Source: http://www.google.com/patents/US7560050?dq=5,583,822
Timestamp: 2016-05-27 01:13:45
Document Index: 385517531

Matched Legal Cases: ['arts\n163', 'arts\n0', 'arts\n2', 'arts\n0', 'arts\n6', 'arts\n34', 'arts\n56', 'arts\n1', 'arts\n32', 'arts\n56', 'Application No. 200480028461']

Patent US7560050 - Conductive paste for a multi-layered ceramic electronic component and a ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsIt is an object of the present invention to provide a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component which can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and form an electrode layer in a desired...http://www.google.com/patents/US7560050?utm_source=gb-gplus-sharePatent US7560050 - Conductive paste for a multi-layered ceramic electronic component and a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic componentAdvanced Patent SearchPublication numberUS7560050 B2Publication typeGrantApplication numberUS 10/590,538PCT numberPCT/JP2005/002881Publication dateJul 14, 2009Filing dateFeb 23, 2005Priority dateFeb 27, 2004Fee statusPaidAlso published asCN1922697A, CN100587856C, US20070172581, WO2005083719A1Publication number10590538, 590538, PCT/2005/2881, PCT/JP/2005/002881, PCT/JP/2005/02881, PCT/JP/5/002881, PCT/JP/5/02881, PCT/JP2005/002881, PCT/JP2005/02881, PCT/JP2005002881, PCT/JP200502881, PCT/JP5/002881, PCT/JP5/02881, PCT/JP5002881, PCT/JP502881, US 7560050 B2, US 7560050B2, US-B2-7560050, US7560050 B2, US7560050B2InventorsShigeki Satou, Takeshi NomuraOriginal AssigneeTdk CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (70), Non-Patent Citations (2), Referenced by (4), Classifications (55), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetConductive paste for a multi-layered ceramic electronic component and a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component
1. A conductive paste comprising: a conductive material; and containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate.
2. A conductive paste in accordance with claim 1, wherein MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 155,000 to 205,000.
3. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component comprising a step of printing a conductive paste comprising: a conductive material; and containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on a ceramic green sheet containing an acrylic system resin as a binder in a predetermined pattern, thereby forming an electrode layer.
4. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with claim 3, wherein MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 155,000 to 205,000.
5. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with claim 3, which further comprises a step of printing a dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on the ceramic green sheet in a complementary pattern to that of the electrode layer after drying the electrode layer, thereby forming a spacer layer.
6. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with claim 3, which further comprises a step of printing a dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X*MWL+(1−X)*MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on the ceramic green sheet in a complementary pattern to that of the electrode layer prior to forming the electrode layer, thereby forming a spacer layer.
7. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with any one of claim 3, wherein the weight-average molecular weight of the acrylic system resin is equal to or larger than 250,000 and equal to or smaller than 500,000.
8. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with claim 7, wherein the weight-average molecular weight of the acrylic system resin is equal to or larger than 450,000 and equal to or smaller than 500,000.
9. A method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component in accordance with any one of claim 3, wherein the acid value of the acrylic system resin is equal to or larger than 5 mgKOH/g and equal to or smaller than 10 mgKOH/g. Description
The present invention relates to a conductive paste for a multi-layered ceramic electronic component and a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component, and particularly to a conductive paste for a multi-layered ceramic electronic component which does not dissolve a binder contained in a layer adjacent to an electrode layer of the multi-layered ceramic electronic component and can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component which can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component.
However, in the case where an electrode layer is formed by printing a conductive paste prepared using terpineol, which is highly popular as a solvent for a conductive paste, on a ceramic green sheet formed using an acrylic system resin, which is the most popular binder for a ceramic green sheet, the binder contained in the ceramic green sheet is dissolved by terpineol contained in the conductive paste and a ceramic green sheet is swollen or partially dissolved, whereby pinholes and cracks are generated in the ceramic green sheet to cause short circuit failure.
One proposed solution for these problems is to employ a hydrocarbon system solvent such as kerosene, decane or the like as the solvent for the conductive paste. However, since a hydrocarbon system solvent such as kerosene, decane or the like does not dissolve the binder component used for the conductive paste, it is impossible to completely replace the conventional solvent such as terpineol with a hydrocarbon system solvent such as kerosene, decane or the like. Therefore, since the acrylic system resin contained in the ceramic green sheet as a binder is still soluble in the solvent contained in the conductive paste to some extent, it is difficult to prevent generation of pinholes and cracks in the ceramic green sheet in the case where the ceramic green sheet is very thin, and since the viscosity of a hydrocarbon system solvent such as kerosene, decane or the like is lower than that of terpineol, it is difficult to control the viscosity of the conductive paste.
Furthermore, Japanese Patent Application Laid Open No. 5-325633, Japanese Patent Application Laid Open No. 7-21833 and Japanese Patent Application Laid Open No. 7-21832 propose a conductive paste prepared using a hydrogenated terpineol such as dihydroterpineol or a terpene system solvent such as dihydroterpineol acetate instead of terpineol as a solvent. However, since the acrylic system resin contained in the ceramic green sheet as a binder is also soluble in a hydrogenated terpineol such as dihydroterpineol or a terpene system solvent such as dihydroterpineol acetate to some extent, it is difficult to prevent generation of pinholes and cracks in a ceramic green sheet in the case where the ceramic green sheet is very thin.
Further, Japanese Patent Application Laid Open No. 2002-270456 discloses a multi-layered ceramic electronic component fabricated by printing a conductive paste containing isobornyl acetate as a solvent, which hardly dissolves a butyral system resin, on a ceramic green sheet containing a butyral system resin as a binder, thereby forming an electrode layer and discloses that it is preferable to employ ethyl cellulose as a binder of the conductive paste. However, since a conductive paste containing ethyl cellulose as a binder and isobornyl acetate as a solvent has low viscosity and high fluidity, when the conductive paste is printed on a ceramic green sheet using a screen printing machine, the conductive paste leaks from a screen printing plate and the electrode layer cannot be printed in a desired manner. Further, the thus printed electrode layer tends to blot.
It is therefore an object of the present invention to provide a conductive paste for a multi-layered ceramic electronic component which does not dissolve a binder contained in a layer adjacent to an electrode layer of the multi-layered ceramic electronic component, can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and has excellent printability.
It is another object of the present invention to provide a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component which can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and form an electrode layer in a desired manner.
The inventors of the present invention vigorously pursued a study for accomplishing the above objects and, as a result, made the discovery that in the case where a conductive paste was prepared using a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X were selected so that X* MWL+(1−X)* MWH fell within a range of 145,000 to 215,000, and at least one kind of solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillyl alcohol and acetoxy-methoxyethoxy-cyclohexanol acetate, it was possible to prepare a conductive paste having a viscosity suitable for printing and dissolve a binder of the conductive paste in a binder in a desired manner and even when the conductive paste was printed on a ceramic green sheet containing an acrylic system resin as a binder, the binder contained in the ceramic green sheet was not dissolved in the solvent contained in the dielectric paste and it was therefore possible to reliably prevent generation of pinholes and cracks in the ceramic green sheet even in the case where the ceramic green sheet was very thin.
The present invention is based on these findings and therefore, the objects of the present invention can be accomplished by a conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)*MWH falls within a range of 145,000 to 215,000 and at least one kind of solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate.
The objects of the present invention can be also accomplished by a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component comprising a step of printing a conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on a ceramic green sheet containing an acrylic system resin as a binder in a predetermined pattern, thereby forming an electrode layer.
According to the present invention, it is possible to prepare a conductive paste having a viscosity suitable for printing and form an electrode layer in a desired manner. Further, according to the present invention, even when the conductive paste is printed on a very thin ceramic green sheet containing an acrylic system resin as a binder, since the binder contained in the ceramic green sheet is not dissolved in the solvent contained in the dielectric paste, it is possible to reliably prevent the ceramic green sheet from being swollen or partially dissolved and it is therefore possible to reliably prevent generation of pinholes and cracks in the ceramic green sheet even in the case where the ceramic green sheet is very thin.
In the present invention, it is preferable for MWL, MWH and X to be selected so that X* MWL+(1−X)* MWH falls within a range of 155,000 to 205,000.
In the present invention, it is preferable for the weight-average molecular weight of an acrylic system resin contained in the ceramic green sheet as a binder to be equal to or larger than 250,000 and equal to or smaller than 500,000 and it is more preferable for the weight-average molecular weight of an acrylic system resin to be equal to or larger than 450,000 and equal to or smaller than 500,000.
In the present invention, it is preferable for the acid value of an acrylic system resin contained in the ceramic green sheet as a binder to be equal to or larger than 5 mgKOH/g and equal to or smaller than 10 mgKOH/g and in the case where an acrylic system resin whose acid value is equal to or larger than 5 mgKOH/g and equal to or smaller than 10 mgKOH/g is employed as the binder of a ceramic green sheet, it is possible to prepare a dielectric paste for forming a ceramic green sheet so as to have a desired viscosity.
In a preferred aspect of the present invention, prior to forming the electrode layer or after forming and drying the electrode layer, a dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate is printed on a ceramic green sheet in a complementary pattern to that of the electrode layer, thereby forming a spacer layer.
Further, since a mixed solvent of terpineol and kerosene, dihydroterpineol, terpineol or like, which is popular as a solvent for a dielectric paste for forming a spacer layer, dissolves an acrylic system resin contained in a ceramic green sheet as a binder, when a spacer layer is formed on a ceramic green sheet, the ceramic green sheet is swollen or partially dissolved, whereby voids are generated at the interface between the ceramic green sheet and the spacer layer or fissures or wrinkles are generated on the surface of the spacer layer. As a result, in the case where a multi-layered ceramic capacitor is fabricated by laminating a number of multi-layered units to fabricate a laminated body and baking the laminated body, voids are generated in the multi-layered ceramic capacitor. Further, in the case where fissures or wrinkles are generated on the surface of the spacer layer, since the portions of the spacer layer where fissures or wrinkles are generated tend to drop off, when a number of multi-layered units are laminated to fabricate a laminated body, the portions of the spacer layer where fissures or wrinkles are generated mix into the laminated body as a foreign substance, thereby causing internal defects in the multi-layered ceramic capacitor and generating voids at portions where the spacer layer is missing. However, according to this preferred aspect of the present invention, since a dielectric paste for forming a spacer layer contains a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves an acrylic system resin contained in a ceramic green sheet as a binder, it is possible to reliably prevent the ceramic green sheet from being swollen or partially dissolved so as to generate voids at the interface between the ceramic green sheet and the spacer layer or generate fissures or wrinkles on the surface of the spacer layer, and it is therefore possible to reliably prevent voids from being generated in a multi-layered ceramic electronic component such as a multi-layered ceramic capacitor.
Moreover, since a dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)*MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate has a viscosity suitable for printing, a spacer layer can be formed on a ceramic green sheet in a desired manner by printing a dielectric paste on the ceramic green sheet in a complimentary pattern to that of an electrode layer.
Further, in a study done by the inventors of the present invention, it was found that in the case of printing a conductive paste on a very thin ceramic green sheet to form an electrode layer, the solvent contained in the conductive paste for forming the electrode layer dissolved or swelled a binder component contained in the ceramic green sheet and, on the other hand, the conductive paste permeated into the ceramic green sheet, thereby causing short circuit failure and that, therefore, it was preferable to form the electrode layer on a support sheet separately from the ceramic green sheet and bond it onto the surface of the ceramic green sheet via an adhesive layer after drying it. However, in the case where the electrode layer is formed on the support sheet separately from the ceramic green sheet in this manner, in order to make the support sheet easy to peel off from the electrode layer, it is preferable to form a release layer containing the same binder as that contained in the ceramic green sheet on the support sheet and print a conductive paste on the release layer, thereby forming an electrode layer. Even in the case of printing a conductive paste on the release layer containing the same binder as that contained in the ceramic green sheet to form an electrode layer, when the release layer contains an acrylic system resin as a binder and the conductive paste contains terpineol as a solvent, the binder contained in the release layer is dissolved by the solvent contained in the conductive paste so that the release layer is swollen or partially dissolved, whereby voids are generated at the interface between the release layer and the electrode layer or fissures or wrinkles are generated on the surface of the electrode layer. As a result, in the case where a multi-layered ceramic capacitor is fabricated by laminating a number of multi-layered units to fabricate a laminated body and baking the laminated body, voids are generated in the multi-layered ceramic capacitor. Furthermore, in the case where fissures or wrinkles are generated on the surface of the electrode layer, since the portions of the electrode layer where fissures or wrinkles are generated tend drop off, when a number of multi-layered units are laminated to fabricate a laminated body, the portions of the electrode layer where fissures or wrinkles are generated mix into the laminated body as a foreign substance, thereby causing internal defects in the multi-layered ceramic capacitor and generating voids at portions where the electrode layer was missing.
However, according to the present invention, the electrode layer is formed using the conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in the ceramic green sheet as a binder. Therefore, even in the case of forming a release layer containing the same binder as that contained in the ceramic green sheet and printing a conductive paste on the release layer to form an electrode layer it is possible to reliably prevent the release layer from being swollen or partially dissolved so as to generate voids at the interface between the release layer and the electrode layer or generate fissures or wrinkles on the surface of the electrode layer and it is therefore possible to effectively prevent defects from being generated in a multi-layered ceramic electronic component such as a multi-layered ceramic capacitor.
According to the present invention, it is possible to provide a conductive paste for a multi-layered ceramic electronic component which does not dissolve a binder contained in a layer adjacent to an electrode layer of the multi-layered ceramic electronic component, can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and has excellent printability.
Further, according to the present invention, it is possible to provide a method for manufacturing a multi-layered ceramic electronic component which can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and form an electrode layer in a desired manner.
It is preferable for the weight-average molecular weight of the acrylic system resin to be equal to or larger than 250,000 and equal to or smaller than 500,000 and it is more preferable for the weight-average molecular weight of the acrylic system resin to be equal to or larger than 450,000 and equal to or smaller than 500,000.
Further, it is preferable for the acid value of the acrylic system resin to be equal to or larger than 5 mgKOH/gram and equal to or smaller than 10 mgKOH/gram.
In this preferred embodiment of the present invention, the conductive paste contains a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate.
Since the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in a ceramic green sheet as a binder, even in the case of printing the conductive paste on a very thin ceramic green sheet, thereby forming an electrode layer, it is possible to effectively prevent the binder contained in the ceramic green sheet from being dissolved by the solvent contained in the conductive paste, whereby the ceramic green sheet is swollen or partially dissolved. It is therefore possible to reliably prevent generation of pinholes and cracks in the ceramic green sheet even in the case where the ceramic green sheet is very thin.
Further, since a conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)*MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate has a viscosity suitable for printing, it is possible to print a conductive paste on a ceramic green sheet using a screen printing machine, a gravure printing machine or the like to form an electrode layer in a predetermined pattern in a desired manner.
Preferably, MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 155,000 to 205,000.
In the present invention, preferably, prior to forming an electrode layer or after forming an electrode layer and drying it, a dielectric paste adapted for forming a spacer layer and containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate is printed on the surface of a ceramic green sheet in a complementary pattern to that of the electrode layer using a screen printing machine, a gravure printing machine or the like, thereby forming a spacer layer.
Furthermore, as described above, since the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in the ceramic green sheet as a binder, it is possible to reliably prevent the ceramic green sheet from being swollen or partially dissolved so as to generate voids at the interface between the ceramic green sheet and the spacer layer or generate fissures or wrinkles on the surface of the spacer layer.
Moreover, since the dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate has a viscosity suitable for printing, a spacer layer can be formed on a ceramic green sheet in a complimentary pattern to that of the electrode layer in a desired manner using a screen printing machine, a gravure printing machine or the like.
According to this embodiment, since the electrode layer is formed by printing the conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on the ceramic green sheet containing an acrylic system resin as a binder in a predetermined pattern and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in a ceramic green sheet as a binder. As a result, even in the case of printing the conductive paste on a very thin ceramic green sheet, thereby forming an electrode layer, it is possible to reliably prevent the binder contained in the ceramic green sheet from being dissolved by the solvent contained in the conductive paste and the ceramic green sheet from being swollen or partially dissolved. Therefore, even in the case where a ceramic green sheet is very thin, it is possible to effectively prevent generation of pinholes or cracks in the ceramic green sheet and it is therefore possible to effectively prevent short circuit failure from occurring in a multi-layered ceramic capacitor fabricated by laminating a number of multi-layered units.
Further, according to this embodiment, the spacer layer is formed by printing the dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate on the ceramic green sheet containing an acrylic system resin as a binder in a complementary pattern to that of the electrode layer and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in a ceramic green sheet as a binder. As a result, even in the case of printing the dielectric paste on a very thin ceramic green sheet, thereby forming a spacer layer, it is possible to reliably prevent the binder contained in the ceramic green sheet from being dissolved by the solvent contained in the dielectric paste and the ceramic green sheet from being swollen or partially dissolved so as to generate voids at the interface between the ceramic green sheet and the spacer layer or generate fissures or wrinkles on the surface of the spacer layer. Therefore, in the case where a multi-layered ceramic capacitor is fabricated by laminating a number of multi-layered units each including a ceramic green sheet and an electrode layer, it is possible to reliably prevent voids from being generated in the multi-layered ceramic capacitor and it is also possible to reliably prevent the portions of the spacer layer where fissures or wrinkles are generated from dropping off during lamination of a number of the multi-layered units to fabricate the laminated body and mixing into the laminated body as a foreign substance so as to cause internal defects in the multi-layered ceramic capacitor.
In this embodiment, the conductive paste contains a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate.
Since the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves an acrylic system resin contained in a ceramic green sheet as a binder, even in the case of forming a release layer containing the same binder as that of the ceramic green sheet and printing the conductive paste on the release layer to form an electrode layer, it is possible to effectively prevent the release layer from being swollen or partially dissolved so as to generate voids at the interface between the release layer and the electrode layer or generate fissures or wrinkles on the surface of the electrode layer.
Further, since the conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate has a viscosity suitable for printing, an electrode layer can be formed on the release layer in a predetermined pattern using a screen printing machine, a gravure printing machine or the like in a desired manner.
In the present invention, preferably, prior to forming an electrode layer or after forming an electrode layer and drying it, a dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate and prepared in the above described manner is printed on the surface of the release layer in a complementary pattern to that of the electrode layer using a screen printing machine, a gravure printing machine or the like, thereby forming a spacer layer.
In the case where the spacer layer is formed on the surface of a release layer in a complementary pattern to that of the electrode layer in this manner, it is possible to prevent a step from being formed between the surface of the electrode layer and the surface of the release layer where no electrode layer is formed. Therefore, even in the case of laminating a number of multi-layered units each including a ceramic green sheet and an electrode layer and fabricating a multi-layered electronic component such as a multi-layered ceramic capacitor, it is possible to effectively prevent the thus fabricated multi-layered electronic component from being deformed and also effectively prevent delamination of layers from occurring.
Further, as described above, since the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves the acrylic system resin contained in the ceramic green sheet as a binder, even in the case of forming the release layer containing the same binder as that of the ceramic green sheet and printing a dielectric paste on the release layer to form a spacer layer, it is possible to effectively prevent the release layer from being swollen or partially dissolved so as to generate voids at the interface between the release layer and the spacer layer or generate fissures or wrinkles on the surface of the spacer layer.
Further, since the dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate has a viscosity suitable for printing, a spacer layer can be formed on the surface of the release layer in a complementary pattern to that of the electrode layer using a screen printing machine, a gravure printing machine or the like in a desired manner.
In the case where the adhesive layer is transferred onto the surface of the electrode layer or the surfaces of the electrode layer and the spacer layer, the ceramic green sheet formed on the long support sheet is bonded onto the adhesive layer and the first support sheet is peeled off from the ceramic green sheet so that the ceramic green sheet is transferred onto the surface of the adhesive layer, thereby fabricating a multi-layered unit including the ceramic green sheet and the electrode layer or the electrode layer and the spacer layer.
Furthermore, according to this preferred embodiment, the electrode layer is formed using the conductive paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 145,000 to 215,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves an acrylic system resin contained in a ceramic green sheet as a binder. As a result, even in the case of forming the release layer containing the same binder as that contained in a ceramic green sheet and printing the conductive paste on the release layer, thereby forming an electrode layer, it is possible to effectively prevent the release layer from being swollen or partially dissolved so as to generate pinholes or cracks in the release layer and effectively prevent defects from being generated in a multi-layered ceramic capacitor.
Further, according to this preferred embodiment, the spacer layer is formed using the dielectric paste containing a binder containing ethyl cellulose having a weight average molecular weight of MWL and ethyl cellulose having a weight average molecular weight of MWH at a weight ratio of X:(1−X), where MWL, MWH and X are selected so that X* MWL+(1−X)* MWH falls within a range of 110,000 to 180,000 and at least one solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate and the solvent selected from the group consisting of isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol and acetoxy-methoxyethoxy-cyclohexanol acetate hardly dissolves an acrylic system resin contained in a ceramic green sheet as a binder. As a result, even in the case of forming a release layer containing the same binder as that contained in the ceramic green sheet and printing a dielectric paste on the surface of the release layer, thereby forming a spacer layer, it is possible to effectively prevent the release layer from being swollen or partially dissolved so as to generate voids at the interface between the release layer and the spacer layer or generate fissures or wrinkles on the surface of the spacer layer. Therefore, in the case where a multi-layered ceramic capacitor is fabricated by laminating a number of multi-layered units each including a ceramic green sheet and an electrode layer, it is possible to reliably prevent voids from being generated in the multi-layered ceramic capacitor and it is also possible to reliably prevent the portions of the spacer layer where fissures or wrinkles are generated from dropping off during lamination of a number of the multi-layered units to fabricate the laminated body and mixing into the laminated body as a foreign substance so as to cause internal defects in the multi-layered ceramic capacitor.
Moreover, according to this preferred embodiment, since it is possible to prevent the release layer from being swollen or partially dissolved, thereby changing the release strength between the release layer and the electrode layer and the spacer layer or the release layer and the electrode layer, it is possible to effectively prevent defects from being generated when a multi-layered unit is fabricated.
Then, an adhesive layer formed on a third support sheet is transferred onto the ceramic green sheet located on the side of the surface of the laminated two multi-layered units and a release layer of another multi-layered unit fabricated by laminating a ceramic green sheet, an adhesive layer, an electrode layer or an electrode layer and a spacer layer, and the release layer on a long support sheet is bonded onto the adhesive layer and the support sheet is peeled off from the release layer.
Then, an adhesive layer formed on a third support sheet is transferred onto the release layer located on the side of the surface of the laminated two multi-layered units and a ceramic green sheet of a multi-layered unit fabricated by laminating a release layer, an electrode layer or an electrode layer and a spacer layer, an adhesive layer and a ceramic green sheet on a long second support sheet is further laminated on the adhesive layer. Then, the second support sheet is peeled off from the release layer.
In a further preferred embodiment of the present invention, in the case where the adhesive layer is transferred onto the surface of the electrode layer or the surfaces of the electrode layer and the spacer layer, an adhesive layer is transferred onto the surface of a ceramic green sheet of a multi-layered unit fabricated by laminating a release layer, an electrode layer or an electrode layer and a spacer layer, an adhesive layer and a ceramic green sheet on a long second support sheet and without cutting the multi-layered unit, an electrode layer or an electrode layer and a spacer layer formed on the second support sheet are bonded onto the adhesive layer and the second support sheet is peeled off from the release layer, whereby the electrode layer and the spacer layer, and the release layer are transferred onto the surface of the adhesive layer.
Further, an adhesive layer formed on the third support sheet is transferred onto the ceramic green sheet transferred onto the adhesive layer and an electrode layer or an electrode layer and a spacer layer formed on the second support sheet are bonded onto the adhesive layer. Then, the second support sheet is peeled off from the release layer, whereby the electrode layer or the electrode layer and the spacer layer, and the release layer are transferred onto the surface of the adhesive layer.
When the additives contained in the slurry were to be pulverized, 11.65 grams of the slurry and 450 grams of ZrO2 beads having a diameter of 2 mm were charged in a polyethylene vessel having an inner volume of 250 cc and the polyethylene vessel was rotated at the circumferential velocity of 45 m/min for sixteen hours, thereby pulverizing the additive powder to prepare the additive slurry.
Then, 15 weight parts of a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. was dissolved into 85 weight parts of ethyl acetate at 50� C., thereby preparing an organic vehicle solution of 8%. Further, a slurry having the composition set out below was mixed with the organic vehicle solution for twenty hours using a polyethylene vessel having an inner volume of 500 cc, thereby preparing a dielectric paste. When the slurry was to be mixed with the organic vehicle solution, 344.1 grams of the slurry and 900 grams of ZrO2 beads having a diameter of 2 mm were charged in the polyethylene vessel and the polyethylene vessel was rotated at the circumferential velocity of 45 m/min.
11.2 weight parts
163.76 weight parts toluene
21.48 weight parts polyethylene glycol system dispersing agent
1.04 weight parts
0.83 weight parts
2.61 weight parts
0.52 weight parts
6.78 weight parts
34.77 weight parts As a polyethylene glycol system dispersing agent, a dispersing agent which was obtained by denaturing polyethylene glycol with aliphatic acid and whose hydrophile-lipophile balance (HLB) was 5 to 6 was employed and as an antistatic auxiliary agent, polyethylene glycol whose average molecular weight was 400.
150 weight parts of acetone, 104.3 weight parts of isobornyl acetate and 1.5 weight parts of polyethylene glycol system dispersing agent were added to 100 weight parts of the thus prepared additive powder to prepare a slurry and the additives contained in the slurry were pulverized using a pulverizer “LMZ0.6” (Product name) manufactured by Ashizawa Finetech Co., Ltd.
When the additives contained in the slurry were to be pulverized, ZrO2 beads having a diameter of 0.1 mm were charged into a vessel so as to occupy 80 volume % of the vessel, the vessel was rotated at the circumferential velocity of 14 m/min and the slurry was circulated between the vessel and a slurry tank until holding time of the whole slurry of two liters became 30 minutes, thereby pulverizing the additives contained in the slurry.
Then, acetone was evaporated using an evaporator and removed from the slurry, thereby preparing an additive paste in which the additives were dispersed in terpineol. The concentration of the additives contained in the additive paste was 49.3 weight %.
Then, 8 weight parts of a binder containing ethyl cellulose having a weight average molecular weight (MWH) of 230,000 and ethyl cellulose having a weight average molecular weight (MWL) of 130,000 at a weight ratio of 75:25, namely, 8 weight parts of ethyl cellulose having an apparent weight average molecular weight of 205,000 defined as X*MWL+(1−X):*MWH, was dissolved in 92 weight parts of isobornyl acetate at 70� C., thereby preparing an 8% organic vehicle solution. Further, a slurry having the composition set out below was dispersed in the organic vehicle solution for sixteen hours using a ball mill. The dispersing conditions were set so that the amount of charged ZrO2 having a diameter of 2.0 mm was 30 volume % of the ball mill, the amount of the slurry in the ball mill was 60 volume % and the circumferential velocity of the ball mill was 45 m/min.
1.77 weight parts
BaTiO3 powder manufactured by
19.14 weight parts
56.25 weight parts
1.19 weight parts
32.19 weight parts
56 weight parts
The viscosity of the thus obtained conductive paste was measured using a rheometer manufactured by HAAKE Co., Ltd. under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 19.4 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 10.4 Ps�s.
The thus prepared conductive paste was printed on the ceramic green sheet using a screen printing machine and dried at 90� C. for five minutes, thereby forming an electrode layer having a thickness of 1 μm. Thus, a multi-layered unit including the ceramic green sheet and the electrode layer laminated on the polyethylene terephthalate film was fabricated.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.143 μm and that the electrode layer having a high surface smoothness was formed.
End surfaces of the thus obtained sintered body were polished by the sandblast and coated with In—Ga alloy, thereby forming a terminal electrode. Thus, a multi-layered ceramic capacitor sample was fabricated.
Measurement of a Short-circuit Failure Ratio
As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 18%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 1 except that a binder containing ethyl cellulose having a weight average molecular weight (MWH) of 230,000 and ethyl cellulose having a weight average molecular weight (MWL) of 130,000 at a weight ratio of 50:50, namely, ethyl cellulose having an apparent weight average molecular weight of 180,000 defined as X*MWL+(1−X):*MWH, was used and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 15.5 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 8.5 Ps�s.
Then, the thus prepared conductive paste was printed on a ceramic green sheet fabricated in the manner of Working Example 1 using a screen printing machine, thereby forming an electrode layer having a thickness of 1 μm. Thus, a multi-layered unit including the ceramic green sheet and the electrode layer laminated on the polyethylene terephthalate film was fabricated.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.088 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 8%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 1 except that a binder containing ethyl cellulose having a weight average molecular weight (MWH) of 230,000 and ethyl cellulose having a weight average molecular weight (MWL) of 130,000 at a weight ratio of 25:75, namely, ethyl cellulose having an apparent weight average molecular weight of 155,000 defined as X*MWL+(1−X):*MWH, was used and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 11.2 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.8 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.065 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 6%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 1 except that dihydroterpinyl methyl ether was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 16.1 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 9.3 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.132 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 16%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 4 except that a binder containing ethyl cellulose having a weight average molecular weight (MWH) of 230,000 and ethyl cellulose having a weight average molecular weight (MWL) of 130,000 at a weight ratio of 50:50 was used and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 12.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 7.3 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.070 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 12%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 4 except that a binder containing ethyl cellulose having a weight average molecular weight (MWH) of 230,000 and ethyl cellulose having a weight average molecular weight (MWL) of 130,000 at a weight ratio of 25:75 was used and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 8.6 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 5.3 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.068 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 1 except that dihydroterpinyl oxyethanol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 16.6 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 9.6 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory. Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.133 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 18%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 3 except that dihydroterpinyl oxyethanol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 13.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 7.7 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.072 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 20%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 8.9 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 5.2 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.081 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 14%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 1 except that terpinyl methyl ether was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 16.2 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 9.4 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.115 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 2 except that terpinyl methyl ether was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 11.7 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.6 Ps�s.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 10%, so that the risk of short-circuit failure could be considered insignificant from the practical viewpoint.
A conductive paste was prepared in the manner of Working Example 3 except that terpinyl methyl ether was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 8.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 4.9 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.060 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 2 except that terpinyl oxyethanol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 10.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.2 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.071 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 2 except that d-dihydrocarveol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 10.6 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.0 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.075 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 2 except that I-menthyl acetate was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 10.6 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 5.8 Ps�s.
A conductive paste was prepared in the manner of Working Example 2 except that I-citronellol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 10.8 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.2 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.069 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 2 except that I-perillylalcohol was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 11.5 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.4 Ps�s.
A conductive paste was prepared in the manner of Working Example 2 except that acetoxy-methoxyethoxy-cyclohexanol acetate was used as a solvent instead of isobornyl acetate and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 16.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 8.9 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.078 μm and that the electrode layer having a high surface smoothness was formed.
A conductive paste was prepared in the manner of Working Example 1 except that ethyl cellulose having a weight average molecular weight of 230,000 was used as a binder of a conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 23.2 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 12.1 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.230 μm, that is, the surface roughness of the electrode layer was high, so that an electrode layer having a high surface smoothness could not be formed.
It was reasonable to conclude that this was because the viscosity of the conductive paste at the shearing velocity of 50 sec−1 was too high to print the conductive paste in a desired manner.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 36% and it was found that the short-circuit failure was very high.
A conductive paste was prepared in the manner of Working Example 1 except that ethyl cellulose having a weight average molecular weight of 130,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 7.1 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 4.7 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.070 μm, i.e., that the surface smoothness of the electrode layer was high. However, it was found that since the viscosity of the conductive paste at the shearing velocity of 50 sec−1 was too low and the fluidity of the conductive paste was too high, the conductive paste leaked from a screen printing plate and the electrode layer could not be formed in a desired pattern.
A dielectric paste for forming a ceramic green sheet was prepared in the manner of Working Example 1 except that a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 230,000 and Tg was 70� C. was used as a binder of the dielectric paste for forming a ceramic green sheet, thereby forming a ceramic green sheet.
Further, a conductive paste was prepared in the manner of Working Example 2 and the viscosity of the thus prepared dielectric paste for forming a ceramic green sheet was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 15.5 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 9.8 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.112 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in the manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 36% and it was found that the short-circuit failure was so high that the samples were of no practical use.
It is reasonable to conclude that this was because the weight-average molecular weight of the binder of the dielectric paste for forming the ceramic green sheet was 230,000, which is too low, so that part of the ceramic green sheet was swollen and dissolved by the solvent.
A conductive paste was prepared in the manner of Working Example 4 except that ethyl cellulose having a weight average molecular weight of 230,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 20.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 11.3 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.221 μm and that since the surface roughness of the electrode layer was too high, the electrode layer having a high surface smoothness could not be formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 38% and it was found that the short-circuit failure was very high.
A conductive paste was prepared in the manner of Working Example 4 except that ethyl cellulose having a weight average molecular weight of 130,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 5.3 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 3.2 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.066 μm and that the surface smoothness of the electrode layer was high. However, it was found that since the viscosity of the conductive paste at the shearing velocity of 50 sec−1 was too low and the fluidity of the conductive paste was too high, the conductive paste leaked from a screen printing plate and the electrode layer could not be formed in a desired pattern.
A dielectric paste for forming a ceramic green sheet was prepared in the manner of Working Example 1 except that a copolymer of methyl methacrylate and butyl acrylate whose weight-average molecular weight was 230,000, copolymerization ratio (weight ratio) was 82:18 and Tg was 70� C. was used as a binder of a dielectric paste for forming a ceramic green sheet, thereby forming a ceramic green sheet.
Further, a conductive paste was prepared in the manner of Working Example 5 and the viscosity of the thus prepared dielectric paste for forming a ceramic green sheet was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.120 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 34% and it was found that the short-circuit failure was so high that the samples were of no practical use.
It is reasonable to conclude that this was because the weight-average molecular weight of the binder of the dielectric paste for forming a ceramic green sheet was 230,000, which was too low, so that part of the ceramic green sheet was swollen and dissolved by the solvent.
A conductive paste was prepared in the manner of Working Example 7 except that ethyl cellulose having a weight average molecular weight of 230,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 21.1 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 11.9 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.241 μm and that since the surface roughness of the electrode layer was too high, the electrode layer having a high surface smoothness could not be formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 40% and it was found that the short-circuit failure was very high.
A conductive paste was prepared in the manner of Working Example 7 except that ethyl cellulose having a weight average molecular weight of 130,000 was used as a binder of a conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 5.5 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 3.1 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.069 μm and that the surface smoothness of the electrode layer was high. However, it was found that since the viscosity of the conductive paste at the shearing velocity of 50 sec−1 was too low and the fluidity of the conductive paste was too high, the conductive paste leaked from a screen printing plate and the electrode layer could not be printed in a desired manner.
A dielectric paste for forming a ceramic green sheet was prepared in the manner of Working Example 1 except that a copolymer of methyl methacrylate and butyl acrylate whose weight-average molecular weight was 230,000, copolymerization ratio (weight ratio) was 82:18, and Tg was 70� C. was used as a binder of a dielectric paste for forming a ceramic green sheet, thereby forming a ceramic green sheet.
Further, a conductive paste was prepared in the manner of Working Example 8 and the viscosity of the thus prepared dielectric paste for forming a ceramic green sheet was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.145 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 42% and it was found that the short-circuit failure was so high that the samples were of no practical use.
A conductive paste was prepared in the manner of Working Example 10 except that ethyl cellulose having a weight average molecular weight of 230,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 20.5 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 11.8 Ps�s.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 39% and it was found that the short-circuit failure was very high.
A conductive paste was prepared in the manner of Working Example 10 except that ethyl cellulose having a weight average molecular weight of 130,000 was used as a binder of the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 5.2 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 3.0 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.063 μm and that the surface smoothness of the electrode layer was high. However, it was found that since the viscosity of the conductive paste at the shearing velocity of 50 sec−1 was too low and the fluidity of the conductive paste was too high, the conductive paste leaked from a screen printing plate and the electrode layer could not be formed in a desired pattern.
Further, a conductive paste was prepared in the manner of Working Example 11 and the viscosity of the thus prepared dielectric paste for forming a ceramic green sheet was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.189 μm.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 56% and it was found that the short-circuit failure was so high that the samples were of no practical use.
It is reasonable to conclude that this was because the weight-average molecular weight of the binder of the dielectric paste for forming a ceramic green sheet was 230,000, which was too low, so that part of the ceramic green sheet was swollen and dissolved by the solvent
A conductive paste was prepared in the manner of Comparative Example 2 except that a mixed solvent of terpineol and kerosene (mixture ratio (mass ratio) of 50:50) was used instead of isobornyl acetate as the solvent for preparing the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 10.7 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.7 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.130 μm and that the electrode layer having a high surface smoothness was formed.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 46% and it was found that the short-circuit failure was so high that the samples were of no practical use.
It is reasonable to conclude that this was because the mixed solvent of terpineol and kerosene used as a solvent of the conductive paste dissolved a copolymer of methyl methacrylate and butyl acrylate used as the binder of the ceramic green sheet.
A conductive paste was prepared in the manner of Comparative Example 2 except that terpineol was used instead of isobornyl acetate as the solvent for preparing the conductive paste and the viscosity of the thus prepared conductive paste was measured under conditions of a temperature of 25� C. and shearing velocity of 8 sec−1 and was also measured under conditions of a temperature of 25� C. and shearing velocity of 50 sec−1.
As a result, it was found that the viscosity of the conductive paste measured under condition of the shearing velocity of 8 sec−1 was 13.1 Ps�s and that the viscosity of the conductive paste measured under condition of the shearing velocity of 50 sec−1 was 6.9 Ps�s.
The surface roughness (Ra) of the thus formed electrode layer was measured using the “SURFCORDER (SE-30D)” (Product Name) manufactured by Kosaka Laboratory Ltd. in the manner of Working Example 1. As a result, it was found that the surface roughness (Ra) of the electrode layer was 0.192 μm and that since the surface roughness of the electrode layer was too high, the electrode layer having a high surface smoothness could not be formed.
It is reasonable to conclude that this was because terpineol used as a solvent of the conductive paste dissolved a copolymer of methyl methacrylate and butyl acrylate used as the binder of the ceramic green sheet.
Further, a total of fifty multi-layered ceramic capacitor samples were fabricated and the resistance value of each of the thus fabricated multi-layered ceramic capacitor samples was measured using a multi-meter in a manner of Working Example 1 to check whether or not short-circuit failure occurred therein. As a result, the short-circuit failure ratio of the multi-layered ceramic capacitor samples was found to be 76% and it was found that the short-circuit failure was so high that the samples were of no practical use.
It was found from Working Examples 1 to 18 and Comparative Examples 13 and 14 that in the case where the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and the mixed solvent of terpineol and kerosene (mixture ratio (mass ratio) of 50:50) as a solvent or the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and terpineol as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the solvent of the conductive paste dissolved a copolymer of methyl methacrylate and butyl acrylate contained in the ceramic green sheet as a binder, so that the ceramic green sheet was swollen or partially dissolved, thereby generating pinholes or cracks in the ceramic green sheet and causing the short-circuit failure ratio of the multi-layered ceramic capacitors to become extremely high, while in the case where the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 155,000 to 205,000 defined by X* MWL+(1−X)* MWH as a binder and isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol or acetoxy-methoxyethoxy-cyclohexanol acetate as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the solvent of the conductive paste hardly dissolved a copolymer of methyl methacrylate and butyl acrylate contained in the ceramic green sheet as a binder, so that the ceramic green sheet was not swollen or partially dissolved, thereby preventing generation of pinholes or cracks in the ceramic green sheet and markedly decreasing the short-circuit failure ratio of the multi-layered ceramic capacitors.
Further, it was found from Working Examples 1 to 18 and Comparative Examples 1, 4, 7 and 10 that in the case where the conductive paste containing ethyl cellulose having a weight average molecular weight of 230,000 as a binder and isobornyl acetate as a solvent, the conductive paste containing ethyl cellulose having a weight average molecular weight of 230,000 as a binder and dihydroterpinyl methyl ether as a solvent, the conductive paste containing ethyl cellulose having a weight average molecular weight of 230,000 as a binder and dihydroterpinyl oxyethanol as a solvent or the conductive paste containing ethyl cellulose having a weight average molecular weight of 230,000 as a binder and terpinyl methyl ether as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the viscosity of the conductive paste was so high that it was impossible to print the conductive paste on the ceramic green sheet in a desired manner to form an electric layer having a high surface smoothness, so that the short-circuit failure ratio of the multi-layered ceramic capacitors became extremely high, while in the case where the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 155,000 to 205,000 defined by X* MWL+(1−X)* MWH as a binder and isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol or acetoxy-methoxyethoxy-cyclohexanol acetate as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the conductive paste had a viscosity suitable for printing, so that it was possible to form an electric layer on a ceramic green sheet in a predetermined pattern using a screen printing machine in a desired manner and fabricate multi-layered ceramic capacitors whose short-circuit failure ratio was low.
Furthermore, it was found from Working Examples 1 to 18 and Comparative Examples 2, 5, 8 and 11 that in the case where the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and isobornyl acetate as a solvent, the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and dihydroterpinyl methyl ether as a solvent, the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and dihydroterpinyl oxyethanol as a solvent or the conductive paste containing ethyl cellulose having a weight average molecular weight of 130,000 as a binder and terpinyl methyl ether as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, the viscosity of the conductive paste was too low and the fluidity of the conductive paste was too high, so that the conductive paste leaked from a screen printing plate and the electrode layer could not be formed in a desired pattern, while in the case where the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 155,000 to 205,000 defined by X* MWL+(1−X)* MWH as a binder and isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol or acetoxy-methoxyethoxy-cyclohexanol acetate as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the conductive paste had a viscosity suitable for printing, so that it was possible to form an electric layer on a ceramic green sheet in a predetermined pattern using a screen printing machine in a desired manner and fabricate multi-layered ceramic capacitors whose short-circuit failure ratio was low.
Moreover, it was found from Working Examples 1 to 18 and Comparative Examples 3, 6 and 9 that in the case where the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 180,000 as a binder and isobornyl acetate as a solvent, the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 180,000 as a binder and dihydroterpinyl methyl ether as a solvent, the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 180,000 as a binder and dihydroterpinyl oxyethanol as a solvent or the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 180,000 as a binder and terpinyl methyl ether as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, the short-circuit failure ratio of the multi-layered ceramic capacitors became very high, while in the case where the conductive paste containing ethyl cellulose having an apparent weight average molecular weight of 155,000 to 205,000 defined by X* MWL+(1−X)*MWH as a binder and isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol or acetoxy-methoxyethoxy-cyclohexanol acetate as a solvent was printed on the ceramic green sheet formed by using the dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate whose acid value was 5 mgKOH/gram, copolymerization ratio (weight ratio) was 82:18, weight-average molecular weight was 450,000 and Tg was 70� C. as a binder, thereby fabricating the multi-layered unit, and fifty of the multi-layered units were laminated, thereby fabricating the multi-layered ceramic capacitor, the short-circuit failure ratio of the multi-layered ceramic capacitors markedly decreased. It is reasonable to assume that this was because the weight-average molecular weight of the binder of the dielectric paste for forming a ceramic green sheet was 230,000, which is too low, so that part of the ceramic green sheet was swollen and dissolved by the solvent.
Further, it was found that in the case where a dielectric paste adapted for forming a spacer layer and containing ethyl cellulose having an apparent weight average molecular weight of 110,000 to 180,000 defined by X* MWL+(1−X)* MWH as a binder and isobornyl acetate, dihydroterpinyl methyl ether, dihydroterpinyl oxyethanol, terpinyl methyl ether, terpinyl oxyethanol, d-dihydrocarveol, I-menthyl acetate, I-citronellol, I-perillylalcohol or acetoxy-methoxyethoxy-cyclohexanol acetate as a solvent was prepared and the dielectric paste was printed on the ceramic green sheet in a complimentary pattern to that of the electrode layer, thereby forming a spacer layer, the same results as those above were obtained.
Further, according to the present invention, it is possible to provide a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component which can reliably prevent short circuit failure from occurring in a multi-layered ceramic electronic component and form an electrode layer in a desired manner.
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Du Pont De Nemours And CompanyThick film conductor composition(s) and processing technology thereof for use in multilayer electronic circuits and devicesUS9088014 *Jan 30, 2013Jul 21, 2015Toyota Jidosha Kabushiki KaishaMethod of manufacturing secondary batteryUS20070113952 *Nov 16, 2006May 24, 2007Nair Kumaran MThick film conductor composition(s) and processing technology thereof for use in multilayer electronic circuits and devicesUS20130193371 *Jan 30, 2013Aug 1, 2013Toyota Jidosha Kabushiki KaishaMethod of manufacturing secondary battery* Cited by examinerClassifications U.S. Classification252/512, 427/96.1International ClassificationC04B35/632, C04B35/00, H01G4/12, H01G4/008, H01B1/16, B05D5/12, H01B1/22, H01G4/30Cooperative ClassificationC04B35/632, C04B2235/662, C04B35/4682, C04B2235/5445, H01B1/22, H01G4/0085, C04B2235/3225, C04B2235/6025, C04B35/6264, C04B2235/3208, C04B2235/6582, C04B35/6365, C04B35/6261, C04B2235/3206, C04B35/63424, H01G4/008, C04B2235/6562, H01G4/30, H01G4/12, H01B1/16, C04B35/638, C04B2235/3454, C04B2235/3215, C04B2235/5454, C04B35/63488, C04B2235/3262, C04B2235/6565, C04B2235/3239, C04B2235/3436, B82Y30/00European ClassificationC04B35/468B, C04B35/626A10M, C04B35/638, C04B35/632, C04B35/634D14, C04B35/636B, C04B35/634B10, C04B35/626A6, B82Y30/00, H01G4/008, H01B1/16, H01G4/008F, H01G4/12, H01B1/22, H01G4/30Legal EventsDateCodeEventDescriptionAug 25, 2006ASAssignmentOwner name: TDK CORPORATION, JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SATOU, SHIGEKI;NOMURA, TAKESHI;REEL/FRAME:018229/0069Effective date: 20060725Oct 2, 2012FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services