JP4569100B2 - Conductor paste for multilayer ceramic electronic component and method for manufacturing multilayer unit for multilayer ceramic electronic component - Google Patents

Description

  The present invention relates to a conductor paste for an electrode layer of a multilayer ceramic electronic component and a method of manufacturing a multilayer unit for the multilayer ceramic electronic component, and more specifically, a layer adjacent to the electrode layer of the multilayer ceramic electronic component. The conductive paste for the electrode layer and the multilayer ceramic electronic component can be surely prevented from causing a short circuit failure in the multilayer ceramic electronic component without dissolving the binder contained in the multilayer ceramic electronic component. The present invention relates to a method for manufacturing a multilayer unit for a multilayer ceramic electronic component that can be reliably prevented from occurring.

  In recent years, along with the miniaturization of various electronic devices, there has been a demand for miniaturization and high performance of electronic components mounted on electronic devices, and even in multilayer ceramic electronic components such as multilayer ceramic capacitors, There is a strong demand for an increase in the number of layers and a thinner layer unit.

  To manufacture multilayer ceramic electronic components represented by multilayer ceramic capacitors, first, ceramic powder, binders such as acrylic resin and butyral resin, and plastics such as phthalates, glycols, adipic acid, and phosphates are used. A dielectric paste for a ceramic green sheet is prepared by mixing and dispersing an agent and an organic solvent such as toluene, methyl ethyl ketone, and acetone.

  Next, the dielectric paste is applied onto a support sheet formed of polyethylene terephthalate (PET) or polypropylene (PP) using an extrusion coater or gravure coater, and heated to dry the coating film. A ceramic green sheet is prepared.

Furthermore, a conductive powder such as nickel and a binder are dissolved in a solvent such as terpineol to prepare a conductive paste, and the conductive paste is applied to the ceramic green sheet in a predetermined pattern by a screen printer or the like. Print and dry to form the electrode layer.

  When the electrode layer is formed, the ceramic green sheet on which the electrode layer is formed is peeled from the support sheet to form a laminate unit including the ceramic green sheet and the electrode layer, and a desired number of laminate units are laminated. The resulting laminate is cut into chips to produce a green chip.

  Finally, the binder is removed from the green chip, the green chip is fired, and external electrodes are formed, whereby a multilayer ceramic electronic component such as a multilayer ceramic capacitor is manufactured.

  Due to the demand for miniaturization and high performance of electronic components, it is now required that the thickness of the ceramic green sheet that determines the interlayer thickness of the multilayer ceramic capacitor be 3 μm or 2 μm or less, and more than 300 ceramic green sheets And a laminate unit including an electrode layer are required to be laminated.

However, as a binder for ceramic green sheets, the most commonly used terpineol is used as a solvent as a solvent for conductor paste on a ceramic green sheet using a widely used butyral resin as a binder. When forming the electrode layer by printing the prepared conductor paste for internal electrodes, the binder of the ceramic green sheet is dissolved by the terpineol in the conductor paste, and pinholes and cracks are formed in the ceramic green sheet. Occurred, causing a short circuit failure.

In order to solve such a problem, it has been proposed to use a carbon hydrogen solvent such as kerosene or decane as a solvent for the conductor paste, but a carbon hydrogen solvent such as kerosene or decane is used for the conductor paste. Since the binder component does not dissolve, a conventionally used solvent such as terpineol cannot be completely replaced by a carbon-hydrogen solvent such as kerosene or decane, and therefore the solvent in the conductor paste is still ceramic. Since it has a certain degree of solubility in butyral resin, which is the binder of the green sheet, it prevents pinholes and cracks from occurring when the ceramic green sheet is extremely thin. In addition, it is difficult to make carbon hydrogen-based solutions such as kerosene and decane. Is different from the terpineol, because of its low viscosity, the viscosity control of the conductive paste has a problem that it is difficult.

Further, JP-A-5-325633 publication, etc. JP-A 7-21833 and JP-A No. 7-21832 discloses, instead of terpineol, hydrogenated terpineol and the like dihydro terpineol, terpene-based solvents such as dihydro terpineol acetate It proposes a conductive paste using, hydrogenated terpineol and the like dihydro terpineol, terpene-based solvents such as dihydro terpineol acetate, still against butyral resin as a binder of the ceramic green sheet, a certain degree of solubility Therefore, when the thickness of the ceramic green sheet is extremely thin, there is a problem that it is difficult to prevent pinholes and cracks from occurring in the ceramic green sheet.

  Therefore, the present invention does not dissolve the binder contained in the layer adjacent to the electrode layer of the multilayer ceramic electronic component, and can reliably prevent the occurrence of short-circuit defects in the multilayer ceramic electronic component. An object of the present invention is to provide a conductor paste for an electrode layer.

  Another object of the present invention is to provide a method of manufacturing a multilayer unit for a multilayer ceramic electronic component that can reliably prevent a short circuit failure from occurring in the multilayer ceramic electronic component.

  As a result of intensive studies to achieve the object of the present invention, the present inventor has used an acrylic resin as a binder and α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton as a solvent. When the conductor paste is prepared using at least one solvent selected from the group consisting of I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate, Even if a conductive paste is printed on a ceramic green sheet using a butyral resin as a binder to form an electrode layer, the ceramic green can be dissolved by the solvent contained in the conductive paste. The binder contained in the sheet is not melted, so the ceramic green In the case the thickness of the bets is very thin was also found that the ceramic green sheet pinholes or cracks can reliably prevent the occurrence.

Accordingly, the object of the present invention includes nickel powder as a conductor, acrylic resin as a binder, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i- This is achieved by a conductor paste comprising at least one solvent selected from the group consisting of carbyl acetate and d-dihydrocarbyl acetate .

The object of the present invention is also to include, as a binder, a ceramic green sheet containing a butyral resin, nickel powder as a conductor, acrylic resin as a binder, α-terpinyl acetate, I-dihydrocarbyl acetate. A conductive paste containing at least one solvent selected from the group consisting of I-menton, I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate in a predetermined pattern, Is achieved by a method of manufacturing a multilayer unit for a multilayer ceramic electronic component.

  According to the present invention, even when a conductive paste is printed on a very thin ceramic green sheet containing a butyral resin as a binder to form an electrode layer, the solvent contained in the conductive paste Since the binder contained in the ceramic green sheet is not melted, pinholes and cracks can be reliably prevented from occurring even when the ceramic green sheet is extremely thin. It becomes possible.

  In a preferred embodiment of the present invention, prior to the formation of the electrode layer, or after the electrode layer is formed and dried, the ceramic green sheet further includes an acrylic resin as a binder, limonene, A dielectric paste containing at least one solvent selected from the group consisting of α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate The spacer layer is formed by printing in a pattern complementary to the electrode layer.

  According to a preferred embodiment of the present invention, since the spacer layer is formed on the ceramic green sheet in a pattern complementary to the electrode layer, the surface of the electrode layer and the ceramic green sheet on which the electrode layer is not formed are formed. It is possible to prevent a step from being formed between the surface and the laminate formed by laminating a multilayer unit, each of which includes a multilayer unit including a ceramic green sheet and an electrode layer. It is possible to effectively prevent the multilayer electronic component such as a ceramic capacitor from being deformed, and to effectively prevent the occurrence of delamination.

Further, as the solvent contained in the dielectric paste for forming a conductive paste and the spacer layer to form the electrode layer, heretofore, terpineol which have been used and kerosene mixed solvent, dihydro terpineol, etc. terpineol In order to dissolve the acrylic resin contained as a binder in the ceramic green sheet, the solvent contained in the dielectric paste for forming the spacer layer dissolves in the ceramic green sheet, or dissolves the ceramic green sheet. As a result, the surface of the spacer layer is swelled and cracks and wrinkles are formed. As a result, a multilayer ceramic capacitor produced by laminating a multilayer unit including a multilayer unit including a ceramic green sheet and an electrode layer, etc. Voids easily occur in multilayer electronic components However, according to a preferred embodiment of the present invention, the dielectric paste used to form the spacer layer contains an acrylic resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl. Containing at least one solvent selected from the group consisting of acetate, I-menton, I-perillyl acetate, i-carbyl acetate, and d-dihydrocarbyl acetate, limonene, α-terpinyl acetate, I-di A solvent selected from the group consisting of hydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves butyral resin contained as a binder in the ceramic green sheet. For ceramic green Can be surely prevented from dissolving or swelling and causing cracks and wrinkles on the surface of the spacer layer. Therefore, each of the multilayer units including a ceramic green sheet and an electrode layer can be It is possible to reliably prevent the occurrence of voids in the laminated electronic component such as the laminated ceramic capacitor that is laminated.

  In the present invention, the molecular weight of the acrylic resin contained in the conductive paste and the acrylic resin contained in the dielectric paste for the spacer layer as the binder as the binder is preferably 450,000 or more and 900,000 or less, By using an acrylic resin having a molecular weight of 450,000 or more and 900,000 or less as a binder for a conductive paste and a dielectric paste for a spacer layer, a conductive paste having a desired viscosity and a dielectric for the spacer layer A paste can be prepared.

  In the present invention, as the binder, the acid value of the acrylic resin contained in the conductor paste and the dielectric paste for the spacer layer is preferably 5 mgKOH / g or more and 25 mgKOH / g or less, and the acid value is 5 mgKOH / g or more. By using an acrylic resin of 25 mgKOH / g or less as a binder of the dielectric paste for the conductor paste and the spacer layer, the conductor paste and the dielectric paste for the spacer layer having a desired viscosity can be prepared. .

  In this invention, it is preferable that the polymerization degree of the butyral resin contained in a ceramic green sheet is 1000 or more as a binder.

  In the present invention, the butyral resin contained in the ceramic green sheet as the binder preferably has a butyral degree of 64% or more and 78% or less.

In addition, when a conductive paste for internal electrodes is printed on a very thin ceramic green sheet to form an electrode layer, and a dielectric paste is printed to form a spacer layer, a solvent in the conductive paste is used. In addition, the solvent in the dielectric paste for the sepage layer dissolves or swells the binder component of the ceramic green sheet, while the ceramic green sheet has a defect that the conductive paste and the dielectric paste penetrate into the ceramic green sheet. Since there is a problem of causing defects, it is desirable that the electrode layer and the spacer layer be formed on another support sheet and dried and then adhered to the surface of the ceramic green sheet via the adhesive layer. As has been found by the inventors' studies, in this way, the electrode layer and the spacer layer are formed on a separate support sheet. In the case of forming, a release layer containing the same binder as the ceramic green sheet is formed on the surface of the support sheet so that the support sheet can be easily peeled off from the electrode layer and the spacer layer, and the conductor paste is formed on the release layer. Is preferably printed to form an electrode layer, and a dielectric paste is printed to form a spacer layer. In this way, the conductive paste is printed on the release layer having the same composition as the ceramic green sheet to form the electrode layer, and the dielectric paste is printed to form the spacer layer. When the layer contains butyral resin as a binder, and the conductor paste and dielectric paste contain terpineol as a solvent, the binder contained in the release layer contains the solvent contained in the conductor paste and dielectric paste. As a result, there is a problem that pinholes and cracks are generated in the release layer, causing problems in the multilayer ceramic electronic component such as a multilayer ceramic capacitor.

  However, according to the present invention, an acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dicarboxyl. An electrode layer is formed using a conductive paste containing at least one solvent selected from the group consisting of hydrocarbyl acetate, and preferably further contains an acrylic resin as a binder, and limonene, α-terpinyl acetate, I A spacer layer is formed using a dielectric paste containing at least one solvent selected from the group consisting of dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate. , Limonene, α-terpinyl acetate The solvent selected from the group consisting of I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate, and d-dihydrocarbyl acetate contains almost no butyral resin contained as a binder in the ceramic green sheet. Since it does not dissolve, a release layer containing the same binder as the ceramic green sheet is formed, and a conductive paste is printed on the release layer, an electrode layer is formed, and a dielectric paste is printed to form a spacer layer. Even in this case, it is possible to effectively prevent the occurrence of pinholes and cracks in the release layer, and it is possible to effectively prevent defects in the multilayer ceramic electronic component such as the multilayer ceramic capacitor. .

  According to the present invention, the binder contained in the layer adjacent to the electrode layer of the multilayer ceramic electronic component is not melted, and it is possible to reliably prevent occurrence of a short circuit defect in the multilayer ceramic electronic component. It becomes possible to provide a conductor paste for the electrode layer.

  Furthermore, according to the present invention, it is possible to provide a method for manufacturing a multilayer unit for a multilayer ceramic electronic component that can reliably prevent a short circuit defect from occurring in the multilayer ceramic electronic component.

  In a preferred embodiment of the present invention, a dielectric paste containing an acrylic resin as a binder is prepared and applied on a long support sheet using an extrusion coater or a wire bar coater to form a coating film. Is done.

  The degree of polymerization of the butyral resin is preferably 1000 or more, and the degree of butyralization of the butyral resin is preferably 64% or more and 78% or less.

  As the support sheet to which the dielectric paste is applied, for example, a polyethylene terephthalate film or the like is used, and a silicon resin, an alkyd resin, or the like is coated on the surface in order to improve the peelability.

  The coating is then dried, for example, at a temperature of about 50 ° C. to about 100 ° C. for about 1 minute to about 20 minutes to form a ceramic green sheet on the support sheet.

  The thickness of the ceramic green sheet after drying is preferably 3 μm or less, and more preferably 1.5 μm or less.

  Next, on the ceramic green sheet formed on the surface of the long support sheet, a conductor paste for internal electrodes is printed in a predetermined pattern using a screen printer, a gravure printer, etc. Is formed.

  The electrode layer is preferably formed to a thickness of about 0.1 μm to about 5 μm after drying, and more preferably about 0.1 μm to about 1.5 μm.

  In this embodiment, the conductive paste contains an acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate, and d. -It contains at least one solvent selected from the group consisting of dihydrocarbyl acetate.

  A solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is added to the ceramic green sheet as a binder. Since the butyral resin contained in the resin paste is hardly dissolved, even when an electrode layer is formed by printing a conductive paste on a very thin ceramic green sheet, the ceramic green is removed by the solvent contained in the conductive paste. It is possible to effectively prevent the binder contained in the sheet from being melted. Therefore, even when the thickness of the ceramic green sheet is very thin, pinholes and cracks are generated in the ceramic green sheet. Effectively prevent Door is possible.

  The molecular weight of the acrylic resin contained in the conductor paste is preferably 450,000 or more and 900,000 or less, and by using an acrylic resin having a molecular weight of 450,000 or more and 900,000 or less as a binder of the conductor paste. A conductor paste having a desired viscosity can be prepared.

  The acid value of the acrylic resin contained in the conductor paste is preferably 5 mgKOH / g or more and 25 mgKOH / g or less, and the acid value is 5 mgKOH / g or more and 25 mgKOH / g or less. By using as a binder, a conductive paste having a desired viscosity can be prepared.

  Preferably, prior to the formation of the electrode layer, or after the electrode layer is formed and dried, an acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton A dielectric paste containing at least one solvent selected from the group consisting of I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is formed on the surface of the ceramic green sheet in a pattern complementary to the electrode layer. The spacer layer is formed by printing using a screen printer or a gravure printer.

  Thus, by forming a spacer layer in a pattern complementary to the electrode layer on the surface of the ceramic green sheet, between the surface of the electrode layer and the surface of the ceramic green sheet on which the electrode layer is not formed. A multilayer electronic component such as a multilayer ceramic capacitor produced by laminating a multilayer unit of a large number of multilayer units each including a ceramic green sheet and an electrode layer. As a result, it is possible to effectively prevent the occurrence of deformation and to effectively prevent the occurrence of delamination.

  Further, as described above, a solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate, and d-dihydrocarbyl acetate. Since the butyral resin contained in the ceramic green sheet as a binder is hardly dissolved, it is included in the dielectric paste even when the spacer layer is formed by printing the dielectric paste on the very thin ceramic green sheet. Therefore, it is possible to effectively prevent the binder contained in the ceramic green sheet from being dissolved by the dissolved solvent. Therefore, even when the thickness of the ceramic green sheet is very thin, pinholes are formed in the ceramic green sheet. And cracks occur It becomes possible to effectively prevent.

  The molecular weight of the acrylic resin contained in the dielectric paste for forming the spacer layer is preferably 450,000 or more and 900,000 or less, and an acrylic resin having a molecular weight of 450,000 or more and 900,000 or less is used as the spacer layer. A dielectric paste having a desired viscosity can be prepared by using it as a binder for a dielectric paste for use.

  The acid value of the acrylic resin is preferably 5 mgKOH / g or more and 25 mgKOH / g or less, and the acid value is 5 mgKOH / g or more and 25 mgKOH / g or less. The acrylic resin is used as a binder for the dielectric paste for the spacer layer. As a result, a dielectric paste having a desired viscosity can be prepared.

  Next, the electrode layer or the electrode layer and the spacer layer are dried to produce a laminate unit in which the ceramic green sheet and the electrode layer or the electrode layer and the spacer layer are laminated on the support sheet.

  In producing a multilayer ceramic capacitor, the support sheet is peeled from the ceramic green sheet of the multilayer unit, cut into a predetermined size, and a predetermined number of multilayer units are stacked on the outer layer of the multilayer ceramic capacitor. Further, the other outer layer is laminated on the laminate unit, and the obtained laminate is press-molded and cut into a predetermined size to produce a large number of ceramic green chips.

  The ceramic green chip thus produced is placed in a reducing gas atmosphere, the binder is removed, and the ceramic green chip is further fired.

  Next, necessary external electrodes and the like are attached to the fired ceramic green chip to produce a multilayer ceramic capacitor.

  According to this embodiment, as a binder, an acrylic resin is included as a binder on a ceramic green sheet containing a butyral resin, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I- A conductive paste containing at least one solvent selected from the group consisting of perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is printed in a predetermined pattern to form an electrode layer. A solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is applied to the ceramic green sheet. Butyral system included as a binder Since the resin is hardly dissolved, even when the conductive paste is printed on a very thin ceramic green sheet to form an electrode layer, it is contained in the ceramic green sheet due to the solvent contained in the conductive paste. Therefore, even if the thickness of the ceramic green sheet is very thin, pinholes and cracks are effectively prevented from occurring in the ceramic green sheet. Thus, it is possible to effectively prevent a short circuit defect from occurring in the multilayer ceramic electronic component.

  Further, according to this embodiment, the spacer layer is formed in a pattern complementary to the electrode layer on the ceramic green sheet, so that the surface of the electrode layer and the surface of the ceramic green sheet on which the electrode layer is not formed Therefore, it is possible to prevent the formation of a step between the laminated ceramic unit and the laminated ceramic unit produced by laminating the multilayer unit, each of which includes a ceramic green sheet and an electrode layer. It is possible to effectively prevent the multilayer electronic component such as a capacitor from being deformed, and to effectively prevent the occurrence of delamination.

  Furthermore, according to this embodiment, on the ceramic green sheet containing a butyral resin as a binder, an acrylic resin is included as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, A dielectric paste containing at least one solvent selected from the group consisting of I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is printed in a pattern complementary to the electrode layer to form a spacer layer. A solvent configured to form and selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate Use ceramic green sheet as a binder Since the butyral resin contained in the dielectric paste is hardly dissolved, even when a dielectric paste is printed on a very thin ceramic green sheet to form a spacer layer, the ceramic green sheet is formed by the solvent contained in the dielectric paste. Therefore, it is possible to reliably prevent the ceramic green sheet from swelling and cracking or wrinkling on the surface of the spacer layer. It is possible to reliably prevent the generation of voids in a multilayer electronic component such as a multilayer ceramic capacitor produced by stacking a multilayer unit including a large number of multilayer units including the multilayer unit.

  In another preferred embodiment of the present invention, a second support sheet different from the long support sheet used to form the ceramic green sheet is prepared, and the long support sheet A dielectric paste containing a dielectric material particle having substantially the same composition as the dielectric material contained in the ceramic green sheet and a binder identical to the binder contained in the ceramic green sheet is formed on the surface of the wire bar. Using a coater or the like, it is applied and dried to form a release layer.

  As the second support sheet, for example, a polyethylene terephthalate film or the like is used, and a silicon resin, an alkyd resin, or the like is coated on the surface in order to improve the peelability.

  The thickness of the release layer is preferably not more than the thickness of the electrode layer, preferably not more than about 60% of the thickness of the electrode layer, and more preferably not more than about 30% of the thickness of the electrode layer.

  After the release layer is dried, a conductor paste for internal electrodes is printed in a predetermined pattern on the surface of the release layer using a screen printing machine or a gravure printing machine, and the electrode layer is dried. It is formed.

  The electrode layer is preferably formed to a thickness of about 0.1 μm to about 5 μm, more preferably about 0.1 μm to about 1.5 μm.

  In this embodiment, the conductive paste contains an acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate, and d. -It contains at least one solvent selected from the group consisting of dihydrocarbyl acetate.

  A solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is added to the ceramic green sheet as a binder. Even if the electrode layer is formed by forming a release layer containing the same binder as the ceramic green sheet and printing a conductor paste on the release layer, the butyral resin contained as It is possible to effectively prevent the occurrence of pinholes and cracks in the multilayer ceramic electronic component such as a multilayer ceramic capacitor.

  The molecular weight of the acrylic resin contained in the conductor paste is preferably 450,000 or more and 900,000 or less, and by using an acrylic resin having a molecular weight of 450,000 or more and 900,000 or less as a binder of the conductor paste. A conductor paste having a desired viscosity can be prepared.

  The acid value of the acrylic resin contained in the conductor paste is preferably 5 mgKOH / g or more and 25 mgKOH / g or less, and the acid value is 5 mgKOH / g or more and 25 mgKOH / g or less. By using as a binder, a conductive paste having a desired viscosity can be prepared.

  Preferably, prior to the formation of the electrode layer, or after the electrode layer is formed and dried, an acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton A dielectric paste containing at least one solvent selected from the group consisting of I-perillyl acetate, i-carbyl acetate and d-dihydrocarbyl acetate is complementary to the electrode layer on the surface of the second support sheet. The pattern is printed using a screen printer, a gravure printer or the like to form a spacer layer.

  Thus, by forming a spacer layer in a pattern complementary to the electrode layer on the surface of the ceramic green sheet, between the surface of the electrode layer and the surface of the ceramic green sheet on which the electrode layer is not formed. A multilayer electronic component such as a multilayer ceramic capacitor produced by laminating a multilayer unit of a large number of multilayer units each including a ceramic green sheet and an electrode layer. As a result, it is possible to effectively prevent the occurrence of deformation and to effectively prevent the occurrence of delamination.

  Further, as described above, a solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i-carbyl acetate, and d-dihydrocarbyl acetate. Since the butyral resin contained in the ceramic green sheet as a binder is hardly dissolved, a release layer containing the same binder as the ceramic green sheet is formed, and a dielectric paste is printed on the release layer to form a spacer layer. In this case, pinholes and cracks can be effectively prevented from occurring in the release layer, and it is possible to effectively prevent defects in multilayer ceramic electronic components such as multilayer ceramic capacitors. Become.

  Further, a long third support sheet is prepared, and the adhesive solution is applied to the surface of the third support sheet by a bar coater, an extrusion coater, a reverse coater, a dip coater, a kiss coater, etc. and dried. An adhesive layer is formed.

  Preferably, the adhesive solution has substantially the same composition as the binder similar to the binder contained in the dielectric paste for forming the ceramic green sheet and the particles of the dielectric material contained in the ceramic green sheet. A dielectric material particle having a particle size equal to or smaller than the thickness of the adhesive layer, a plasticizer, an antistatic agent, and a release agent.

  The adhesive layer is preferably formed to a thickness of about 0.3 μm or less, more preferably from about 0.02 μm to about 0.3 μm, and even more preferably from about 0.02 μm to about 0.2 μm. Is formed.

  Thus, the adhesive layer formed on the long third support sheet was formed on the electrode layer or electrode layer and spacer layer or support sheet formed on the long second support sheet. It adheres to the surface of the ceramic green sheet, and after adhesion, the third support sheet is peeled off from the adhesive layer, and the adhesive layer is transferred.

  When the adhesive layer is transferred to the surface of the electrode layer or the electrode layer and the spacer layer, the ceramic green sheet formed on the surface of the long support sheet is adhered to the surface of the adhesive layer. The support sheet is peeled from the ceramic green sheet, the ceramic green sheet is transferred to the surface of the adhesive layer, and a laminate unit including the ceramic green sheet and the electrode layer is created.

  The adhesive layer is transferred to the surface of the ceramic green sheet of the laminate unit thus obtained, in the same manner as the adhesive layer is transferred to the surface of the electrode layer or the electrode layer and the spacer layer. Is transferred to a predetermined size.

  Similarly, a predetermined number of laminate units having the adhesive layer transferred thereon are produced on the surface, and a prescribed number of laminate units are laminated to produce a laminate block.

  In producing the laminate block, first, the laminate unit is positioned on the support formed of polyethylene terephthalate or the like so that the adhesive layer transferred to the surface of the laminate unit contacts the support. The laminate unit is bonded onto the support through the adhesive layer by being pressurized by a machine or the like.

  Then, a 2nd support sheet peels from a peeling layer, and a laminated body unit is laminated | stacked on a support body.

  Next, the new laminate unit is positioned so that the adhesive layer formed on the surface is in contact with the surface of the release layer of the laminate unit laminated on the support, and is pressed by a press or the like, A new laminate unit is laminated on the release layer of the laminate unit laminated on the support via an adhesive layer, and then the second support sheet is released from the release layer of the new laminate unit. Is done.

  The same process is repeated to produce a laminate block in which a predetermined number of laminate units are laminated.

  On the other hand, when the adhesive layer is transferred to the surface of the ceramic green sheet, the electrode layer or the electrode layer and the spacer layer formed on the second support sheet are adhered to the surface of the adhesive layer. The second support sheet is peeled from the release layer, and the electrode layer or the electrode layer and the spacer layer and the release layer are transferred to the surface of the adhesive layer, and a laminate unit including the ceramic green sheet and the electrode layer is created.

  The adhesive layer is transferred to the surface of the ceramic green sheet of the laminate unit thus obtained, in the same manner as the adhesive layer is transferred to the surface of the electrode layer or the electrode layer and the spacer layer. Is transferred to a predetermined size.

  Similarly, a predetermined number of laminate units having the adhesive layer transferred thereon are produced on the surface, and a prescribed number of laminate units are laminated to produce a laminate block.

  In producing the laminate block, first, the laminate unit is positioned on the support formed of polyethylene terephthalate or the like so that the adhesive layer transferred to the surface of the laminate unit contacts the support. The laminate unit is bonded onto the support through the adhesive layer by being pressurized by a machine or the like.

  Thereafter, the support sheet is peeled from the ceramic green sheet, and the laminate unit is laminated on the support.

  Next, a new laminate unit is positioned so that the adhesive layer formed on the surface is in contact with the surface of the ceramic green sheet of the laminate unit laminated on the support, and is pressed by a press machine or the like. A new laminate unit is laminated on the ceramic green sheet of the laminate unit laminated on the support via an adhesive layer, and then the support sheet is peeled from the ceramic of the new laminate unit. .

  The same process is repeated to produce a laminate block in which a predetermined number of laminate units are laminated.

  A laminate block including a predetermined number of laminate units thus produced is laminated on the outer layer of the multilayer ceramic capacitor, and the other outer layer is laminated on the laminate block. It is press-molded and cut into a predetermined size to produce a large number of ceramic green chips.

  The ceramic green chip thus produced is placed in a reducing gas atmosphere, the binder is removed, and the ceramic green chip is further fired.

  Next, necessary external electrodes and the like are attached to the fired ceramic green chip to produce a multilayer ceramic capacitor.

  According to this embodiment, since the electrode layer formed on the second support sheet is dried, the electrode layer is configured to adhere to the surface of the ceramic green sheet via the adhesive layer. The conductive paste does not soak into the ceramic green sheet as in the case of forming the electrode layer by printing the conductive paste on the surface, and the electrode layer is applied to the surface of the ceramic green sheet as desired. It becomes possible to form.

  In addition, according to this embodiment, an acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate, and d- An electrode layer is formed using a conductive paste containing at least one solvent selected from the group consisting of dihydrocarbyl acetate, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peri. Since the solvent selected from the group consisting of ril acetate, i-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves butyral resin contained as a binder in the ceramic green sheet, the release containing the same binder as the ceramic green sheet Forming a layer, release layer Even when an electrode layer is formed by printing a conductive paste on the top, it is possible to effectively prevent the occurrence of pinholes and cracks in the release layer, and multilayer ceramic electronic components such as multilayer ceramic capacitors It is possible to effectively prevent the occurrence of defects.

  Furthermore, according to this embodiment, an acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate, and d- A spacer layer is formed using a dielectric paste containing at least one solvent selected from the group consisting of dihydrocarbyl acetate, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peri Since the solvent selected from the group consisting of ril acetate, i-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves butyral resin contained as a binder in the ceramic green sheet, the release containing the same binder as the ceramic green sheet Forming a layer, Even when a dielectric paste is printed on the release layer to form a spacer layer, it is possible to effectively prevent the occurrence of pinholes and cracks in the release layer. It is possible to effectively prevent the electronic component from being defective.

  In another embodiment of the present invention, when the adhesive layer is transferred to the surface of the electrode layer or the electrode layer and the spacer layer, the release layer, the electrode layer, or the electrode is formed on the long second support sheet. After the adhesive layer is transferred to the surface of the ceramic green sheet of the laminate unit formed by laminating the layer and the spacer layer, the adhesive layer, and the ceramic green sheet, the adhesive unit is not cut, and the adhesive unit is not cut. The ceramic green sheet, the adhesive layer, the electrode layer or the electrode layer and the spacer layer, and the release layer are laminated on the long support sheet, and the release layer of the formed laminate unit is adhered to the ceramic green sheet. The support sheet is peeled off, and two laminate units are stacked on the long second support sheet.

  Next, the adhesive layer formed on the third support sheet is transferred onto the ceramic green sheet located on the surface of the two laminate units, and further, the ceramic is formed on the long support sheet. The green sheet, the adhesive layer, the electrode layer or electrode layer, the spacer layer, and the release layer are laminated, the release layer of the formed laminate unit is adhered, and the support sheet is released from the ceramic green sheet.

  The same process is repeated to produce a laminate unit set in which a predetermined number of laminate units are laminated, and further on the third support sheet on the surface of the ceramic green sheet located on the surface of the laminate unit set. After the adhesive layer formed on is transferred, it is cut into a predetermined size to produce a laminate block.

  On the other hand, when the adhesive layer is transferred to the surface of the ceramic green sheet, the ceramic green sheet, the adhesive layer, the electrode layer or the electrode layer, the spacer layer, and the release layer are laminated on the long support sheet. After the adhesive layer is transferred to the surface of the release layer of the formed laminate unit, the release unit is formed on the long second support sheet without being cut into the laminate unit. The electrode layer or the electrode layer and the spacer layer, the adhesive layer and the ceramic green sheet are laminated, the ceramic green sheet of the formed laminate unit is adhered, the second support sheet is peeled from the release layer, and the long Two laminated units are laminated on the support sheet.

  Next, the adhesive layer formed on the third support sheet is transferred onto the release layer located on the surface of the two laminate units, and further, the adhesive layer is applied to the long second support sheet. The release layer, the electrode layer or the electrode layer and the spacer layer, the adhesive layer, and the ceramic green sheet are laminated, and the ceramic green sheet of the formed laminate unit is adhered, and the second support sheet is peeled from the release layer. .

  The same process was repeated to produce a laminate unit set in which a predetermined number of laminate units were laminated, and the adhesive layer was transferred to the surface of the ceramic green sheet located on the surface of the laminate unit set. Thereafter, the laminate block is produced by cutting into a predetermined size.

  A multilayer ceramic capacitor is manufactured using the multilayer body block thus manufactured in the same manner as in the above embodiment.

  According to this embodiment, the laminate unit is sequentially laminated on the long second support sheet or the support sheet to produce a laminate unit set including a predetermined number of laminate units, and then In addition, since the laminated body unit set is cut to a predetermined size to create a laminated body block, the laminated body units cut to a predetermined size are laminated one by one to produce a laminated body block. Compared to the case, the manufacturing efficiency of the laminated body block can be greatly improved.

  In still another embodiment of the present invention, when the adhesive layer is transferred to the surface of the electrode layer or the electrode layer and the spacer layer, the release layer, the electrode layer, or the After the electrode layer, spacer layer, adhesive layer and ceramic green sheet are laminated and the adhesive layer is transferred to the surface of the ceramic green sheet of the formed laminate unit, the laminate unit is bonded without being cut. The electrode layer or electrode layer and spacer layer formed on the second support sheet are adhered to the layer, and the second support sheet is peeled from the release layer, so that the electrode layer or electrode layer and spacer layer and release layer are And transferred to the surface of the adhesive layer.

  Next, the adhesive layer formed on the third support sheet is transferred to the surface of the release layer transferred to the surface of the adhesive layer, and the ceramic green sheet formed on the support sheet is adhered to the adhesive layer, The support sheet is peeled from the ceramic green sheet, and the ceramic green sheet is transferred to the surface of the adhesive layer.

  Furthermore, the adhesive layer formed on the third support sheet is transferred to the surface of the ceramic green sheet transferred to the surface of the adhesive layer, and the electrode layer or electrode layer formed on the second support sheet is The spacer layer is bonded to the adhesive layer, the second support sheet is peeled from the release layer, and the electrode layer or the electrode layer and the spacer layer and the release layer are transferred to the surface of the adhesive layer.

  The same process was repeated to produce a laminate unit set in which a predetermined number of laminate units were laminated, and the adhesive layer was transferred to the surface of the ceramic green sheet located on the surface of the laminate unit set. Thereafter, the laminate block is produced by cutting into a predetermined size.

  On the other hand, when the adhesive layer is transferred to the surface of the ceramic green sheet, the ceramic green sheet, the adhesive layer, the electrode layer or the electrode layer, the spacer layer, and the release layer are laminated on the long support sheet. After the adhesive layer is transferred to the surface of the release layer of the formed laminate unit, the ceramic green sheet formed on the support sheet is bonded to the adhesive layer without cutting the laminate unit. The support sheet is peeled from the ceramic green sheet, and the ceramic green sheet is transferred to the surface of the adhesive layer.

  Next, the adhesive layer formed on the third support sheet is transferred to the surface of the ceramic green sheet transferred to the surface of the adhesive layer, and the electrode layer or electrode layer and spacer formed on the second support sheet The layer is adhered to the adhesive layer, the second support sheet is peeled from the release layer, and the electrode layer or the electrode layer and the spacer layer and the release layer are transferred to the surface of the adhesive layer.

  Furthermore, the adhesive layer formed on the third support sheet is transferred to the surface of the release layer transferred to the surface of the adhesive layer, and the ceramic green sheet formed on the support sheet is bonded to the adhesive layer. Then, the support sheet is peeled from the ceramic green sheet, and the ceramic green sheet is transferred to the surface of the adhesive layer.

  After the same process is repeated, a laminate unit set in which a predetermined number of laminate units are laminated is produced, and the adhesive layer is transferred to the surface of the release layer located on the surface of the laminate unit set. The laminate block is manufactured by cutting into a predetermined size.

  A multilayer ceramic capacitor is manufactured using the multilayer body block thus manufactured in the same manner as in the above embodiment.

  According to this embodiment, the adhesive layer is transferred onto the surface of the elongated second support sheet or the laminate unit formed on the support sheet, and the electrode layer or the electrode layer and the spacer layer and the release layer are transferred. Then, the transfer of the adhesive layer and the transfer of the ceramic green sheet are repeated to laminate the laminate units one after another to produce a laminate unit set including a predetermined number of laminate units. Since the laminate block is created by cutting to a predetermined size, the laminate units cut to a predetermined size are laminated one by one, and compared with the case where a laminate block is produced. The production efficiency of the body block can be greatly improved.

  Hereinafter, examples and comparative examples will be given to clarify the effects of the present invention.

Example 1
Preparation of dielectric paste for ceramic green sheet 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 parts by weight of Y ₂ O ₃ , 0.72 parts by weight of MgCO ₃ and 0.13 parts by weight MnO and 0.045 parts by weight of V ₂ O ₅ were mixed to prepare an additive powder.

  72.3 parts by weight of ethyl alcohol, 72.3 parts by weight of propyl alcohol, 25.8 parts by weight of xylene, and 0.93 parts by weight of polyethylene glycol with respect to 100 parts by weight of the additive powder thus prepared. The system dispersant was mixed to prepare a slurry, and additives in the slurry were pulverized.

In crushing the additive in the slurry, 11.65 g of slurry and 450 g of ZrO ₂ beads (diameter 2 mm) are filled in a 250 cc polyethylene container, and the polyethylene container is rotated at a peripheral speed of 45 m / min. Additive slurry was prepared by grinding the additive in the slurry for 16 hours.

  The median diameter of the additive after pulverization was 0.1 μm.

Next, 15 parts by weight of polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) was dissolved in 42.5 parts by weight of ethyl alcohol and 42.5 parts by weight of propyl alcohol at 50 ° C. A 15% solution was prepared, and a slurry having the following composition was further mixed for 20 hours using a 500 cc polyethylene container to prepare a dielectric paste. In mixing, 330.1 g of slurry and 900 g of ZrO ₂ beads (diameter 2 mm) were filled in a polyethylene container, and the polyethylene container was rotated at a peripheral speed of 45 m / min.

BaTiO ₃ powder (manufactured by Sakai Chemical Industry Co., Ltd .: trade name “BT-02”: particle size 0.2 μm)
100 parts by weight additive slurry 11.65 parts by weight ethyl alcohol 35.32 parts by weight propyl alcohol 35.32 parts by weight xylene 16.32 parts by weight benzylbutyl phthalate (plasticizer) 2.61 parts by weight mineral spirit 7.3 parts by weight Part Polyethylene glycol-based dispersant 2.36 parts by weight Imidazoline-based charging aid 0.42 parts by weight Organic vehicle 33.74 parts by weight Methyl ethyl ketone 43.81 parts by weight 2-Butoxyethyl alcohol 43.81 parts by weight As a polyethylene glycol-based dispersant Used a dispersant (HLB = 5 to 6) obtained by modifying polyethylene glycol with a fatty acid.

Formation of ceramic green sheet The obtained dielectric paste was applied onto a polyethylene terephthalate film at a coating speed of 50 m / min using a die coater to form a coating film in a drying oven maintained at 80 ° C. Then, the obtained coating film was dried to form a ceramic green sheet having a thickness of 1 μm.

Preparation of conductor paste for electrodes 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 parts by weight of Y ₂ O ₃ , 0.72 parts by weight of MgCO ₃ , and 0.13 parts by weight of MnO And 0.045 parts by weight of V ₂ O ₅ were mixed to prepare an additive powder.

  To 100 parts by weight of the additive powder thus prepared, 150 parts by weight of acetone, 104.3 parts by weight of limonene, and 1.5 parts by weight of a polyethylene glycol dispersant are mixed to prepare a slurry, The additive in the slurry was pulverized using a pulverizer “LMZ0.6” (trade name) manufactured by Ashizawa Finetech Co., Ltd.

In crushing the additive in the slurry, ZrO ₂ beads (0.1 mm in diameter) are filled into the vessel at 80% of the vessel capacity, and the rotor is rotated at a peripheral speed of 14 m / min. The slurry was circulated between the vessel and the slurry tank until the time for all the slurry to stay in the vessel was 5 minutes, and the additives in the slurry were pulverized.

  The median diameter of the additive after pulverization was 0.1 μm.

  Next, using an evaporator, acetone was evaporated and removed from the slurry to prepare an additive paste in which the additive was dispersed in limonene. The non-volatile component concentration in the additive paste was 49.3% by weight.

Next, 8 parts by weight of a copolymer of methyl methacrylate and butyl acrylate (copolymerization ratio 82:18, molecular weight 700,000) having an acid value of 5 mg KOH / g was dissolved in 92 parts by weight of limonene at 70 ° C. An 8% solution of the vehicle was prepared, and a slurry having the following composition was further dispersed for 16 hours using a ball mill. The dispersion conditions were such that the ZrO ₂ (diameter 2.0 mm) filling amount in the mill was 30% by volume, the slurry amount in the mill was 60% by volume, and the peripheral speed of the ball mill was 45 m / min.

Nickel powder (particle size 0.2 μm) manufactured by Kawatetsu Kogyo Co., Ltd. 100 parts by weight Additive paste 1.77 parts by weight BaTiO ₃ powder (manufactured by Sakai Chemical Industry Co., Ltd .: particle size 0.05 μm)
19.14 parts by weight Organic vehicle 56.25 parts by weight Polyethylene glycol dispersant 1.19 parts by weight Dioctyl phthalate (plasticizer) 2.25 parts by weight
α- Turpinyl acetate 83.96 parts by weight Acetone 56 parts by weight Then, using a stirrer equipped with an evaporator and a heating mechanism, acetone is evaporated from the slurry thus obtained and removed from the mixture. A paste was obtained. The conductor material concentration in the conductor paste was 47% by weight.

Formation of electrode layer and production of laminate unit The conductor paste thus prepared was printed on a ceramic green sheet using a screen printer, dried at 90 ° C. for 5 minutes, and dried to a thickness of 1 μm. An electrode layer was formed, and a laminate unit was produced in which a ceramic green sheet and an electrode layer were laminated on the surface of a polyethylene terephthalate film.

The surface roughness (Ra) of the electrode layer thus formed was 0.069 μm when measured using “Surf Coder (SE-30D)” (trade name) manufactured by Kosaka Laboratory Ltd.

Furthermore, when the surface of the electrode layer was observed using a metal microscope at a magnification of 400, no cracks or wrinkles were observed.
* This is necessary for balance with the spacer layer.

Production of Ceramic Green Chip As described above, the prepared dielectric paste is applied to the surface of a polyethylene terephthalate film using a die coater to form a coating film, and the coating film is dried to obtain a thickness of 10 μm. A ceramic green sheet was formed.

  The ceramic green sheet having a thickness of 10 μm thus prepared is peeled from the polyethylene terephthalate film, cut, and the five cut ceramic green sheets are laminated to form a cover layer having a thickness of 50 μm. Further, the laminate unit was peeled off from the polyethylene terephthalate film, cut, and 50 laminate units cut were laminated on the cover layer.

  Next, the ceramic green sheet having a thickness of 10 μm is peeled off from the polyethylene terephthalate film, cut, and the five cut ceramic green sheets are laminated on the laminated body unit to obtain a thickness of 50 μm. An effective layer having a thickness of 100 μm, in which 50 laminate units including a lower cover layer having a thickness of 1 μm, a ceramic green sheet having a thickness of 1 μm, and an electrode layer having a thickness of 1 μm are stacked; and a thickness of 50 μm The laminated body with which the upper cover layer which has thickness was laminated | stacked was produced.

  Furthermore, the laminated body thus obtained was press-molded under a temperature condition of 70 ° C. by applying a pressure of 100 MPa, and cut into a predetermined size by a dicing machine to produce a ceramic green chip.

Production of Multilayer Ceramic Capacitor Sample The thus produced ceramic green chip was treated in air under the following conditions to remove the binder.

Temperature increase rate: 50 ° C / hour Holding temperature: 240 ° C
Holding time: 8 hours After removing the binder, the ceramic green chip was treated and fired under the following conditions in a mixed gas atmosphere of nitrogen gas and hydrogen gas controlled at a dew point of 20 ° C. The contents of nitrogen gas and hydrogen gas in the mixed gas were 95% by volume and 5% by volume.

Temperature rising rate: 300 ° C / hour Holding temperature: 1200 ° C
Holding time: 2 hours Cooling rate: 300 ° C./hour Further, the fired ceramic green chip was annealed under the following conditions in an atmosphere of nitrogen gas controlled at a dew point of 20 ° C.

Temperature increase rate: 300 ° C / hour Holding temperature: 1000 ° C
Holding time: 3 hours Cooling rate: 300 ° C./hour The end face of the sintered body thus obtained was polished by sand blasting, then coated with an In—Ga alloy to form terminal electrodes, and a multilayer ceramic capacitor sample was produced. .

  In the same manner, a total of 50 multilayer ceramic capacitor samples were produced.

Measurement of short-circuit rate The resistance values of the 50 multilayer ceramic capacitor samples thus produced were measured with a multimeter to inspect the short-circuit failure of the multilayer ceramic capacitor samples.

  When the obtained resistance value was 100 kΩ or less, the short-circuit failure was determined, the number of multilayer ceramic capacitor samples in which the short-circuit failure was observed was determined, the ratio (%) to the total number of multilayer ceramic capacitor samples was calculated, and the short-circuit rate was measured. .

As a result, the short-circuit rate was 14% .

Example 2
In the same manner as in Example 1 except that I-dihydrocarbyl acetate was used in place of α-terpinyl acetate as a solvent in preparing the conductor paste, When the electrode layer was formed on the green sheet and the surface roughness (Ra) of the electrode layer was measured, it was 0.070 μm.

  Moreover, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, no cracks or wrinkles were observed.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 18%.

Example 3
A ceramic green sheet is prepared in the same manner as in Example 1 except that I-menton is used instead of α-terpinyl acetate as a solvent for preparing the conductor paste. An electrode layer was formed thereon, and the surface roughness (Ra) of the electrode layer was measured and found to be 0.066 μm.

  Moreover, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, no cracks or wrinkles were observed.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 10%.

Example 4
In the same manner as in Example 1 except that I-peryl acetate was used in place of α-terpinyl acetate as the solvent for preparing the conductive paste, When the electrode layer was formed on the green sheet and the surface roughness (Ra) of the electrode layer was measured, it was 0.074 μm.

  Moreover, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, no cracks or wrinkles were observed.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 16%.

Example 5
In the same manner as in Example 1 except that i-carbyl acetate was used in place of α-terpinyl acetate as the solvent for preparing the conductor paste, ceramic was prepared. When the electrode layer was formed on the green sheet and the surface roughness (Ra) of the electrode layer was measured, it was 0.076 μm.

  Moreover, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, no cracks or wrinkles were observed.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 8%.

Example 6
In the same manner as in Example 1 except that d-dihydrocarbyl acetate was used in place of α-terpinyl acetate as the solvent for preparing the conductor paste, When the electrode layer was formed on the green sheet and the surface roughness (Ra) of the electrode layer was measured, it was 0.076 μm.

  Further, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 10%.

Comparative Example 1
Except for using a mixed solvent of terpionol and kerosene (mixing ratio 50:50) instead of α-terpinyl acetate as the solvent for preparing the conductor paste, When an electrode layer was formed on the ceramic green sheet and the surface roughness (Ra) of the electrode layer was measured, it was 0.102 μm.

  Further, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 90%.

Comparative Example 2
An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that, instead of α-terpinyl acetate , tarpione was used as the solvent for preparing the conductor paste, The surface roughness (Ra) of the electrode layer was measured and found to be 0.112 μm.

  Further, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer.

  Further, in the same manner as in Example 1, 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 88%.

From Examples 1 to 6 and Comparative Examples 1 and 2, on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, methacrylic acid having a molecular weight of 700,000 was formed. When a conductive paste containing a copolymer of methyl acrylate and butyl acrylate as a binder and a mixed solvent of terpineol and kerosene (mixing ratio 50:50) as a solvent is printed to form an electrode layer and as a binder, polyvinyl butyral A ceramic green sheet formed using a dielectric paste containing a degree of polymerization of 1450 and a degree of butyralization of 69% contains a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and terpineol as a solvent. Conductor paste When the electrode layer is formed by printing, the surface roughness (Ra) of the electrode layer deteriorates, and there is a high possibility that voids are generated in the multilayer ceramic capacitor produced by stacking the multilayer units. As a binder, a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is included as a binder on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%). When an electrode layer is formed by printing a conductive paste containing α-terpinyl acetate as a solvent, a dielectric paste containing polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%) is used as a binder. On the formed ceramic green sheet, methyl methacrylate and acrylic acid with a molecular weight of 700,000 When an electrode layer is formed by printing a conductive paste containing a butyl copolymer as a binder and I-dihydrocarbyl acetate as a solvent, the binder contains polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%). On a ceramic green sheet formed using a dielectric paste, a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-menton as a solvent is printed, and an electrode layer is formed. When formed, a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. Includes as a binder, I- When a conductive paste containing lilylacetate as a solvent is printed to form an electrode layer, a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder When a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and i-carbyl acetate as a solvent is printed to form an electrode layer and as a binder, polyvinyl butyral A ceramic green sheet formed using a dielectric paste containing a polymerization degree of 1450 and a butyralization degree of 69% contains a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder, and d-dihydrocarbyl acetate. As solvent By printing Mushirubedentai paste, in case of forming the electrode layer, the surface roughness of the electrode layer (Ra) is improved has been found.

Further, from Examples 1 to 6 and Comparative Examples 1 and 2, on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, the molecular weight was 700,000. A conductive paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpineol and kerosene (mixing ratio 50:50) as a solvent was printed to produce a laminate unit, When a multilayer ceramic capacitor is produced by laminating multilayer units and a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, the molecular weight is 70. Million methyl methacrylate and butyric acrylate In the case of producing a multilayer ceramic capacitor by printing a conductive paste containing a copolymer of the above as a binder and terpineol as a solvent to produce a multilayer unit, While the short-circuit rate of the capacitor is extremely high, methacrylic acid having a molecular weight of 700,000 is formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A conductor paste containing a copolymer of methyl acrylate and butyl acrylate as a binder and α-terpinyl acetate as a solvent is printed to produce a laminate unit, and 50 laminate units are laminated and laminated. When a ceramic capacitor is manufactured, the binder A ceramic green sheet formed using a dielectric paste containing vinyl butyral (degree of polymerization 1450, degree of butyralization 69%) contains a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder, When a conductive paste containing hydrocarbyl acetate as a solvent is printed to produce a laminate unit and 50 laminate units are laminated to produce a multilayer ceramic capacitor, polyvinyl butyral (degree of polymerization 1450, A conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder, and I-menton as a solvent on a ceramic green sheet formed using a dielectric paste containing a butyralization degree of 69%) Print the laminate In the case where a multilayer ceramic capacitor is manufactured by stacking 50 laminated units, a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) is used as a binder. On the ceramic green sheet, a conductor paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-perylyl acetate as a solvent is printed to produce a laminate unit, 50 sheets When a multilayer ceramic capacitor is produced by laminating the multilayer unit, a molecular weight is formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. 700,000 methyl methacrylate and butyric acrylate The case where a multilayer ceramic capacitor was manufactured by printing a conductor paste containing a copolymer of the above as a binder and i-carbyl acetate as a solvent to produce a laminate unit and laminating 50 laminate units, and As a binder, a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is included as a binder on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%), When a conductive paste containing d-dihydrocarbyl acetate as a solvent is printed to produce a laminated unit and 50 laminated units are laminated to produce a laminated ceramic capacitor, the laminated ceramic capacitor is short-circuited. The rate can be significantly reduced Turned out to be.

This is a dielectric paste in which a mixed solvent of terpineol and kerosene (mixing ratio 50:50) and terpineol used as solvents for the conductive paste in Comparative Examples 1 and 2 were used to form a ceramic green sheet. In order to dissolve the polyvinyl butyral contained in the surface, cracks and wrinkles occur on the surface of the electrode layer, the surface roughness (Ra) deteriorates, and pinholes and cracks occur in the ceramic green sheet, Α-Turpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate used as solvents for the conductive pastes in Examples 1 to 6 Is the dielectric paper used to form the ceramic green sheet. Since the polyvinyl butyral contained in the glass layer is hardly dissolved, cracks and wrinkles are effectively prevented from occurring on the surface of the electrode layer, and pinholes and cracks are prevented from occurring in the ceramic green sheet. it is conceivable that.

Example 7
Preparation of Dielectric Paste for Ceramic Green Sheet A dielectric paste for ceramic green sheet was prepared in the same manner as in Example 1.

Formation of Ceramic Green Sheet In the same manner as in Example 1, a ceramic green sheet dielectric paste was applied on a polyethylene terephthalate film to form a ceramic green sheet having a thickness of 1 μm.

Preparation of dielectric paste for spacer layer 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 parts by weight of Y ₂ O ₃ , 0.72 parts by weight of MgCO ₃ , 0.13 parts by weight of MnO and 0.045 parts by weight of V ₂ O ₅ were mixed to prepare an additive powder.

To 100 parts by weight of the additive powder thus prepared, 150 parts by weight of acetone, 104.3 parts by weight of α-terpinyl acetate , and 1.5 parts by weight of a polyethylene glycol dispersant are mixed, A slurry was prepared, and the additive in the slurry was pulverized using a pulverizer “LMZ0.6” (trade name) manufactured by Ashizawa Finetech Co., Ltd.

In crushing the additive in the slurry, ZrO ₂ beads (0.1 mm in diameter) are filled into the vessel at 80% of the vessel capacity, and the rotor is rotated at a peripheral speed of 14 m / min. The slurry was circulated between the vessel and the slurry tank until the time for all the slurry to stay in the vessel was 5 minutes, and the additives in the slurry were pulverized.

  The median diameter of the additive after pulverization was 0.1 μm.

  Next, using an evaporator, acetone was evaporated and removed from the slurry to prepare an additive paste in which the additive was dispersed in limonene. The non-volatile component concentration in the additive paste was 49.3% by weight.

Next, 8 parts by weight of a copolymer of methyl methacrylate and butyl acrylate (copolymerization ratio 82:18, molecular weight 700,000) having an acid value of 5 mg KOH / g was dissolved in 92 parts by weight of limonene at 70 ° C. An 8% solution of vehicle was prepared, and a slurry having the following composition was dispersed using a ball mill for 16 hours. The dispersion conditions were such that the ZrO ₂ (diameter 2.0 mm) filling amount in the mill was 30% by volume, the slurry amount in the mill was 60% by volume, and the peripheral speed of the ball mill was 45 m / min.

Additive paste 8.87 parts by weight BaTiO ₃ powder (manufactured by Sakai Chemical Industry Co., Ltd .: trade name “BT-02”: particle size 0.2 μm)
95.70 parts by weight Organic vehicle 104.36 parts by weight Polyethylene glycol dispersant 1.0 part by weight Dioctyl phthalate (plasticizer) 2.61 parts by weight Imidazoline surfactant 0.4 part by weight Acetone 57.20 parts by weight Next, using a stirring device equipped with an evaporator and a heating mechanism, acetone was evaporated from the slurry thus obtained and removed from the mixture to obtain a dielectric paste.

Preparation of Conductive Paste for Electrode Layer A conductive paste for electrode layer was prepared in the same manner as in Example 1.

Formation of Spacer Layer The dielectric paste thus prepared is printed in a predetermined pattern on a ceramic green sheet using a screen printer, and is dried at 90 ° C. for 5 minutes. A spacer layer was formed on the green sheet.

Subsequently, when the surface roughness (Ra) of the spacer layer was measured using “Surf Coder (SE-30D)” (trade name) manufactured by Kosaka Laboratory Ltd., it was 0.069 μm .

  Furthermore, when the surface of the spacer layer was observed with a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed on the surface of the spacer layer.

Formation of electrode layer and production of laminate unit Further, using a screen printer, the conductive paste was printed on the ceramic green sheet in a pattern complementary to the spacer layer, and at 90 ° C. for 5 minutes. It dried and formed the electrode layer which has thickness of 1 micrometer, and produced the laminated body unit by which the ceramic green sheet and the electrode layer were laminated | stacked on the surface of the polyethylene terephthalate film.

The thus formed electrode layer surface roughness (Ra), using the Corporation Kosaka Laboratory Ltd. "Surf coder (SE-30D)" (trade name) where it was measured, was 0.069μm.

  Furthermore, when the surface of the electrode layer was observed by magnifying 400 times using a metal microscope, no cracks or wrinkles were observed on the surface of the electrode layer.

Production of Ceramic Green Chip In the same manner as in Example 1, a dielectric paste was applied to the surface of a polyethylene terephthalate film to produce a ceramic green sheet having a thickness of 10 μm.

  The ceramic green sheet having a thickness of 10 μm thus prepared is peeled from the polyethylene terephthalate film, cut, and the five cut ceramic green sheets are laminated to form a cover layer having a thickness of 50 μm. Further, the laminate unit was peeled off from the polyethylene terephthalate film, cut, and 50 laminate units cut were laminated on the cover layer.

  Next, the ceramic green sheet having a thickness of 10 μm is peeled off from the polyethylene terephthalate film, cut, and the five cut ceramic green sheets are laminated on the laminated body unit to obtain a thickness of 50 μm. 100 μm thickness in which 50 laminate units including a lower cover layer having a thickness, a ceramic green sheet having a thickness of 1 μm, an electrode layer having a thickness of 1 μm, and a spacer layer having a thickness of 1 μm are stacked. A laminate was produced in which an effective layer having a thickness of 50 μm and an upper cover layer having a thickness of 50 μm were laminated.

  Next, the laminated body thus obtained was press-molded under a temperature condition of 70 ° C. by applying a pressure of 100 MPa, and cut into a predetermined size by a dicing machine to produce a ceramic green chip.

Production of Multilayer Ceramic Capacitor Sample A multilayer ceramic capacitor sample was produced in the same manner as in Example 1 using the ceramic green chip thus produced.

  In the same manner, a total of 50 multilayer ceramic capacitor samples were produced.

Measurement of short-circuit rate In the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples thus produced were measured with a multimeter, and the multilayer ceramic capacitor samples were measured. The short rate of the sample was measured.

As a result, the short-circuit rate was 14% .

Example 8
As a solvent in preparing a dielectric paste for a conductive paste and a spacer layer for the electrode layer, alpha-coater instead of pin-yl acetate, except using I- dihydrocarbyl acetate, similarly to Example 7 Then, the spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured. It was 070 μm.

  Moreover, when the surface of the electrode layer and the spacer layer was observed using a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 18%.

Example 9
As in Example 7 , except that I-menton was used in place of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer. The spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured to be 0.066 μm and 0.066 μm, respectively. there were.

  Moreover, when the surface of the electrode layer and the spacer layer was observed using a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 10%.

Example 10
As in Example 7 , except that I-peryl acetate was used in place of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer. Then, the spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured. 074 μm.

  Moreover, when the surface of the electrode layer and the spacer layer was observed using a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 16%.

Example 11
As in Example 7 , except that i-carbyl acetate was used in place of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer. Then, the spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured. It was 076 μm.

  Moreover, when the surface of the electrode layer and the spacer layer was observed using a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 8%.

Example 12
As in Example 7 , except that d-dihydrocarbyl acetate was used in place of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer. Then, the spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured. It was 076 μm.

  Moreover, when the surface of the electrode layer and the spacer layer was observed using a metal microscope at a magnification of 400 times, no cracks or wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 10%.

Comparative Example 3
The use of a mixed solvent of terpineol and kerosene (mixing ratio 50:50) instead of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer In the same manner as in Example 7 except that the spacer layer and the electrode layer were formed on the ceramic green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured. They were 0.102 μm and 0.102 μm, respectively.

  In addition, when the surface of the electrode layer and the spacer layer was observed with a metal microscope at a magnification of 400 times, the surface of the electrode layer and the spacer layer, cracks and wrinkles were observed.

Further, in the same manner as in Example 7 , 50 multilayer ceramic capacitor samples were prepared, and the resistance values of the 50 multilayer ceramic capacitor samples were measured with a multimeter to measure the short-circuit rate of the multilayer ceramic capacitor sample. As a result, the short-circuit rate was 90%.

Comparative Example 4
In the same manner as in Example 7 , except that terpineol was used in place of α-terpinyl acetate as a solvent in preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer, A spacer layer and an electrode layer were formed on the green sheet, and the surface roughness (Ra) of the spacer layer and the surface roughness (Ra) of the electrode layer were measured and found to be 0.112 μm and 0.112 μm, respectively. .

  In addition, when the surface of the electrode layer and the spacer layer was observed with a metal microscope at a magnification of 400 times, the surface of the electrode layer and the spacer layer, cracks and wrinkles were observed.

Further, in the same manner as in Example 7, to produce a 50 multilayer ceramic capacitor samples, the resistance value of 50 of the multilayer ceramic capacitor samples, by multimeter measures, measures short of the laminated ceramic capacitor samples As a result, the short-circuit rate was 88%.

From Examples 7 to 12 and Comparative Examples 3 and 4, on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, methacrylic acid having a molecular weight of 700,000 was formed. A dielectric paste containing a copolymer of methyl acrylate and butyl acrylate as a binder and a mixed solvent of terpineol and kerosene (mixing ratio 50:50) as a solvent is printed to form a spacer layer, and methacrylic acid having a molecular weight of 700,000 When a conductive paste containing a copolymer of methyl and butyl acrylate as a binder and a mixed solvent of terpineol and kerosene (mixing ratio 50:50) as a solvent is printed to form an electrode layer and as a binder, polyvinyl butyral ( Degree of polymerization 1450, degree of butyralization 6 The dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and a terpineol as a solvent is printed on a ceramic green sheet formed using a dielectric paste containing When the electrode layer is formed by printing a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and terpineol as a solvent, the surface roughness of the electrode layer (Ra) deteriorates and there is a high possibility that voids are generated in the multilayer ceramic capacitor produced by laminating the multilayer unit, whereas polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%) is used as a binder. Ceramic green sheet formed using dielectric paste containing In addition, a dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and α-terpinyl acetate as a solvent is printed to form a spacer layer, and a methacrylic acid having a molecular weight of 700,000 is formed. When an electrode layer is formed by printing a conductive paste containing a copolymer of methyl and butyl acrylate as a binder and α-terpinyl acetate as a solvent, polyvinyl butyral (degree of polymerization 1450, degree of butyralization) is formed as the binder. 69%) and a dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-dihydrocarbyl acetate as a solvent. Print to form spacer layer and When an electrode layer is formed by printing a conductive paste containing a 700,000,000 copolymer of methyl methacrylate and butyl acrylate as a binder and I-dihydrocarbyl acetate as a solvent, a polyvinyl butyral (polymerization degree) Dielectric containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-menton as a solvent on a ceramic green sheet formed using a dielectric paste containing 1450 and a butyral degree of 69%) A body paste is printed to form a spacer layer, and an electrode layer is formed by printing a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-menton as a solvent. In this case, polyvinyl butyra as a binder On a ceramic green sheet formed using a dielectric paste containing a rubber (polymerization degree 1450, butyralization degree 69%), a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is included as a binder. A dielectric paste containing ril acetate as a solvent is printed to form a spacer layer, and a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and I-peryl acetate as a solvent. When the electrode layer is formed by printing a methacrylic acid having a molecular weight of 700,000 on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. Copolymer of methyl and butyl acrylate as binder A dielectric paste containing i-carbyl acetate as a solvent is printed to form a spacer layer, a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is contained as a binder, and i-carbyl acetate is used as a solvent. In the case where the electrode paste is formed by printing the conductor paste containing as a molecular weight on the ceramic green sheet formed using the dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder A dielectric paste containing 700,000 methyl methacrylate and butyl acrylate copolymer as a binder and d-dihydrocarbyl acetate as a solvent is printed to form a spacer layer. The molecular weight of 700,000 methyl methacrylate and acrylic acid Contains butyl copolymer as binder , By printing a conductive paste containing d- dihydrocarbyl acetate as the solvent, in case of forming the electrode layer, the surface roughness of the electrode layer (Ra) is improved has been found.

Further, from Examples 7 to 12 and Comparative Examples 3 and 4, on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, the molecular weight was 700,000. A dielectric paste and a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpineol and kerosene (mixing ratio 50:50) as a solvent are printed to produce a laminate unit. When a multilayer ceramic capacitor is produced by laminating 50 laminate units, and on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder And methacryl with a molecular weight of 700,000. A dielectric ceramic body containing a copolymer of methyl and butyl acrylate as a binder and a terpineol as a solvent and a conductive paste are printed to produce a laminated body unit, 50 laminated body units are laminated, and a laminated ceramic capacitor In contrast, the short-circuit rate of the multilayer ceramic capacitor is significantly increased, whereas the ceramic green formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A dielectric unit and a conductor paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and α-terpinyl acetate as a solvent are printed on a sheet to produce a laminate unit. , Stacking 50 laminate units When a multilayer ceramic capacitor is manufactured, methyl methacrylate having a molecular weight of 700,000 is formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A dielectric paste and a conductive paste containing a copolymer of butyl acrylate as a binder and I-dihydrocarbyl acetate as a solvent are printed to produce a laminate unit, and 50 laminate units are laminated and laminated. When a ceramic capacitor is prepared, methyl methacrylate and butyl acrylate having a molecular weight of 700,000 are formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. The copolymer When a dielectric unit and a conductive paste containing I-menton as a solvent are printed to produce a laminated unit and 50 laminated units are laminated to produce a laminated ceramic capacitor, a binder As a binder, a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 is formed on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%). -When a dielectric paste and a conductive paste containing peryl acetate as a solvent are printed to produce a multilayer unit and 50 multilayer units are laminated to produce a multilayer ceramic capacitor, polyvinyl as a binder Butyral (degree of polymerization 1450, butyralization) 69%) and a dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and i-carbyl acetate as a solvent. When a conductive paste is printed to produce a laminated unit, 50 laminated units are laminated to produce a laminated ceramic capacitor, and as a binder, polyvinyl butyral (degree of polymerization 1450, degree of butyralization 69%) Dielectric paste and conductor paste containing a copolymer of methyl methacrylate and butyl acrylate having a molecular weight of 700,000 as a binder and d-dihydrocarbyl acetate as a solvent on a ceramic green sheet formed using a dielectric paste containing Print and product It has been found that when a multilayer unit is manufactured by manufacturing a multilayer unit and stacking 50 multilayer units, the short-circuit rate of the multilayer ceramic capacitor can be significantly reduced.

This is because, in Comparative Examples 3 and 4, the terpineol and kerosene mixed solvent (mixing ratio 50:50) and the terpineol used as the solvent for the spacer layer dielectric paste and conductor paste form a ceramic green sheet. In order to dissolve the polyvinyl butyral contained in the dielectric paste used for this purpose, cracks and wrinkles occur on the surfaces of the spacer layer and the electrode layer, and the surface roughness (Ra) of the spacer layer and the surface of the electrode layer and roughness (Ra) is deteriorated, the ceramic green sheet pinholes or cracks whereas occurs, in example 7-12, was used as a solvent for the dielectric paste and conductive paste for spacer layers α- Turpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perylylacete I-carbyl acetate and d-dihydrocarbyl acetate hardly dissolve the polyvinyl butyral contained in the dielectric paste used to form the ceramic green sheet, and thus the surface of the spacer layer and the electrode layer. It is considered that cracks and wrinkles are effectively prevented and pin holes and cracks are prevented from occurring in the ceramic green sheet.

  The present invention is not limited to the above embodiments and examples, and various modifications can be made within the scope of the invention described in the claims, and these are also included in the scope of the present invention. It goes without saying that it is a thing.

Claims (10)

Nickel powder as a conductor, acrylic resin as a binder, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peryl acetate, i-carbyl acetate and d-dihydrocarbyl acetate A conductor paste comprising at least one solvent selected from the group consisting of: 2. The conductor paste according to claim 1, wherein the acrylic resin has a molecular weight of 450,000 or more and 900,000 or less. The conductor paste according to claim 1 or 2, wherein an acid value of the acrylic resin is 5 mgKOH / g or more and 25 mgKOH / g or less. As a binder, on a ceramic green sheet containing a butyral resin, nickel powder is contained as a conductor, acrylic resin is contained as a binder, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-peri A conductive paste containing at least one solvent selected from the group consisting of ril acetate, i-carbyl acetate and d-dihydrocarbyl acetate is printed in a predetermined pattern to form an electrode layer. A method for producing a multilayer unit for a multilayer ceramic electronic component. Further, after the electrode layer is dried, the ceramic green sheet contains an acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i- A spacer paste is formed by printing a dielectric paste containing at least one solvent selected from the group consisting of carbyl acetate and d-dihydrocarbyl acetate in a pattern complementary to the electrode layer. The manufacturing method of the laminated body unit for multilayer ceramic electronic components of Claim 4. Prior to the formation of the electrode layer, an acrylic resin is included as a binder on the ceramic green sheet, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-menton, I-perillyl acetate, i A dielectric paste containing at least one solvent selected from the group consisting of carbyl acetate and d-dihydrocarbyl acetate is printed in a pattern complementary to the electrode layer to form a spacer layer. The manufacturing method of the laminated body unit for multilayer ceramic electronic components of Claim 4 to do. The method for producing a multilayer unit for a multilayer ceramic electronic component according to any one of claims 4 to 6, wherein the acrylic resin has a molecular weight of 450,000 or more and 900,000 or less. The method for producing a multilayer unit for a multilayer ceramic electronic component according to any one of claims 4 to 7, wherein an acid value of the acrylic resin is 5 mgKOH / g or more and 25 mgKOH / g or less. The method for producing a multilayer unit for a multilayer ceramic electronic component according to any one of claims 4 to 8, wherein the degree of polymerization of the butyral resin is 1000 or more. 10. The method for manufacturing a multilayer unit for a multilayer ceramic electronic component according to claim 4, wherein the butyral resin has a butyral degree of 64% or more and 78% or less. 11.