the adhesive layer stronger than the adhesive strength of the release layer and by making the adhesive strength of the release layer stronger than the adhesive strength between the green sheet and the support sheet.
- the support sheet on the Darling sheet side can be selectively and easily peeled off.
- the release layer, the adhesive layer, the electrode layer and the green sheet may contain a plasticizer together with the binder resin, and the plasticizer is preferably used in an amount of 100 parts by mass of the binder resin. 25 to 100 parts by mass.
- the content ratio of the binder to the dielectric contained in the release layer is equal to or lower than the content ratio of the binder to the dielectric contained in the green sheet.
- the content ratio of the release agent to the dielectric contained in the release layer is higher than the content ratio of the release agent to the dielectric contained in the green sheet.
- the strength of the release layer is lower than the breaking strength of the green sheet, even for an extremely thin and brittle green sheet. Therefore, when the electrode layer is transferred, the release layer is partially broken or peeled off from the electrode layer without breaking the green sheet, and the electrode layer is transferred satisfactorily toward the green sheet. .
- the thickness of the release layer is equal to or less than the thickness of the electrode layer.
- the thickness of the release layer is set to preferably 60% or less, more preferably 30% or less of the thickness of the electrode layer.
- the lower limit of the thickness of the release layer is determined by the particle size of the dielectric material that can be used for the release layer, and is preferably 0.05 to 0.3 ⁇ .
- the pressure at which the electrode layer is adhered to the surface of the daline sheet is 0.2 to 15 MPa.
- the temperature during pressurization is preferably about 40 to 100 ° C.
- the transfer tends to be difficult. If the pressurizing temperature is too low, the transfer tends to be difficult. If the pressurizing temperature is too high, the support sheet may be thermally deformed, and it is difficult to transfer the electrode layer of a predetermined pattern to the green sheet with high accuracy. Become. On the other hand, if the pressing force is too small, the transfer may be difficult, and if the pressing force is too high, the possibility that the green sheet is broken is increased, which is not preferable. In particular, when the thickness of the green sheet is small, it is preferable that the electrode layer can be adhered to the surface of the green sheet with a low pressure.
- the pressurization is preferably performed by a pair of rolls.
- the electrode layer is formed on the surface of the release layer by a thick film method using an electrode paste.
- the thick film method is not particularly limited, and examples thereof include screen printing. It should be noted that a film may be formed on the surface of the release layer by a thin film method.
- the thin film method is not particularly limited, but examples include a sputtering method, a vacuum evaporation method, and a CVD method. [0 0 4 6]
- the binder and the plasticizer component evaporate under vacuum, and the peeling layer on the surface of the first support sheet is damaged by sputtered particles and evaporated particles. Will receive it. However, this works in the direction of weakening the strength of the release layer, which is convenient because the electrode layer is transferred to the surface of the green sheet.
- the material and the production method of the green sheet are not particularly limited. It may be a porous ceramic green sheet obtained by biaxial stretching.
- electrode layer is used as a concept including an electrode paste film that becomes an internal electrode layer after firing.
- FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention
- FIGS. 2A to 2C and FIGS. 3A to 3C are main-part cross-sectional views illustrating a method of transferring an electrode layer
- 4A to 4C, 5A to 5C, 6A to 6C, 7 and 8 are cross-sectional views of a main part showing a method of laminating a green sheet to which electrode layers are bonded. is there.
- the multilayer ceramic capacitor 2 has a capacitor body 4, a first terminal electrode 6, and a second terminal electrode 8.
- the capacitor body 4 has a dielectric layer 10 and an internal electrode layer 12, and these elements are disposed between the dielectric layers 10.
- the internal electrode layers 12 are alternately stacked.
- One of the alternately laminated internal electrode layers 1 2 is electrically connected to the inside of the first terminal electrode 6 formed outside the first end 4 a of the capacitor body 4.
- the other alternately laminated internal electrode layers 12 are electrically connected to the inside of the second terminal electrode 8 formed outside the second end 4 b of the capacitor body 4. is there.
- the internal electrode layer 12 is formed by transferring the electrode layer 12a to a ceramic Darline sheet 10a as shown in FIGS. 2 to 6, as will be described later in detail. You.
- the material of the dielectric layer 10 is not particularly limited, and is made of, for example, a dielectric material such as calcium titanate, strontium titanate and Z or parium titanate.
- the thickness of each dielectric layer 10 is not particularly limited, but is generally several ⁇ to several hundred ⁇ . In particular, in the present embodiment, the thickness is reduced to preferably 5 ⁇ or less, more preferably 3 ⁇ or less.
- the material of the terminal electrodes 6 and 8 is also not particularly limited. Usually, copper, a copper alloy, a nickel-nickel alloy, or the like is used, but silver or an alloy of silver and palladium can also be used.
- the thickness of the terminal electrodes 6 and 8 is not particularly limited, but is usually about 10 to 50 Atm.
- the shape and size of the multilayer ceramic capacitor 2 may be appropriately determined depending on the purpose and application.
- the multilayer ceramic capacitor 2 has a rectangular parallelepiped shape, it is usually vertical (0.6 to 5.6 mm, preferably 0.6 to 3.2 mm) X horizontal (0.3 to 5.0 mm, preferably 0.3 to 0.5 mm). 3 to 1.6 mm) X thickness (0.1 to 1.9 mm, preferably 0.3 to 1.6 mm).
- a dielectric paste is prepared in order to produce a ceramic green sheet that will constitute the dielectric layer 10 shown in FIG. 1 after firing.
- the dielectric paste is usually composed of an organic solvent-based paste or an aqueous paste obtained by kneading a dielectric material and an organic vehicle.
- the dielectric material various compounds that can be used as composite oxides and oxides, for example, carbonates, nitrates, hydroxides, organometallic compounds, and the like can be appropriately selected and used as a mixture.
- the dielectric material is usually used as a powder having an average particle diameter of 0.4 ⁇ or less, preferably about 0.1 to 3.0 m. In order to form an extremely thin green sheet, it is desirable to use a powder finer than the green sheet thickness.
- the organic vehicle is obtained by dissolving a binder in an organic solvent.
- the binder used in the organic vehicle is not particularly limited, and ordinary various binders such as ethyl cellulose, polyvinyl butyral, and acrylic resin are used, and preferably, a plastic resin such as polyvinyl butyral is used.
- the organic solvent used in the organic vehicle is not particularly limited, and organic solvents such as terbineol, alcohol, butyl carbitol, acetone, and toluene are used.
- the vehicle in the aqueous paste is obtained by dissolving water-soluble pinda in water.
- the water-soluble binder is not particularly limited, and polyvinyl alcohol, methinolecellulose, hydroxyethyl cellulose, water-soluble acrylic resin, emulsion and the like are used.
- the content of each component in the dielectric paste is not particularly limited, and is usually a content, for example, 1 to 5 mass of a binder. /.
- the solvent (or water) should be about 10 to 50% by mass.
- the dielectric paste various dispersants, plasticizers, dielectrics, An additive selected from a lit, an insulator and the like may be contained.
- the total content thereof is desirably 10% by mass or less.
- the content of the plasticizer is preferably 25 to 100 parts by mass with respect to 100 parts by mass of the pinda resin. If the amount of the plasticizer is too small, the green sheet tends to be brittle, and if the amount is too large, the plasticizer oozes out and is difficult to handle.
- a carrier sheet 30 as a second support sheet, preferably 0.5 to 30 / im, more preferably Has a thickness of about 0.5 to 10 zm and forms a green sheet 10a.
- the green sheet 10a is dried after being formed on the carrier sheet 30.
- the drying temperature of the green sheet 10a is preferably 50 to 100 ° C, and the drying time is preferably 1 to 20 minutes.
- the thickness of the green sheet 10a after drying shrinks to 5 to 25% of the thickness before drying.
- the thickness of the green sheet after drying is preferably 3 inches or less.
- a carrier sheet 20 as a first support sheet is prepared, and a release layer 22 is formed thereon.
- the electrode layer 12a having a predetermined pattern is formed thereon, and before and after that, on the surface of the release layer 22 where the electrode layer 12a is not formed, the thickness is substantially the same as the electrode layer 12a.
- a blank pattern layer 24 is formed.
- the carrier sheets 20 and 30 for example, PET films or the like are used, and those coated with silicon or the like to improve the releasability are preferable.
- the thickness of the carrier sheets 20 and 30 is not particularly limited, but is preferably 5 to 100 ⁇ . The thicknesses of these carrier sheets 20 and 30 may be the same or different.
- the release layer 22 is preferably made of a dielectric material constituting the green sheet 10a shown in FIG. Contains the same dielectric particles as the body.
- the release layer 22 contains a binder, a plasticizer, and a release agent in addition to the dielectric particles.
- the particle size of the dielectric particles may be the same as the particle size of the dielectric particles contained in the green sheet, but is preferably smaller.
- the thickness t2 of the release layer 22 is preferably not more than the thickness of the electrode layer 12a, preferably not more than 6%, more preferably not more than 30%. I do.
- the method for applying the release layer 22 is not particularly limited, but is preferably an application method using a wire bar coater or a die coater because it is necessary to form the release layer 22 very thin.
- the thickness of the release layer can be adjusted by selecting a wire and a bar coater having different diameters. That is, in order to reduce the coating thickness of the release layer, one having a small diameter of the wire may be selected, and in order to form a thick layer, one having a large diameter of the wire may be selected.
- the release layer 22 is dried after the application.
- the drying temperature is preferably between 50 and 100 ° C. and the drying time is preferably between 1 and 10 minutes.
- binder for the release layer 22 for example, acrylic resin, polyvinyl butyralone, polyvinylinolea cetanolle, polyvinylinoleanole konore, polyolefin, polyurethane, polystyrene, or an organic material composed of these copolymers, Or consist of an emulsion.
- the binder contained in the release layer 22 may be the same as or different from the binder contained in the green sheet 10a, but is preferably the same.
- plasticizer for the release layer 22 examples include, but are not particularly limited to, phthalic acid esters, adipic acid, phosphoric acid esters, and glycols.
- the plasticizer contained in the release layer 22 may be the same as or different from the plasticizer contained in the green sheet 10a.
- the release agent for the release layer 22 is not particularly limited, and examples thereof include paraffin, wax, and silicone oil.
- the release agent contained in the release layer 22 may be the same as or different from the release agent contained in the green sheet 10a.
- the binder is contained in the release layer 22 in an amount of preferably 2.5 to 200 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 8 to 3 parts by mass with respect to 100 parts by mass of the dielectric particles. It is contained in about 0 parts by mass.
- the content ratio of the binder to the dielectric particles included in the release layer 22 is preferably lower than the content ratio of the binder to the dielectric particles included in the green sheet 10a by about 10 to 50%. . This is for weakening the peel strength of the release layer 22.
- the plasticizer is contained in the release layer 22 in an amount of 0 to 200 parts by mass, preferably 20 to 200 parts by mass, more preferably 50 to 100 parts by mass, based on 100 parts by mass of the binder. It is preferred that it is included in a part.
- the content ratio of the plasticizer to the binder contained in the release layer 22 is preferably about 10 to 100% higher than the content ratio of the plasticizer to the binder contained in the green sheet 10a. This is for reducing the strength of the release layer 22.
- the release agent is contained in the release layer 22 in an amount of 0 to 100 parts by mass, preferably 2 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the binder. This is preferred.
- the content ratio of the release agent with respect to the binder contained in the release layer 22 is preferably higher than the content ratio of the release agent with respect to the binder contained in the green sheet 10a to about 10 to 400%. This is for weakening the strength of the release layer 22.
- the electrode layer 1 2 a that forms the internal electrode layer 12 after firing is formed on the surface of the release layer 22. Is formed in a predetermined pattern.
- the thickness of the electrode layer 12a is preferably about 0.1 to 2 ⁇ m, more preferably about 0.1 to 1.1 ⁇ .
- Electrode layer 1 2a is a single layer Or may be composed of two or more layers having different compositions.
- the electrode layer 12a can be formed on the surface of the release layer 22 by a thick film forming method such as a printing method using an electrode paste, or a thin film method such as vapor deposition or sputtering.
- a thick film forming method such as a printing method using an electrode paste, or a thin film method such as vapor deposition or sputtering.
- a screen printing method or a Daravia printing method which is one of the thick film methods, the following is performed.
- an electrode paste is prepared.
- the electrode paste is prepared by kneading an organic vehicle with a conductive material made of various conductive metals or alloys, or various oxides, organic metal compounds, or resinates that become the above-described conductive material after firing.
- Ni, Ni alloy, or a mixture thereof is used as the conductor material used in producing the electrode paste.
- a conductive material is not particularly limited in its shape, such as a sphere or a scale, and may be a mixture of these shapes.
- the average particle diameter of the conductive material is as follows: Usually, a material of about 0.1 to 2 m, preferably about 0.2 to 1 / xm may be used.
- the organic vehicle contains a pinda and a solvent.
- the binder include ethyl cellulose, acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, and copolymers thereof, and in particular, polyvinyl butyral and the like. Is preferred.
- the binder is preferably contained in the electrode paste in an amount of 8 to 20 parts by mass with respect to 100 parts by mass of the conductive material (metal powder).
- the solvent any of known solvents such as terbineol, butyrcarbitol, and kerosene can be used.
- the solvent content is preferably about 20 to 55% by mass based on the entire paste. [0 0 8 1]
- the electrode paste contains a plasticizer.
- the plasticizer include phthalic esters such as benzyl butyl phthalate (BBP), adipic acid, phosphoric esters, and glycols.
- the plasticizer is preferably used in an amount of 100 to 300 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the binder in the electrode base. If the amount of the plasticizer or the pressure-sensitive adhesive is too large, the strength of the electrode layer 12a tends to be significantly reduced.
- a plasticizer or adhesive is added to the electrode paste to improve the adhesion or Z of the electrode paste. It is preferable to do so.
- the electrode layer 1 2a is formed on the surface of the release layer 22 where the electrode layer 12a is not formed.
- the blank pattern layer 24 is made of the same material as the green sheet 10a shown in FIG. 3A, and is formed by a similar method.
- the electrode layer 12a and the blank pattern layer 24 are dried if necessary.
- the drying temperature is not particularly limited, but is preferably 70 to 120 ° C., and the drying time is preferably 5 to 15 minutes.
- an adhesive layer 28 is formed on the surface of a carrier sheet 26 as a third support sheet. Prepare a sheet for use.
- the carrier sheet 26 is formed of a sheet similar to the carrier sheets 20 and 30.
- the composition of the adhesive layer 28 is the same as that of the release layer 22 except that it does not contain a release agent. That is, the adhesive layer 28 includes a binder, a plasticizer, and a release agent.
- the adhesive layer 28 may contain the same dielectric particles as the dielectric constituting the green sheet 10a, but when an adhesive layer having a thickness smaller than the particle diameter of the dielectric particles is formed, It is better not to include dielectric particles. If the adhesive layer 28 contains dielectric particles, The particle size of the dielectric particles is preferably smaller than the particle size of the dielectric particles contained in the green sheet.
- the plasticizer is contained in the adhesive layer 28 in an amount of 0 to 200 parts by mass, preferably 20 to 200 parts by mass, more preferably 50 to 100 parts by mass, based on 100 parts by mass of the binder. It is preferred that it is included in a part.
- the adhesive layer 28 further contains an antistatic agent.
- the antistatic agent includes one of imidazoline-based surfactants, and the amount of the antistatic agent added based on the weight of the pinda (organic polymer material) It is preferable that the amount is not more than the weight-based addition amount. That is, the antistatic agent is contained in the adhesive layer 28 in an amount of 0 to 200 parts by mass, preferably 20 to 200 parts by mass, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the binder. It is preferably contained in 100 parts by mass.
- the thickness of the adhesive layer 28 is preferably about 0.02 to 0.3 m, and more preferably smaller than the average particle diameter of the dielectric particles contained in the green sheet.
- the thickness of the adhesive layer 28 is preferably 1/5 or less of the thickness of the green sheet 10a.
- the thickness of the adhesive layer 28 is too thin, the adhesive strength is reduced, and if it is too thick, a gap is easily formed inside the element body after sintering depending on the thickness of the adhesive layer. The capacity tends to decrease significantly.
- the adhesive layer 28 is formed on the surface of the carrier sheet 26 as a third support sheet by, for example, a bar coater method, a die coater method, a reppers coater method, a dip coater method, a kiss coater method, and dried as necessary. Is done.
- the drying temperature is not particularly limited, but is preferably room temperature to 80 ° C., and the drying time is preferably 1 to 5 minutes.
- a transfer method is employed in the present embodiment. That is, as shown in FIG. 2B, the adhesive layer 28 of the carrier sheet 26 is pressed against the surface of the electrode layer 12a and the margin pattern layer 24 as shown in FIG. By peeling the carrier sheet 26, the adhesive layer 28 is transferred to the surface of the electrode layer 12a and the margin pattern layer 24 as shown in FIG. 2C.
- the transfer of the adhesive layer 28 may be performed on the surface of the green sheet 10a shown in FIG. 3A.
- the heating temperature during the transfer is preferably from 40 to 100 ° C., and the pressure is preferably from 0.2 to 15 MPa.
- the pressurization may be performed by a press or a calender roll, but is preferably performed by a pair of rolls.
- the electrode layer 12a is adhered to the surface of the green sheet 10a formed on the surface of the carrier sheet 30 shown in FIG. 3A.
- the electrode layer 12 a and the blank pattern layer 24 of the carrier sheet 20 are pressed together with the carrier sheet 20 onto the surface of the green sheet 10 a via the adhesive layer 28.
- the electrode layer 12a and the blank pattern layer 24 are transferred to the surface of the green sheet 10a by heating and pressing as shown in FIG. 3C.
- the carrier sheet 30 on the green sheet side is peeled off, when viewed from the green sheet 10a side, the green sheet 10a is bonded to the electrode layer 12a and the margin pattern layer 24 by the adhesive layer 28. Transcribed via
- the heating and pressurizing at the time of transfer may be pressurizing and heating by a press or pressurizing and heating by a calendar roll, but are preferably performed by a pair of rolls.
- the heating temperature and the pressure are the same as in the transfer of the adhesive layer 28.
- an electrode layer 12a having a single layer and a predetermined pattern is formed on the single green sheet 10a.
- the steps shown in FIGS. 4A to 6C are repeated. I should do it.
- members common to those shown in FIGS. 3A to 4C are denoted by the same reference numerals, and description thereof is partially omitted.
- the adhesive layer 28 is transferred to the front surface (rear surface) of the green sheet 10a on the side opposite to the electrode layer. Thereafter, as shown in FIGS. 5A to 5C, the electrode layer 12a and the blank pattern layer 24 are transferred to the back surface of the green sheet 10a via the adhesive layer 28.
- the green sheet 10a is transferred to the surfaces of the electrode layer 12a and the margin pattern layer 24 via the adhesive layer 28. Thereafter, by repeating these transfers, a laminated block in which a large number of electrode layers 12a and green sheets 10a are alternately laminated as shown in FIG. 7 is obtained.
- the laminate unit U1 shown in FIG. 4C may be laminated. Thereafter, the upper carrier sheet 20 is again peeled off, the laminate unit U1 shown in FIG. 4C is laminated thereon, and the operation of peeling the upper carrier sheet 20 again is repeated. As shown in FIG. 7, a laminated block in which a large number of the electrode layers 12a and the green sheets 10a are alternately laminated is obtained.
- the method of laminating the laminate unit U1 shown in FIG. 4C is superior in lamination work efficiency.
- the firing step in the next step is performed using the stacked block alone. Further, if necessary, such a plurality of laminated blocks may be laminated via an adhesive layer 28 formed by a transfer method in the same manner as described above to form a more multilayer laminated body.
- a green sheet 40 for the outer layer (a thick laminate obtained by laminating a plurality of green sheets on which no electrode layer is formed) is provided. Are stacked, and the whole of the stacked body is supported by the suction holding table 50. Thereafter, the upper carrier sheet 20 is peeled off, and a green sheet 40 for an outer layer is similarly formed on the top of the laminate, followed by final pressing.
- the pressure at the time of final pressurization is preferably 10 to 200 MPa.
- the heating temperature is preferably 40 to 100 ° C.
- the laminate is cut into a predetermined size to form green chips.
- the green chip is subjected to a binder removal process and a firing process, and is then subjected to a heat treatment to reoxidize the dielectric layer.
- the binder removal treatment may be performed under ordinary conditions. However, when a base metal such as Ni or Ni alloy is used as the conductor material of the internal electrode layer, it is particularly preferable to perform the treatment under the following conditions. [0102]
- Heating rate 5 ⁇ 300 ° CZ time, especially 10 ⁇ 50 ° CZ time,
- Holding temperature 200 ⁇ 400 ° C, especially 250 ⁇ 350 ° C,
- Holding time 0.5-20 hours, especially 1-10 hours
- Atmosphere wet mixed gas of N 2 and H 2.
- the firing conditions are preferably as follows.
- Heating rate 50 ⁇ 500 ° CZ time, especially 200 ⁇ 300 ° C / hour,
- Holding temperature 1 100-1300 ° C, especially 1 150-1250 ° C
- Holding time 0.5-8 hours, especially 1-3 hours
- Cooling rate 50 ⁇ 500 ° C time, especially 200 ⁇ 300 ° CZ time,
- Atmosphere gas Humidified gas mixture of N 2 and H 2 .
- the oxygen partial pressure in an air atmosphere at firing is less 10- 2 P a, it is preferably carried out in particular 10- 2 ⁇ 10- 8 P a. If it exceeds the above range, the internal electrode layer tends to be oxidized. If the oxygen partial pressure is too low, the electrode material of the internal electrode layer tends to be abnormally sintered and cut off.
- the heat treatment after the calcination is performed at a holding temperature or a maximum temperature of preferably 100 ° C. or more, more preferably 100 ° C. to 110 ° C. . If the holding temperature or the maximum temperature during the heat treatment is less than the above range, the insulation resistance life tends to be short due to insufficient oxidation of the dielectric material, and if it exceeds the above range, Ni of the internal electrode is oxidized. However, not only does the capacity decrease, but it also reacts with the dielectric substrate, and the life tends to be shortened.
- Oxygen partial pressure at the thermal treatment is higher oxygen partial pressure than the reduction Kiri ⁇ gas at firing, preferably 1 0- 3 P a ⁇ l P a, more preferably 1 0- Z P a ⁇ l P a. Below this range, re-oxidation of the dielectric layer 2 is difficult, and beyond this range, the internal electrode layer 3 tends to be oxidized.
- the other heat treatment conditions are preferably as follows.
- Retention time 0-6 hours, especially 2-5 hours
- Cooling rate 500 ⁇ 500 ° CZ time, especially at 100 ⁇ 300 / hour,
- Atmosphere gas Humidified N 2 gas, etc.
- a wetter In order to humidify the N 2 gas or the mixed gas, for example, a wetter may be used.
- the water temperature is preferably about 0 to 75 ° C.
- the debinding treatment and the baking treatment may be performed continuously or independently. When performing these steps continuously, after removing the binder, the atmosphere is changed without cooling, the temperature is raised to the holding temperature during firing, firing is performed, and then cooling is performed to reach the holding temperature for heat treatment. It is preferable to change the atmosphere when performing the heat treatment.
- the temperature is raised in an N gas or humidified N 2 gas atmosphere to the holding temperature at the time of binder removal processing, and then the atmosphere is changed and the temperature is further raised
- the atmosphere be changed again to the N gas or humidified N 2 gas atmosphere to continue the cooling.
- the thermal treatment after raising the temperature to the holding temperature under N 2 gas atmosphere, then change the atmosphere or a wet N 2 gas atmosphere the entire process of the heat treatment.
- the sintered body (element body 4) obtained in this manner is, for example, barrel-polished,
- the end surfaces are polished with a doplast or the like, and the terminal electrode paste is baked to form terminal electrodes 6 and 8.
- the firing conditions of the terminal electrode paste are preferably, for example, about 10 minutes to 1 hour at 600 to 800 ° C. in a humidified mixed gas of N 2 and H 2.
- a pad layer is formed by performing plating or the like on the terminal electrodes 6 and 8.
- the terminal electrode paste may be prepared in the same manner as the above-mentioned electrode paste.
- the multilayer ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board or the like by soldering or the like, and is used for various electronic devices and the like.
- the green sheet In the method for manufacturing a multilayer ceramic capacitor according to the present embodiment, the green sheet
- the dry type electrode layer 12a can be easily and accurately transferred onto the surface of the green sheet 10a without breaking or deforming the 10a.
- the adhesive layer 28 is formed on the surface of the electrode layer or the green sheet by a transfer method, and the electrode layer 12 a is connected to the Darin sheet 10 a via the adhesive layer 28. Adhere to the surface.
- the formation of the adhesive layer 28 eliminates the need for high pressure and heat when bonding and transferring the electrode layer 12a to the surface of the green sheet 10a. Becomes possible. Therefore, even when the green sheet 10a is extremely thin, the green sheet 10a is not destroyed, and the electrode layer 12a and the green sheet 10a can be satisfactorily laminated. No short circuit failure occurs.
- the adhesive force of the adhesive layer 28 is made stronger than the adhesive force of the release layer 22, and the adhesive force of the release layer 22 is also the adhesive force between the green sheet 10 a and the carrier sheet 30. By making it stronger, the carrier sheet 30 on the green sheet 10a side can be selectively and easily peeled off.
- the surface of the electrode layer 12 a or the green sheet 10 a Since the adhesive layer 28 is not formed directly by a coating method or the like but is formed by a transfer method, the components of the adhesive layer 28 do not permeate into the electrode layer 12a or the green sheet 10a and have an extremely thin adhesion. The formation of the layer 28 becomes possible. For example, the thickness of the adhesive layer 28 can be reduced to about 0.02 to 0.3 zm. Even if the thickness of the adhesive layer 28 is thin, the components of the adhesive layer 28 do not penetrate into the electrode layer 12a or the green sheet 10a, so that the adhesive strength is sufficient and the electrode layer 12a or green There is no possibility that the composition of the sheet 10a is adversely affected.
- a laminate U1 of a green sheet 10a, an adhesive layer 28, an electrode layer 12a, and a blank pattern layer 24 was formed. Thereafter, a plurality of the laminate UET U1 may be laminated and press-molded with a mold or the like to form a laminated block, and the laminated block may be further laminated via an adhesive layer 28 to form a green chip.
- the laminate may be laminated without using the adhesive layer 28. However, when stacking the stacked blocks, it is preferable to use the adhesive layer 28 for stacking.
- the method of the present invention is not limited to a method for manufacturing a multilayer ceramic capacitor, but can be applied to a method for manufacturing other multilayer electronic components.
- Green sheet paste (same for blank pattern paste)
- B a T i 0 3 powder (BT-O 2 Z Sakai Chemical Industry Co., Ltd.) and, Mg C0 3, MnC 0 3 , (B a o. EC a o. 4) S i 0 3 Oyopi rare earth ( G d 2 0 3, T b 4 0 7, D y 2 Oa, H o 2 0 3, E r 2 O a, Tm 2 0 3, Yb 2 0 3, L u 2 0 3, Y 2 0 3)
- the powder selected from the above was wet-mixed with a ball mill for 16 hours and dried to obtain a dielectric material.
- the average particle size of these raw material powders was 0.1 to 1 ⁇ m.
- organic vehicle 100 parts by mass of dielectric material, 6 parts by mass of polybutyral resin (PVB) as binder and 3 parts by mass of bis (2-ethylhexyl) phthalate (DOP) as plasticizer , Ethanol: 55 parts by mass, toluene: 10 parts by mass, and paraffin: 0.5 part by mass as a release agent.
- DOP bis (2-ethylhexyl) phthalate
- Ethanol 55 parts by mass
- toluene 10 parts by mass
- paraffin 0.5 part by mass as a release agent.
- the content of DOP as a plasticizer is 50 parts by mass (PHR) when PVB is 100 parts by mass.
- PVB is included at a ratio of 6 PHP because it is 6 parts by mass with respect to 100 parts by mass of the dielectric material.
- the dielectric green sheet paste was diluted 4 times with ethanol / toluene (55/10) to obtain a release layer paste.
- Organic vehicle was used as the adhesive layer paste.
- Organic vehicle Polyviel 100 parts by mass of butyral resin, bis (2-hexyl hexyl) phthalate as plasticizer DOP: 50 parts by mass (50 PHR), ethanol: 1050 parts by mass, toluene 300 parts by mass, paraffin as release agent : 10 parts by mass, diluted 5 times with a mixed solvent of ethanol: 350 parts by mass and toluene: 100 parts by mass.
- the mixture was kneaded with a three-roll mill at the mixing ratio shown below, and slurried to obtain a paste for internal electrodes. That is, based on 100 parts by mass of Ni particles having an average particle diameter of 0.4 m, 40 parts by mass of an organic vehicle (8 parts by mass of ethyl cellulose resin as a binder dissolved in 92 parts by mass of turbineol). Then, 10 parts by mass of a plastic pinner was added, and the mixture was kneaded with a three-roll mill to form a slurry to obtain a cost for an internal electrode.
- a green sheet having a thickness of 1. Oxm was formed on a PET film (second support sheet) using the above-mentioned paste for a dielectric green sheet using a wire bar coater.
- the above-mentioned paste for the release layer is applied and dried by a wire per coater to form a release layer of 0.2 ⁇ . Was formed.
- the electrode layer 12a and the blank pattern layer 24 were formed on the surface of the release layer.
- the electrode layer 12a was formed to a thickness of 1.2 IX m by a printing method using the above-mentioned internal electrode paste.
- the blank pattern layer 24 was formed with a thickness of 1.2 ⁇ m by a printing method using the paste for a dielectric green sheet described above.
- An adhesive layer 28 was formed on another PET film (third support sheet).
- the adhesive layer 28 was formed with a thickness of 0.1 ⁇ using a wire bar coater using the above-mentioned adhesive layer paste.
- the bonding layer 28 was transferred onto the surfaces of the electrode layer 12a and the blank pattern layer 24 by the method shown in FIG. At the time of transfer, a pair of rolls was used, the pressing force was IMPa, and the temperature was 80 ° C., and it was confirmed that the transfer was performed well.
- the internal electrode layer 12a and the blank pattern layer 24 were bonded (transferred) to the surface of the green sheet 10a via the bonding layer 28 by the method shown in FIG.
- a pair of rolls was used, the applied pressure was lMPa, and the temperature was 80 ° C. It was confirmed that the transfer was performed well.
- the internal electrode layer 12a and the green sheet 10a are sequentially laminated by the method shown in FIGS. 4 to 6, and finally, the five internal electrode layers 12a are laminated. A sample of the laminate block was obtained.
- the surface of the green sheet 10a was formed in the same manner as in Example 1.
- the inner electrode layer 12a and the blank pattern layer 24 were bonded (transferred).
- Table 1 shows the results of a transferability test performed in the same manner as in Example 1 and observation of the presence or absence of delamination.
- Example 1 As shown in Table 1, as in Example 1, except that the average particle size of the dielectric particles contained in the green sheet was changed and the thickness of the adhesive layer was changed. The internal electrode layer 12a and the blank pattern layer 24 were bonded (transferred) to the surface. A transferability test was performed in the same manner as in Example 1, and the presence or absence of delamination was observed. Table 1 shows the results.
- the thickness of the green sheet is 3 / xm or less, it is preferable that the thickness of the adhesive layer is 1 to 5 (0.2) or less of the thickness of the green sheet. D confirmed
- the internal electrode layer 12a and the blank pattern layer 24 were bonded (transferred) to the surface of the green sheet 10a in the same manner as in Example 1 except that the adhesive layer 28 was not formed.
- the pressure for bonding (transferring) the internal electrode layer 12a and the blank pattern layer 24 to the surface of the green sheet 10a without forming the adhesive layer 28 is 1 OMPa, and the temperature is 120.
- the internal electrode layer 12a and the blank pattern layer 24 were adhered (transferred) to the surface of the green sheet 10a in the same manner as in Example 1 except that C was used.
- Table 1 shows the results of the evaluation of the transferability performed in the same manner as in Example 1. When the adhesive layer was not formed, it was confirmed that the pressing pressure and the heating temperature were high and the green sheet was broken.
- a laminate block was formed in the same manner as in Examples 1 to 3 except that the unit U1 was laminated and pressed in a mold in five layers. Got. The same 20 samples were tested for transferability in the same manner as in Example 1, and the presence or absence of delamination was observed. Table 1 shows the results.
- an acrylic resin was used as the binder for the adhesive layer paste, and bis (2-hexylhexyl) phthalate DOP or (benzylbutyl phthalate) BBP was used as a plasticizer for green sheets.
- a transferability test was performed in the same manner as in Example 1 except that the kind of the paste piner was changed, and the presence or absence of delamination was observed. Table 1 shows the results.
- the adhesive layer is made of the same organic polymer material as the binder contained in the green sheet. It was confirmed that the transferability was improved and the occurrence of delamination was reduced when the ingredients were included.
- the plasticizer contained in the adhesive layer paste is preferably at least one of phthalic acid ester, glycol and adipic acid.
- the adhesive layer paste contains dielectric particles, and the dielectric particles preferably have an average particle size equal to or smaller than the average particle size of the dielectric particles contained in the green sheet paste.
- the transferability test was performed in the same manner as in Example 1 except that the dielectric particles (composite powder) of 0. were included at 20 to 50 PHR and the thickness of the adhesive layer was 0. At the same time, the presence or absence of delamination was observed. Table 2 shows the results.
- the addition amount of the common material powder was preferably 30 PHR or less. It was also confirmed that the weight-based addition ratio of the dielectric particles contained in the adhesive layer paste was preferably smaller than the weight-based addition ratio of the dielectric particles contained in the green sheet paste. The amount of dielectric particles contained in the green sheet paste was 1667 PHR.
- a laminate block was obtained in the same manner as in Examples 1 to 3, except that the laminate cut U1 shown in FIG. 4C was laminated and pressed in 50 layers in a mold. After that, the 50-layer laminate block is laminated by stacking 8 blocks via a 0.1 m adhesive layer 28, and the outer layer green sheets 40 (see FIG. 8) are laminated above and below the lamination direction. Then, final pressing was performed to obtain a laminated body in which 400 laminated units U1 were laminated. Dali The proportion of non-destruction of the heat sheet was 60-95% ( ⁇ ).
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- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Abstract
Description
Claims
Priority Applications (2)
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JP2004564558A JP4317820B2 (ja) | 2002-12-27 | 2003-12-26 | 積層型電子部品の製造方法 |
US10/540,774 US7491283B2 (en) | 2002-12-27 | 2003-12-26 | Production method of multilayer electronic device |
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JP2002-378816 | 2002-12-27 | ||
JP2002378816 | 2002-12-27 |
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US (1) | US7491283B2 (ja) |
JP (1) | JP4317820B2 (ja) |
KR (2) | KR100899748B1 (ja) |
CN (1) | CN100538937C (ja) |
TW (1) | TWI249753B (ja) |
WO (1) | WO2004061880A1 (ja) |
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JP2006080496A (ja) * | 2004-08-10 | 2006-03-23 | Tdk Corp | 剥離層用ペースト及び積層型電子部品の製造方法 |
JP2006077233A (ja) * | 2004-08-10 | 2006-03-23 | Tdk Corp | 剥離層用ペースト及び積層型電子部品の製造方法 |
JP2006185975A (ja) * | 2004-12-27 | 2006-07-13 | Kyocera Corp | 積層電子部品素体の製造方法 |
JP2007073777A (ja) * | 2005-09-07 | 2007-03-22 | Tdk Corp | 積層型電子部品の製造方法 |
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JP4483508B2 (ja) * | 2004-07-27 | 2010-06-16 | Tdk株式会社 | 積層型電子部品の製造方法 |
US20060286696A1 (en) * | 2005-06-21 | 2006-12-21 | Peiffer Joel S | Passive electrical article |
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- 2003-12-26 JP JP2004564558A patent/JP4317820B2/ja not_active Expired - Fee Related
- 2003-12-26 CN CNB2003801099796A patent/CN100538937C/zh not_active Expired - Fee Related
- 2003-12-26 US US10/540,774 patent/US7491283B2/en not_active Expired - Fee Related
- 2003-12-26 KR KR1020057012153A patent/KR100848436B1/ko not_active IP Right Cessation
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- 2003-12-26 TW TW092137037A patent/TWI249753B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
---|---|
KR100899748B1 (ko) | 2009-05-27 |
KR100848436B1 (ko) | 2008-07-28 |
CN100538937C (zh) | 2009-09-09 |
US20060044731A1 (en) | 2006-03-02 |
JPWO2004061880A1 (ja) | 2006-05-18 |
KR20050088236A (ko) | 2005-09-02 |
US7491283B2 (en) | 2009-02-17 |
TW200414242A (en) | 2004-08-01 |
JP4317820B2 (ja) | 2009-08-19 |
TWI249753B (en) | 2006-02-21 |
KR20070065450A (ko) | 2007-06-22 |
CN1754234A (zh) | 2006-03-29 |
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