KR100816787B1 - Conductive paste for electrode layer of multilayer ceramic electronic component and method for producing multilayer unit for multilayer ceramic electronic component - Google Patents

Abstract

An object of this invention is to provide the manufacturing method of the laminated unit for laminated ceramic electronic components which can reliably prevent a short defect from generating in a laminated ceramic electronic component. According to the present invention, a laminate unit for laminated ceramic electronic components includes acrylic resin as a binder on a ceramic green sheet containing butyral resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate By printing a conductor paste containing at least one solvent selected from the group consisting of I-menton, I-peryl acetyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate in a predetermined pattern to form an electrode layer Are manufactured.

Lamination, Ceramic, Electrode Layer, Spacer Layer, Butyral, Resin, Green Sheet, Binder, Limonene, Conductor, Paste

Description

TECHNICAL FIELD OF THE INVENTION A method of manufacturing a conductive paste for an electrode layer of a multilayer ceramic electronic component and a laminate unit for a multilayer ceramic electronic component

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a conductive paste for an electrode layer of a multilayer ceramic electronic component and a laminate unit for a multilayer ceramic electronic component, and more particularly, to a binder contained in a layer adjacent to an electrode layer of a multilayer ceramic electronic component. Conductor paste for electrode layers that can reliably prevent short defects from occurring in laminated ceramic electronic components without melting, and laminates for laminated ceramic electronic components that can reliably prevent short defects from occurring in laminated ceramic electronic components. It relates to a manufacturing method of the unit.

Recently, with the miniaturization of various electronic apparatuses, miniaturization and high performance of electronic components mounted in electronic apparatuses have been demanded, and multilayer ceramic electronic components such as multilayer ceramic capacitors have also been strongly demanded for increasing the number of laminated layers and thinning of laminated units.

In order to manufacture a multilayer ceramic electronic component represented by a multilayer ceramic capacitor, first, ceramic powders, binders such as acrylic resins and butyral resins, phthalic acid esters, glycols, adipic acid, and phosphoric acid esters are used. A dielectric paste is prepared by mixing and dispersing a plasticizer and organic solvents such as toluene, methyl ethyl ketone and acetone.

Subsequently, the dielectric paste is applied onto a support sheet formed by polyethylene terephthalate (PET), polypropylene (PP), or the like using an extrusion coater, a gravure coater, or the like to dry the coating film to produce a ceramic green sheet.

Further, a conductive powder such as nickel and a binder are dissolved in a solvent such as terpionel to prepare a conductive paste, and the conductive paste is printed and dried in a predetermined pattern on a ceramic green sheet by a screen printing machine or the like to form an electrode layer. Form.

When the electrode layer is formed, the ceramic green sheet on which the electrode layer is formed is peeled off from the support sheet to form a laminate unit including the ceramic green sheet and the electrode layer, the desired number of laminate units are laminated and pressed, and the obtained laminate is in the form of a chip. The green chip is produced by cutting with

Finally, a multilayer ceramic electronic component such as a multilayer ceramic capacitor is manufactured by removing the binder from the green chip, firing the green chip, and forming an external electrode.

In accordance with the request for miniaturization and high performance of electronic components, it is currently required that the thickness of the ceramic green sheet, which determines the interlayer thickness of the multilayer ceramic capacitor, be 3 μm or 2 μm or less, and the laminate including 300 or more ceramic green sheets and electrode layers. There is a demand for stacking units.

However, the prepared conductor paste is prepared using terpionel which is most commonly used as a solvent for a conductor paste for forming an electrode layer on a ceramic green sheet using butyral resin, which is widely used as a binder for ceramic green sheets. When printing and forming an electrode layer, there existed a problem that the binder of a ceramic green sheet melt | dissolved by the terpionel in a conductor paste, and pinholes or a crack generate | occur | produce in a ceramic green sheet, and it becomes a cause of a short defect.

In order to solve this problem, it has been proposed to use a carbon hydrogen solvent such as kerosene and decane as a solvent of the conductor paste, and the carbon hydrogen solvent such as kerosene and decane may also be used as the binder component used in the conductor paste. Since it does not dissolve, solvents such as terpionel, which are conventionally used, cannot be completely replaced by carbon hydrogen solvents such as kerosene and decane, so that the solvent in the conductor paste is still a binder of the ceramic green sheet. Because of its solubility to some extent, when the thickness of the ceramic green sheet is very thin, it is difficult to prevent the formation of pinholes or cracks in the ceramic green sheet, and carbon hydrogen solvents such as kerosene and decane are terpionel It also has a problem that viscosity control of the conductor paste becomes difficult because of its low viscosity. It was.

In addition, Japanese Patent Application Laid-open No. Hei 5-325633, Japanese Patent Laid-Open No. 7-21833, and Japanese Patent Laid-Open No. 7-21832 disclose hydrogenated terpionels such as dihydroterpionel instead of terpionel, A conductor paste using a terpene-based solvent such as dihydroterpionel acetate is proposed, but a terpene-based solvent such as hydrogenated terpionel such as dihydroterpionel or dihydroterpionel acetate is still a ceramic green sheet. Since it has some solubility with respect to butyral resin which is a binder of, when the thickness of a ceramic green sheet is very thin, there existed a problem that it was difficult to prevent pinholes or a crack from generating in a ceramic green sheet.

Accordingly, the present invention provides a conductive paste for an electrode layer that can reliably prevent short defects from occurring in a multilayer ceramic electronic component without dissolving a binder contained in a layer adjacent to the electrode layer of the multilayer ceramic electronic component. It is for the purpose.

 Another object of the present invention is to provide a method for manufacturing a laminated unit for laminated ceramic electronic parts, which can reliably prevent short defects from occurring in the laminated ceramic electronic part.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching this invention in order to achieve this objective, the present inventors used acrylic resin as a binder, and limonene, (alpha)-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I- as a solvent. When the conductor paste is prepared using at least one solvent selected from the group consisting of peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate, the binder can be dissolved in the solvent as desired, and the butyral type Even when the conductive paste is printed on the ceramic green sheet using the resin as the binder to form the electrode layer, the binder contained in the ceramic green sheet is not dissolved by the solvent contained in the conductive paste, so that the thickness of the ceramic green sheet is increased. Ensure pinholes or cracks in the ceramic green sheet even when very thin It was found that it can be prevented.

The present invention is according to this realization, and thus the object of the present invention comprises acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, It is achieved by a conductor paste comprising at least one solvent selected from the group consisting of I-carbyl acetate and d-dihydrocarbyl acetate.

The above object of the present invention also includes acrylic resin as a binder on a ceramic green sheet containing butyral resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I- A multilayer ceramic electron characterized in that an electrode layer is formed by printing a conductor paste containing at least one solvent selected from the group consisting of peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate in a predetermined pattern. It is achieved by the manufacturing method of the laminated body unit for components.

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, a binder contained in the ceramic green sheet by a solvent contained in the conductive paste is used. Since it does not melt | dissolve, even when the thickness of a ceramic green sheet is very thin, it becomes possible to reliably prevent pinholes or a crack from generate | occur | producing in a ceramic green sheet.

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, acrylic resin is included as a binder on the ceramic green sheet, and limonene, α-terpinyl acetate, I-dihydro A dielectric paste containing at least one solvent selected from the group consisting of carbyl acetate, I-mentone, I-peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate in a pattern complementary to the pattern of the electrode layer The spacer layer is further formed by printing.

According to a preferred embodiment of the present invention, since the spacer layer is formed in a pattern complementary to the pattern of the electrode layer on the ceramic green sheet, a step is prevented from being formed between the surface of the electrode layer and the surface of the ceramic green sheet in which the electrode layer is not formed. Therefore, it becomes possible to effectively prevent deformation of a laminated electronic component such as a multilayer ceramic capacitor produced by stacking a plurality of laminate units each including a ceramic green sheet and an electrode layer, and to perform lamination ( It is possible to effectively prevent the occurrence of delamination.

In addition, as a solvent contained in the conductor paste for forming the electrode layer and the dielectric paste for forming the spacer layer, a mixed solvent of terpionel and kerosene, dihydroterpionel, terpionel, and the like, which have been used so far, Since the butyral resin contained in the ceramic green sheet is dissolved in the binder, when these solvents are used as the solvent for the dielectric paste for forming the spacer layer, the solvent contained in the dielectric paste for forming the spacer layer is the ceramic green sheet. Melted or swelled in the ceramic green sheet to cause cracking or wrinkles on the surface of the spacer layer, and as a result, a multilayer ceramic capacitor produced by laminating a plurality of laminate units each including a ceramic green sheet and an electrode layer. The problem that voids are likely to occur in laminated electronic components According to a preferred embodiment of the present invention, the dielectric paste used to form the spacer layer includes an acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I It contains at least one solvent selected from the group consisting of peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone , The solvent selected from the group consisting of I-peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves butyral resin contained as a binder in the ceramic green sheet, so that the ceramic green sheet is dissolved or swelled. To prevent cracks or wrinkles on the surface of the spacer layer. And, therefore, it is possible to reliably prevent each of the ceramic green sheet with voids in multilayer electronic components such as a multilayer ceramic capacitor produced by laminating a plurality of laminate units including the electrode layer and the spacer layer occurs.

In this invention, it is preferable that the weight average molecular weights of the acrylic resin contained in the electrically conductive paste for electrode layers as a binder, and the acrylic resin contained in the dielectric paste for spacer layers as a binder are all 450,000 or more and 900,000 or less, and the weight average molecular weight is 45 By using the acrylic resin of 10,000 or more and 900,000 or less as a binder of the electrode paste conductor paste and the spacer layer dielectric paste, an electrode layer conductor paste and a spacer layer dielectric paste having a desired viscosity can be prepared.

 In the present invention, it is preferable that the acid value of the acrylic resin contained in the electrode layer conductor paste and the spacer layer dielectric paste as a binder is 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 it as a binder of the conductor paste for electrode layers and the dielectric paste for spacer layers, a conductor paste having a desired viscosity and a dielectric paste for spacer layers can be prepared.

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

In this invention, it is preferable that the butyralization degree of butyral-type resin contained in a ceramic green sheet as a binder is 64 mol% or more and 78 mol% or less.

In the case where the electrode layer is formed by printing the electrode layer conductor paste on a very thin ceramic green sheet, and the spacer layer is formed by printing the dielectric layer paste for the spacer layer, the solvent in the electrode paste for the electrode layer and the dielectric paste for the spacer layer are ceramic. Since the binder component of the green sheet is dissolved or swelled, and there is a problem that the conductive paste and the dielectric paste are soaked in the ceramic green sheet, which causes a short defect, the electrode layer and the spacer layer are formed on separate support sheets. The inventors have found that it is preferable to adhere to the surface of the ceramic green sheet through the adhesive layer after drying, and in the case of forming the electrode layer and the spacer layer on separate support sheets, the electrode layer and the spacer layer In order to easily peel off the support sheet, a release layer including the same binder as the ceramic green sheet is formed on the surface of the support sheet, a conductor paste is printed on the release layer to form an electrode layer, and a dielectric paste is printed to form a spacer. It is preferable to form a layer. As described above, even when 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, the release layer contains butyral resin as a binder. When the paste and the dielectric paste contain terpionel as a solvent, the binder contained in the release layer is dissolved by the solvent contained in the conductor paste and the dielectric paste to generate pinholes or cracks in the release layer, and the multilayer ceramic capacitor or the like. There was a problem that a problem occurs in the multilayer ceramic electronic component.

According to the present invention, however, acrylic resins are included as binders, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate An electrode layer is formed using a conductor paste containing at least one solvent selected from the group consisting of, preferably acrylic resin as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate The spacer is further formed by using a dielectric paste comprising at least one solvent selected from the group consisting of I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate, limonene, I -Terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, I-carbyl acetate and d-diha Since the solvent selected from the group consisting of idrocarbyl acetate hardly dissolves the butyral resin contained in the ceramic green sheet as a binder, a release layer containing the same binder as the ceramic green sheet is formed, and a conductor is formed on the release layer. Even when the paste is printed to form the electrode layer, and the dielectric paste is printed to form the spacer layer, pinholes or cracks can be effectively prevented from occurring in the release layer, and problems occur in the multilayer ceramic electronic components such as the multilayer ceramic capacitor. It is possible to effectively prevent that.

In a preferred embodiment of the manufacturing method of the laminate unit of the present invention, first, a dielectric paste for ceramic green sheets containing butyral resin as a binder is prepared, and the support is long using an extrusion coater, a wire bar coater, or the like. It is applied onto a sheet to form a coating film.

The dielectric paste for forming a ceramic green sheet is usually prepared by kneading a dielectric material (ceramic powder) and an organic vehicle in which butyral resin is dissolved in an organic solvent.

It is preferable that the polymerization degree of butyral-type resin is 1000 or more, and it is preferable that butyralization degree of butyral-type resin is 64 mol% or more and 78 mol% or less.

The organic solvent used for the organic vehicle is not particularly limited, and organic solvents such as terpineol, butyl carbitol, acetone, toluene and ethyl acetate are used.

The dielectric material is appropriately selected from complex oxides and various compounds to be oxides such as carbonates, nitrates, hydroxides, organometallic compounds, and the like, and can be used by mixing them. The dielectric material is usually used as a powder having an average particle diameter of about 0.1 μm to about 3.0 μm. The particle diameter of the dielectric material is preferably smaller than the thickness of the ceramic green sheet.

The content of each component in the dielectric paste is not particularly limited, and the dielectric paste may be, for example, about 2.5 parts by weight to about 10 parts by weight of butyral resin and about 50 parts by weight to about 300 parts by weight of the solvent based on 100 parts by weight of the dielectric material. I can prepare it.

The dielectric paste may contain additives selected from various dispersants, plasticizers, subcomponent compounds, glass frits, insulators, and the like as necessary. In the case where these additives are added in the dielectric paste, the total content is preferably about 10% by weight or less.

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

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

It is preferable that the thickness of the ceramic green sheet after drying is 3 micrometers or less, More preferably, it is 1.5 micrometers or less.

Subsequently, the conductor paste for electrode layers is printed in a predetermined pattern on a ceramic green sheet formed on the surface of the long supporting sheet using a screen printing machine, a gravure printing machine, or the like to form an electrode layer.

 After drying, 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.

The conductive paste for electrode layers is an organic vehicle in which an acrylic resin is dissolved in a solvent such as a conductive material made of various conductive metals or alloys, various oxides, organic metal compounds or resins, etc., which become conductive materials made of various conductive metals or alloys after firing. It is prepared by kneading.

In the present embodiment, the conductor paste contains an acrylic resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, I-carbyl acetate and d- At least 1 sort (s) of solvent chosen from the group which consists of dihydrocarbyl acetate is contained.

A solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate as a binder on a ceramic green sheet Since the contained butyral resin is hardly dissolved, the binder contained in the ceramic green sheet is dissolved by the solvent contained in the conductor paste even when the electrode paste is formed by printing the conductor paste on a very thin ceramic green sheet. Can be effectively prevented, and therefore, even when the thickness of the ceramic green sheet is very thin, it is possible to effectively prevent the occurrence of pinholes or cracks in the ceramic green sheet.

It is preferable that the weight average molecular weight of acrylic resin contained in a conductor paste is 450,000 or more and 900,000 or less, The conductor which has a desired viscosity by using acrylic resin whose weight average molecular weights are 450,000 or more and 900,000 or less as a binder of a conductor paste. Paste can be prepared.

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

As a conductor material used when manufacturing a conductor paste, Ni, a Ni alloy, or a mixture thereof is used preferably. The shape of the conductor material is not particularly limited, and may be spherical, scaly, or may be mixed with these shapes. In addition, the average particle diameter of the conductor material is not particularly limited, but usually a conductive material of about 0.1 μm to about 2 μm, preferably about 0.2 μm to about 1 μm is used.

The conductor paste preferably contains about 2.5 parts by weight to about 20 parts by weight of the binder based on 100 parts by weight of the conductor material.

The content of the solvent is preferably about 35% by weight to about 220% by weight based on the entire conductor paste.

In order to improve adhesiveness, it is preferable that the conductor paste contains a plasticizer. The plasticizer contained in the conductor paste is not particularly limited, and examples thereof include phthalic acid esters, adipic acid, phosphate esters and glycols. The conductor paste preferably contains about 10 parts by weight to about 100 parts by weight, more preferably about 10 parts by weight to about 70 parts by weight of plasticizer based on 100 parts by weight of the binder. If the amount of the plasticizer added is too large, the strength of the electrode layer tends to be significantly lowered, which is not preferable.

The conductor paste may contain an additive selected from various dispersants, accessory compounds, and the like as necessary.

Preferably, prior to the formation of the electrode layer or after the electrode layer is formed and dried, acrylic resin is included as a binder, limonene, I-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, I A dielectric paste for spacer layers comprising at least one solvent selected from the group consisting of carbyl acetate and d-dihydrocarbyl acetate is a screen printing machine or gravure printing machine in a pattern complementary to the pattern of the electrode layer on the surface of the ceramic green sheet. It is printed using to form a spacer layer.

Thus, by forming the spacer layer in a pattern complementary to the pattern of the electrode layer on the surface of the ceramic green sheet, it is possible to prevent the step is formed between the surface of the electrode layer and the surface of the ceramic green sheet in which the electrode layer is not formed. It is possible to effectively prevent deformation of a laminated electronic component such as a multilayer ceramic capacitor manufactured by stacking a plurality of laminate units including a ceramic green sheet and an electrode layer, and to prevent the occurrence of delamination. Become.

Further, as described above, a solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate Since the butyral resin contained as a binder in the ceramic green sheet 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 included in the ceramic green sheet by a solvent contained in the dielectric paste. It is possible to effectively prevent the binder from being dissolved, and thus it is possible to effectively prevent pinholes or cracks from occurring in the ceramic green sheet even when the thickness of the ceramic green sheet is very thin.

The dielectric paste for forming the spacer layer is prepared in the same manner as the dielectric paste for forming the ceramic green sheet except that other binders and solvents are used.

The weight average 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 by using an acrylic resin having a weight average molecular weight of 450,000 or more and 900,000 or less as a binder for the dielectric paste for the spacer layer. A dielectric paste having a desired viscosity can be prepared.

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

Subsequently, 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 manufacturing a multilayer ceramic capacitor, the support sheet is peeled from the ceramic green sheet of the laminate unit and cut to a predetermined size so that a predetermined number of laminate units are laminated on the outer layer of the multilayer ceramic capacitor, and on the laminate unit. The other outer layer is further laminated, and the obtained laminate is press molded and cut to a predetermined size to produce a plurality of ceramic green chips.

 The ceramic green chip thus produced is placed in a reducing gas atmosphere to remove the binder and to fire.

Subsequently, an external electrode or the like necessary for the fired ceramic green chip is attached to produce a multilayer ceramic capacitor.

According to this embodiment, acrylic resin is included as a binder on a ceramic green sheet containing butyral resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl A conductor paste comprising at least one solvent selected from the group consisting of acetate, I-carbyl acetate and d-dihydrocarbyl acetate in a predetermined pattern to form an electrode layer, limonene, α-terfinyl A solvent selected from the group consisting of acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate, and d-dihydrocarbyl acetate, butyral resin contained as a binder in the ceramic green sheet Almost does not dissolve, printing the conductive paste on a very thin ceramic green sheet Even if it is, the binder contained in the ceramic green sheet can be effectively prevented from being dissolved by the solvent contained in the conductor paste, so that even if the thickness of the ceramic green sheet is very thin, pinholes or cracks may be formed in the ceramic green sheet. It is possible to effectively prevent the occurrence of short circuits and to effectively prevent the occurrence of short defects in the multilayer ceramic electronic component.

In addition, according to the present embodiment, since the spacer layer is formed on the ceramic green sheet in a pattern complementary to the pattern of the electrode layer, it is possible to prevent the formation of a step between the surface of the electrode layer and the surface of the ceramic green sheet on which the electrode layer is not formed. Therefore, it becomes possible to effectively prevent deformation of the laminated electronic component such as a multilayer ceramic capacitor manufactured by stacking a plurality of laminate units each including a ceramic green sheet and an electrode layer, and to prevent the occurrence of delamination. It becomes possible to prevent effectively.

Furthermore, according to this embodiment, acrylic resin is included as a binder on a ceramic green sheet containing butyral resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, and I-fe A dielectric paste comprising at least one solvent selected from the group consisting of aryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate in a pattern complementary to the pattern of the electrode layer to form a spacer layer, limonene , a solvent selected from the group consisting of α-terpinyl acetate, I-dihydrocarbyl acetate, 1-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate as a binder in the ceramic green sheet It hardly dissolves the butyral resin, which is a dielectric material on a very thin ceramic green sheet Even when the paste is printed and the spacer layer is formed, the binder contained in the ceramic green sheet is dissolved by the solvent contained in the dielectric paste so that the ceramic green sheet swells and cracks or wrinkles are generated on the surface of the spacer layer. Therefore, it becomes possible to reliably prevent the generation of voids in a laminated electronic component such as a multilayer ceramic capacitor produced by stacking a plurality of laminate units each including a ceramic green sheet and an electrode layer.

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

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

It is preferable that the thickness of a peeling layer is below the thickness of an electrode layer, Preferably it is about 60% or less of the thickness of an electrode layer, More preferably, it is about 30% or less of the thickness of an electrode layer.

After the release layer is dried, the electrode paste for electrode layer prepared on the surface of the release layer in the same manner as described above is printed and dried in a predetermined pattern using a screen printing machine, a gravure printing machine, or the like to form an electrode layer.

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 the present embodiment, the conductor paste contains an acrylic resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarnosyl acetate, I-mentone, I-peryl acetate, I-carbyl acetate and d-di At least one solvent selected from the group consisting of hydrocarbyl acetate is included.

The solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate is bound to the ceramic green sheet. Since the butyral resin contained as a resin is hardly dissolved, a pinhole or crack is formed in the peeling layer even when a peeling layer including the same binder as the ceramic green sheet is formed and a conductive paste is printed on the peeling layer to form an electrode layer. It can effectively prevent generation, and it becomes possible to effectively prevent a problem generate | occur | producing in the multilayer ceramic electronic components, such as a multilayer ceramic capacitor.

It is preferable that the weight average molecular weight of acrylic resin contained in a conductor paste is 450,000 or more and 900,000 or less, The conductor which has a desired viscosity by using acrylic resin whose weight average molecular weights are 450,000 or more and 900,000 or less as a binder of a conductor paste. Paste can be prepared.

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

Preferably, prior to the formation of the electrode layer or after the electrode layer is formed and dried, acrylic resin is included as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, I A dielectric paste for a spacer layer comprising at least one solvent selected from the group consisting of carbyl acetate and d-dihydrocarbyl acetate and prepared in the same manner as described above is complementary to the pattern of the electrode layer on the surface of the second support sheet. In a typical pattern, a spacer layer is formed by printing using a screen printing machine, a gravure printing machine, or the like.

Thus, by forming the spacer layer in a pattern complementary to the pattern of the electrode layer on the surface of the ceramic green sheet, it is possible to prevent the step is formed between the surface of the electrode layer and the surface of the ceramic green sheet in which the electrode layer is not formed. It is possible to effectively prevent deformation of a laminated electronic component such as a multilayer ceramic capacitor manufactured by stacking a plurality of laminate units including a ceramic green sheet and an electrode layer, and to prevent the occurrence of delamination. Become.

In addition, as described above, a solvent selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate Since the butyral resin contained as a binder is hardly dissolved in the green sheet, 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. It is possible to effectively prevent the occurrence of pinholes and cracks, and to effectively prevent the occurrence of problems in multilayer ceramic electronic components such as multilayer ceramic capacitors.

The weight average molecular weight of the acrylic resin included in the dielectric paste for forming the spacer layer is preferably 450,000 or more and 900,000 or less, and the acrylic resin having a weight average molecular weight of 450,000 or more and 900,000 or less is used as a binder for the conductor paste. A dielectric paste having a viscosity can be prepared.

The acid value of the acrylic resin contained in the dielectric paste is preferably 5 mgKOH / g or more and 25 mgKOH / g, and a dielectric paste having a desired viscosity can be obtained by using an acrylic resin having an acid value of 5 mgKOH / g or more and 25 mgKOH / g or less as a binder for the dielectric paste. I can prepare it.

Furthermore, a long length of the 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, and the like to form an adhesive layer.

 Preferably, the adhesive solution has a composition substantially the same as that of the binder included in the dielectric paste for forming the ceramic green sheet and the particles of the dielectric material contained in the ceramic green sheet and the binder of the same series, the particle diameter of the adhesive layer being Particle | grains of the dielectric material below thickness, a plasticizer, an antistatic agent, and a peeling agent are contained.

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, even more preferably from about 0.02 μm to about 0.2 μm.

In this way, the adhesive layer formed on the long third support sheet is adhered to the surface of the ceramic green sheet formed on the electrode layer or the electrode layer and the spacer layer or the support sheet formed on the second long support sheet, and from the adhesive layer after adhesion The third support sheet is peeled off to transfer the adhesive layer.

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, and after the adhesion, the support sheet is peeled off from the ceramic green sheet so that the ceramic green sheet Is transferred to the surface of the adhesive layer and manufactured into a laminate unit including a ceramic green sheet and an electrode layer.

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

In the same manner, a predetermined number of stacking units in which an adhesive layer is transferred to the surface thereof is produced, and a predetermined number of stacking units are stacked to produce a stacking block.

In manufacturing the laminate block, the laminate unit is first positioned on a support formed by polyethylene terephthalate or the like so that the adhesive layer transferred to the surface of the laminate unit is in contact with the support, and is pressed by a press or the like to laminate the laminate unit to the adhesive layer. Is adhered to the support through.

Then, the second support sheet is peeled from the release layer and the laminate unit is laminated on the support.

Subsequently, a new laminate unit is positioned on the surface of the release layer of the laminate unit laminated on the support such that the adhesive layer formed on the surface is brought into contact with the release layer of the laminate unit laminated on the support by pressing a press or the like. A new laminate unit is laminated through the adhesive layer, and then the second support sheet is peeled from the release layer of the new laminate unit.

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

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, and after the adhesion, the second support sheet is peeled off from the peeling layer to form the electrode layer or the electrode layer. And a spacer layer and a release layer are transferred to the surface of the adhesive layer, thereby producing a laminate unit including a ceramic green sheet and an electrode layer.

The adhesive layer is transferred in the same manner as the transfer of the adhesive layer onto the surface of the ceramic green sheet on the surface of the release layer of the laminate unit thus obtained, and the laminate unit on which the adhesive layer is transferred is cut to a predetermined size.

In the same manner, a predetermined number of stacking units in which an adhesive layer is transferred to the surface thereof is produced, and a predetermined number of stacking units are stacked to produce a stacking block.

In manufacturing the laminate block, first, the laminate unit is positioned so that the adhesive layer transferred to the surface of the laminate unit is in contact with the support body on a support body formed of polyethylene terephthalate or the like, and is pressed by a press or the like so that the laminate unit is an adhesive layer. Is adhered to the support through.

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

Subsequently, a new laminate unit is positioned on the surface of the ceramic green sheet of the laminate unit laminated on the support such that the adhesive layer formed on the surface is brought into contact with each other, and the ceramic green of the laminate unit laminated on the support is pressed by a press or the like. The new laminate unit is laminated to the sheet via an adhesive layer, and then the support sheet is peeled off 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 stacked.

The laminate block including the predetermined number of laminate units produced in this manner is laminated on the outer layer of the multilayer ceramic capacitor, and the laminate obtained by further laminating another outer layer on the laminate block is press-molded, and Cut to the size of a large number of ceramic green chips are produced.

The ceramic green chip thus produced is placed in a reducing gas atmosphere to remove the binder and to fire.

Subsequently, an external electrode or the like necessary for the fired ceramic green chip is attached to produce a multilayer ceramic capacitor.

According to this embodiment, since the electrode layer and the spacer layer formed on the second support sheet are dried to adhere to the surface of the ceramic green sheet through the adhesive layer, the electrode layer is printed by printing a conductor paste on the surface of the ceramic green sheet. The conductive paste and the dielectric paste do not penetrate into the ceramic green sheet as in the case of forming the spacer layer by printing the dielectric paste, and the electrode layer and the spacer layer can be formed on the surface of the ceramic green sheet as desired.

According to this embodiment, acrylic resin is included as a binder, and limonene, I-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl An electrode layer is formed using a conductor paste containing at least one solvent selected from the group consisting of acetate, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perrylyl acetate , The solvent selected from the group consisting of I-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves the butyral resin contained as a binder in the ceramic green sheet, thereby forming a release layer comprising the same binder as the ceramic green sheet. In addition, even when a conductive paste is printed on the release layer to form an electrode layer, a pinhole or It is possible to effectively prevent the rack has occurred, it is possible to effectively prevent the problem in a multilayer ceramic electronic device, such as a multilayer ceramic capacitor.

Furthermore, according to this embodiment, acrylic resin is included as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl A spacer layer is formed using a dielectric paste containing at least one solvent selected from the group consisting of acetate, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-peryl acetate , The solvent selected from the group consisting of I-carbyl acetate and d-dihydrocarbyl acetate hardly dissolves the butyral resin contained as a binder in the ceramic green sheet, thereby forming a release layer comprising the same binder as the ceramic green sheet. And a release layer even when a dielectric paste is printed on the release layer to form a spacer layer It is possible to effectively prevent a pinhole or crack, so that it is possible to effectively prevent the problem in a multilayer ceramic electronic device, such as a multilayer ceramic capacitor.

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 layer and the spacer layer, the adhesive layer and the ceramic green sheet are formed on the second long supporting sheet After the adhesive layer is transferred onto the surface of the ceramic green sheet of the laminate unit, 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 to the adhesive layer without cutting the laminate unit. The peeling layer of the formed laminated body unit is adhere | attached, a support sheet is peeled from a ceramic green sheet, and two laminated body units are laminated | stacked on the long 2nd support sheet.

Subsequently, the adhesive layer formed on the third support sheet is transferred onto the ceramic green sheet positioned on the surfaces of the two laminate units, and the ceramic green sheet, the adhesive layer, the electrode layer or the electrode layer, and the spacer layer are formed on the support sheet having a long length to the adhesive layer. And a release layer of the laminate unit formed by laminating the release layer, and the support sheet is peeled off from the ceramic green sheet.

 After repeating the same process, a laminate unit set in which a predetermined number of laminate units are stacked is produced, and the adhesive layer formed on the third support sheet is transferred to the surface of the ceramic green sheet located on the surface of the laminate unit set. The laminated block is further produced by cutting to 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 to the surface of the release layer of the laminate unit. After the adhesive layer is transferred, the ceramic green of the laminate unit is formed by laminating a release layer, an electrode layer or an electrode layer and a spacer layer, an adhesive base, and a ceramic green sheet on the second support sheet having a long length to the adhesive layer without cutting the laminate unit. The sheet is bonded, the second support sheet is peeled off from the release layer, and two laminate units are laminated on the long support sheet.

Subsequently, the adhesive layer formed on the third support sheet is transferred onto the release layer located on the surfaces of the two laminate units, and the release layer, the electrode layer or the electrode layer, and the spacer layer are formed on the second support sheet, which is long in the adhesive layer. The ceramic green sheet of the laminate unit formed by laminating the adhesive layer and the ceramic green sheet is bonded, and the second support sheet is peeled off from the peeling layer.

After repeating the same process, a laminate unit set in which a predetermined number of laminate units are stacked is produced, and after the adhesive layer formed on the third support sheet is transferred to the surface of the release layer located on the surface of the laminate unit set, the predetermined The laminate block is further produced by cutting to the size of.

A multilayer ceramic capacitor is produced in the same manner as the above embodiment using the laminated block produced in this way.

According to this embodiment, the laminated unit is successively laminated on the second long supporting sheet or the supporting sheet, a laminate unit set including a predetermined number of laminate units is produced, and then the laminate unit Since the set is cut to a predetermined size to produce a laminate block, it is much more efficient to manufacture the laminate block compared to the case of manufacturing a laminate block by laminating the laminated units cut to a predetermined size one by one. It becomes possible.

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, a release layer, an electrode layer or an electrode layer and a spacer layer, an adhesive layer, and a ceramic green sheet are laminated on the long second supporting sheet. After the adhesive layer is transferred onto the surface of the ceramic green sheet of the laminate unit formed, the laminate unit is not cut and the electrode layer or the electrode layer and the spacer layer formed on the second support sheet are adhered to the adhesive layer, and the second support is supported from the release layer. The sheet is peeled off so that the electrode layer or the electrode layer, the spacer layer and the peeling layer are transferred to the surface of the adhesive layer.

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

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 the electrode layer and the spacer layer formed on the second support sheet sheet are adhered to the adhesive layer, and the second layer is separated from the release layer. The support sheet is peeled off so that the electrode layer or the electrode layer, the spacer layer and the peeling layer are transferred to the surface of the adhesive layer.

By repeating the same process, a laminate unit set in which a predetermined number of laminate units are stacked is fabricated, the adhesive layer is transferred onto the surface of the ceramic green sheet located on the surface of the laminate unit set, and then cut to a predetermined size. The laminate block is further produced.

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 to the surface of the release layer of the laminate unit. After the adhesive layer is transferred, the ceramic green sheet formed on the support sheet is adhered to the adhesive layer without the laminate unit being cut, the support sheet is peeled off from the ceramic green sheet, and the ceramic green sheet is transferred to the surface of the adhesive layer.

Subsequently, 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 the electrode layer and the spacer layer formed on the second support sheet are adhered to the adhesive layer, and the second layer is separated from the release layer. The support sheet is peeled off so that the electrode layer or the electrode layer, the spacer layer and the peeling layer are transferred to the surface of the adhesive layer.

Further, 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, the ceramic green sheet formed on the support sheet sheet is adhered to the adhesive layer, and the support sheet is peeled off from the ceramic green sheet so that the ceramic The green sheet is transferred to the surface of the adhesive layer.

The same process is repeated to produce a laminate unit set in which a predetermined number of laminate units are stacked, and the adhesive layer is transferred to the surface of the release layer located on the surface of the laminate unit set, and then cut and laminated to a predetermined size. More sieve blocks are made.

A multilayer ceramic capacitor is produced in the same manner as the above embodiment using the laminated block produced in this way.

According to the present embodiment, the transfer of the adhesive layer, the transfer of the electrode layer or the electrode layer and the spacer layer and the release layer, the transfer of the adhesive layer, and the ceramic green sheet on the surface of the laminate body formed on the second support sheet or the support sheet having a long length Since the transfer is repeated to stack the stacking units continuously to produce a stack unit set including a predetermined number of stack units, and then the stack unit sets are cut to a predetermined size to produce a stack block. As compared with the case of stacking laminated body units cut to a predetermined size one by one to produce a laminated body block, the manufacturing efficiency of the laminated body block can be significantly improved.

EXAMPLE

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

Example 1

Preparation of Dielectric Paste for Ceramic Green Sheet

An additive powder was prepared by mixing 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 part by weight of Y ₂ 0 ₃ , 0.72 part by weight of MgCO ₃ , 0.13 part by weight of MnO, and 0.045 part by weight of V ₂ O ₅ .

The slurry was prepared by mixing 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 dispersant based on 100 parts by weight of the additive powder prepared in this way, and the additive in the slurry. Was ground.

In pulverizing the additive in the slurry, 11.65 g of slurry and 450 g of ZrO ₂ beads ( ₂ mm in diameter) were charged into a 250 cc polyethylene container, and the polyethylene container was rotated at 45 m / min. Grinding to prepare an additive slurry.

The median diameter of the additives after grinding was 0.1 μm.

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

BaTiO ₃ powder (SAKAI CHEMICAL INDUSTRY CO., LTD.manufacturer: trade name "BT-02": particle diameter 0.2μm) 100 parts by weight

11.65 parts by weight of additive slurry

35.32 parts by weight of ethyl alcohol

Propyl alcohol 35.32 parts by weight

Xylene 16.32 parts by weight

Benzyl butyl phthalate (plasticizer) 2.61 parts by weight

Mineral Spirit 7.3 parts by weight

2.36 parts by weight of polyethylene glycol dispersant

0.42 parts by weight of imidazoline-based charging aid

33.74 parts by weight of organic vehicle

43.81 parts by weight of methyl ethyl ketone

43.81 parts by weight of 2-butoxyethyl alcohol

As the polyethylene glycol dispersant, a dispersant (HLB = 5 to 6) in which polyethylene glycol was modified with fatty acid was used.

Formation of ceramic green sheets

The resulting dielectric paste was applied onto a polyethylene terephthalate film at a coating rate of 50 m / min using a die coater to produce a coating film, and the coating film obtained in a drying furnace maintained at 80 ° C. was dried to have a ceramic green sheet having a thickness of 1 μm. Was formed.

Preparation of Conductor Paste for Electrode

An additive powder was prepared by mixing 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 part by weight of Y ₂ O ₃ , 0.72 part by weight of MgCO ₃ , 0.13 part by weight of MnO, and 0.045 part by weight of V ₂ O ₅ .

The slurry was prepared by mixing 150 parts by weight of acetone, 104.3 parts by weight of limonene, and 1.5 parts by weight of polyethylene glycol dispersant based on 100 parts by weight of the additive powder thus prepared, and prepared by ASHIZAWA FINETECH LTD. Additives in the slurry were ground using a production mill "LMZ 0.6" (trade name).

In grinding the additives in the slurry, ZrO ₂ beads (0.1 mm in diameter) are charged in the vessel to 80% of the vessel capacity, and the rotor is rotated at a circumferential speed of 14 m / min to allow 5 minutes for the entire slurry to remain in the vessel. The additive in the slurry was pulverized by circulating between the vessel and the slurry tank until it was.

The median diameter of the additives after grinding was 0.1 μm.

Subsequently, acetone was evaporated to remove from the slurry using an evaporator to prepare an additive paste in which the additive was dispersed in limonene. The nonvolatile matter concentration in the additive paste was 49.3 wt%.

Subsequently, a copolymer of 8 parts by weight of an acid value of 5 mg KOH / g of methyl methacrylate and butyl acrylate (copolymerization ratio (molar ratio) 82:18, weight average molecular weight of 700,000) was dissolved in 92 parts by weight of limonene at 70 ° C. to prepare an organic vehicle. An 8% solution was prepared, and the slurry having the following composition was dispersed over 16 hours using a ball mill. Dispersing conditions, the amount of charge of the ZrO ₂ (diameter 2.0mm) of the mill the slurry in the amount of 30 vol%, 60 vol% and to wheat, ball mill, the main flux were 45m / min.

KAWATETSU INDUSTRY CO., LTD. Nickel powder of manufacture (particle diameter 0.2μm)

100 parts by weight

1.77 parts by weight of additive paste

BaTiO ₃ powder (SAKAI CHEMICAL INDUSTRY CO., LTD.

19.14 parts by weight

56.25 parts by weight of organic vehicle

Polyethylene glycol-based dispersant 1.19 parts by weight

2.25 parts by weight of dioctyl phthalate (plasticizer)

Limonene 83.96 parts by weight

Acetone 56 parts by weight

Subsequently, acetone was evaporated and removed from the mixture from the slurry thus obtained using a stirring apparatus equipped with an evaporator and a heating mechanism to obtain a conductor paste. The conductor material concentration in the conductor paste was 47% by weight.

Formation of electrode layer and fabrication of laminate unit

The conductive paste thus prepared is printed in a predetermined pattern on a ceramic green sheet using a screen printing machine, dried at 90 ° C. for 5 minutes to form an electrode layer having a thickness of 1 μm, and the surface of the polyethylene terephthalate film. The laminate unit in which the ceramic green sheet and the electrode layer were laminated was produced.

The surface roughness Ra of the electrode layer thus formed was measured using a "surfcoder (SE-30D)" (trade name) manufactured by KOSAKA LABORATORY LTD., Which was 0.070 µm.

In addition, when the surface of the electrode layer was observed magnified 400 times using a metal microscope, no cracking or wrinkles were observed.

Fabrication of Ceramic Green Chips

The dielectric paste prepared as described above was applied to the surface of the polyethylene terephthalate film using a die coater to form a coating film, and the coating film was dried to form a ceramic green sheet having a thickness of 10 μm.

The ceramic green sheet having a thickness of 10 μm thus produced was peeled off from the polyethylene terephthalate film, and cut. Then, the cut five ceramic green sheets were laminated to form a cover layer having a thickness of 50 μm. It peeled and cut | disconnected from the polyethylene terephthalate film, and cut | disconnected 50 laminated body units were laminated | stacked on the cover layer.

Subsequently, the ceramic green sheet having a thickness of 10 μm was peeled off from the polyethylene terephthalate film and cut, and the cut five ceramic green sheets were laminated on the laminated laminate unit to have a lower cover layer having a thickness of 50 μm, An effective layer having a thickness of 100 μm in which 50 laminate units including a ceramic green sheet having a thickness and an electrode layer having a thickness of 1 μm was laminated, and a laminate in which an upper cover layer having a thickness of 50 μm were laminated.

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

Fabrication of Multilayer Ceramic Capacitor Samples

The ceramic green chip thus produced was treated in air under the following conditions to remove the binder.

Temperature rise rate: 50 ℃ / hour

Holding temperature: 240 ℃

Retention time: 8 hours

After removing the binder, each ceramic green chip was treated by firing under the following conditions under a mixed gas atmosphere of nitrogen gas and hydrogen gas controlled at a dew point of 20 ° C. The content of nitrogen gas and hydrogen gas in the mixed gas was 95% by volume and 5% by volume.

Temperature rise rate: 300 ℃ / hour

Holding temperature: 1200 ℃

Holding time: 2 hours

Cooling rate: 300 ℃ / hour

Furthermore, the baked ceramic green chip was subjected to annealing treatment under the following conditions under an atmosphere of nitrogen gas controlled at a dew point of 20 ° C.

Temperature rise rate: 300 ℃ / hour

Holding temperature: 1000 ℃

Retention time: 3 hours

Cooling rate: 300 ℃ / hour

After the end surface of each sintered compact thus obtained was polished by sand blasting, an In—Ga alloy was applied to form a terminal electrode to prepare a multilayer ceramic capacitor sample.

A total of 50 multilayer ceramic capacitor samples were produced in the same manner.

Short ratio

The resistance value of the 50 multilayer ceramic capacitor samples produced in this way was measured with the multimeter, and the short defect of the multilayer ceramic capacitor sample was examined.

When the obtained resistance value was 100 kΩ or less, it was set as the short defect, the number of the laminated ceramic capacitor samples which showed the short defect was calculated | required, the ratio (%) with respect to the total number of laminated ceramic capacitor samples was calculated, and the short ratio was measured.

As a result, the short rate was 16%.

Example 2

An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that α-terpinyl acetate was used instead of limonene as a solvent when preparing the conductor paste, and the surface roughness Ra of the electrode layer was measured. It was 0.069 μm.

In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 14%.

Example 3

The surface roughness (Ra) of the electrode layer was measured by forming an electrode layer on the ceramic green sheet in the same manner as in Example 1 except that I-dihydrocarbyl acetate was used instead of limonene as a solvent when preparing the conductor paste. It was 0.070 micrometer.

In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed.

Furthermore, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 18%.

Example 4

An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that I-mentone was used instead of limonene as a solvent when preparing the conductor paste, and the surface roughness Ra of the electrode layer was measured. 0.066 μm.

In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were prepared in the same manner as in Example 1, and the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter to measure the short rate of the multilayer ceramic capacitor sample. Was 10%.

Example 5

The surface roughness (Ra) of the electrode layer was measured by forming an electrode layer on the ceramic green sheet in the same manner as in Example 1, except that I-peryl acetate was used instead of limonene as a solvent when preparing the conductor paste. Moreover, it was 0.074 micrometers.

 In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed.

 In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 16%.

Example 6

An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that I-carbyl acetate was used instead of limonene as a solvent when preparing the conductor paste, and the surface roughness Ra of the electrode layer was measured. Moreover, it was 0.076 micrometers.

In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 8%.

Example 7

An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that d-dihydrocarbyl acetate was used instead of limonene as a solvent when preparing the conductor paste, and the surface roughness Ra of the electrode layer was reduced. When measured, it was 0.076 micrometers.

In addition, when the surface of the electrode layer was observed magnified 400 times using a metal microscope, cracks and wrinkles were not observed on the surface of the electrode layer.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 10%.

Comparative Example 1

An electrode layer was formed on the ceramic green sheet in the same manner as in Example 1 except that a mixed solvent of terpionel and kerosine (mixing ratio (mass ratio) 50:50) was used instead of limonene as a solvent when preparing the conductor paste. It was formed, and the surface roughness Ra of the electrode layer was measured, and found to be 0.102 µm.

In addition, when the surface of the electrode layer was observed magnified 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. 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 terpionel was used instead of limonene as a solvent when preparing the conductor paste, and the surface roughness Ra of the electrode layer was measured. , 0.112 μm.

In addition, when the surface of the electrode layer was observed magnified 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 88%.

From Examples 1 to 7 and Comparative Examples 1 and 2, meta with a weight average 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. When an electrode layer is formed by printing a conductor paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) as a solvent; and Copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate was included as a binder on a ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. In the case where an electrode layer is formed by printing a conductor paste containing terpionel as a solvent, the surface roughness Ra of the electrode layer deteriorates and is laminated. Voids are likely to form in the multilayer ceramic capacitors produced by stacking units, whereas ceramic green sheets formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. Polyvinyl butyral (polymerization degree 1450) as a binder when a conductive paste containing a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and limonene as a solvent was printed on the substrate. And a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder on a ceramic green sheet formed using a dielectric paste containing butyralization degree (69%), and a -terpinyl acetate solvent Polyvinyl butyral (polymerization) is used as a binder when the electrode paste is formed by printing a conductor paste containing 1450, butyralization degree (69%), comprising a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder on a ceramic green sheet formed using a dielectric paste containing I-dihydrocarbyl acetate When the electrode paste was formed by printing a conductor paste containing a solvent as a solvent, the weight average on the ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. Polyvinyl butyral (polymerization degree 1450, buty) as a binder when a conductive paste containing a copolymer of a molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and containing I-mentone as a solvent was printed. Weight average molecular weight of 700,000 on ceramic green sheets formed using a dielectric paste containing Polyvinyl butyral (polymerization degree 1450, butyral) as a binder when a conductive paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and I-peryl acetate as a solvent is printed. A conductive material comprising a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and a I-carbyl acetate as a solvent on a ceramic green sheet formed using a dielectric paste containing Methyl methacrylate with a weight average molecular weight of 700,000 on a ceramic green sheet in which a sieve paste was printed to form an electrode layer and polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) was formed using a dielectric paste as a binder. A copolymer of butyl acrylate as a binder and d-dihydrocarbyl acetate as a solvent It has been found that when the conductor paste is printed to form the electrode layer, the surface roughness Ra of the electrode layer is improved.

Further, from Examples 1 to 7 and Comparative Examples 1 and 2, a weight average 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 A laminate unit was produced by printing a conductor paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) as a solvent. 50 laminated units were laminated to form a multilayer ceramic capacitor, and the weight was placed 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 methacrylate and butyl acrylate as an average molecular weight of 700,000 as a binder and terpionel as a solvent was printed. In the case where a laminate unit was fabricated and 50 laminate units were laminated to produce a multilayer ceramic capacitor, the short ratio of the multilayer ceramic capacitor was remarkably increased, whereas polyvinyl butyral (polymerization degree 1450, butyralization degree) was used as the binder. A conductive paste comprising a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and a limonene as a solvent is printed on a ceramic green sheet formed using a dielectric paste containing To produce a laminate unit, and to stack 50 laminate units to produce a multilayer ceramic capacitor, a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) was used as a binder. Copolymer of methyl methacrylate and butyl acrylate with a weight average molecular weight of 700,000 on a ceramic green sheet as a binder In addition, in the case of producing a laminate unit by printing a conductor paste containing α-terpinyl acetate as a solvent and laminating 50 laminate units, a polyvinyl butyral ( (I-dihydrocarbyl) comprising a copolymer of methyl methacrylate and butyl acrylate as a binder having a weight average molecular weight of 700,000 on a ceramic green sheet formed using a dielectric paste having a degree of polymerization of 1450 and a degree of butyralization (69%). In the case of producing a laminate unit by printing a conductor paste containing acetate as a solvent and laminating 50 laminate units, a polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) was used as a binder. Methyl methacrylate with a weight average molecular weight of 700,000 on a ceramic green sheet formed using a dielectric paste containing In the case of manufacturing a laminate unit by printing a conductor paste containing a copolymer of butyl methacrylate as a binder and containing I-mentone as a solvent, and stacking 50 laminate units, a binder is produced. On the ceramic green sheet formed using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder, a copolymer of a copolymer of methyl methacrylate and butyl acrylate having a weight average molecular weight of 700,000 In the case of producing a laminate unit by printing a conductor paste containing I-peryl acetate as a solvent and laminating 50 laminate units, a polyvinyl butyral (polymerization degree 1450, Methaek having a weight average molecular weight of 700,000 on a ceramic green sheet formed using a dielectric paste containing butyralization degree 69%) A laminate paste was prepared by printing a conductor paste containing a copolymer of methyl lylate and butyl acrylate as a binder and containing I-carbyl acetate as a solvent, and laminating 50 laminate units to produce a multilayer ceramic capacitor. Copolymer of methyl methacrylate and butyl acrylate with a weight average 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 and a binder. In the case of producing a laminate unit by printing a conductor paste containing as a and containing d-dihydrocarbylate as a solvent, and stacking 50 laminate units, a multilayer ceramic capacitor is used. It has been found that the shot rate can be significantly reduced.

This is because the mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) used as the solvent of the conductor paste in Comparative Examples 1 and 2 and the dielectric paste used by the terpionel to form the ceramic green sheet. In order to dissolve the polyvinyl butyral contained therein, cracking and wrinkles occur on the surface of the electrode layer, surface roughness (Ra) is deteriorated, and pinholes or cracks are generated in the ceramic green sheet. Limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-peryl acetate, I-carbyl acetate and d-dihydro carbyl acetate, used as solvents for the sieve paste, form ceramic green sheets. It hardly dissolves the polyvinyl butyral contained in the dielectric paste used for this purpose, so that cracks or wrinkles occur on the surface of the electrode layer. It is thought that it is effectively prevented, so that pinholes or cracks are prevented from occurring in the ceramic green sheet.

Example 8

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 sheets

In the same manner as in Example 1, the dielectric paste for ceramic green sheet was applied onto a polyethylene terephthalate film to form a ceramic green sheet having a thickness of 1 μm.

Preparation of Dielectric Paste for Spacer Layer

An additive powder was prepared by mixing 1.48 parts by weight of (BaCa) SiO ₃ , 1.01 part by weight of Y ₂ 0 ₃ , 0.72 part by weight of MgCO ₃ , 0.13 part by weight of MnO, and 0.045 part by weight of V ₂ 0 ₅ .

The slurry was prepared by mixing 150 parts by weight of acetone, 104.3 parts by weight of tapionel, and 1.5 parts by weight of polyethylene glycol dispersant based on 100 parts by weight of the additive powder prepared in this way, and prepared by ASHIZAWA FINETECH LTD. Additives in the slurry were ground using a production mill "LMZ 0.6" (trade name).

In grinding the additives in the slurry, Zr0 ₂ beads (0.1 mm in diameter) are charged in the vessel to 80% of the vessel capacity, and the rotor is rotated at a circumferential speed of 14 m / min to allow the entire slurry to remain in the vessel for 5 minutes. The additive in the slurry was pulverized by circulating between the vessel and the slurry tank until it was.

 The median diameter of the additives after grinding was 0.1 μm.

Subsequently, acetone was evaporated to remove from the slurry using an evaporator to prepare an additive paste in which the additive was dispersed in limonene. The nonvolatile matter concentration in the additive paste was 49.3 wt%.

Subsequently, a copolymer of 8 parts by weight of an acid value of 5 mg KOH / g of methyl methacrylate and butyl acrylate (copolymerization ratio (weight ratio) 82:18, weight average molecular weight of 700,000) was dissolved in 92 parts by weight of limonene at 70 ° C. to prepare an organic vehicle. An 8% solution was prepared, and the slurry having the following composition was dispersed over 16 hours using a ball mill. Dispersion conditions were mill of ZrO ₂ (diameter 2.0mm) 45m / min to the slurry in the amount of 30% by volume, mill charge to 60% by volume, and the state of flux of the ball mill.

8.87 parts by weight of additive paste

BaTi0 ₃ powder (SAKAI CHEMICAL INDUSTRY CO., LTD.manufacture: brand name "BT-02" = particle diameter 0.2μm) 95.70 parts by weight

104.36 parts by weight of organic vehicle

1.0 part by weight of polyethylene glycol dispersant

2.61 parts by weight of dioctyl phthalate (plasticizer)

0.4 part by weight of imidazoline surfactant

Acetone 57.20 parts by weight

Subsequently, using a stirring apparatus 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 Conductor Paste for Electrode Layer

In the same manner as in Example 1, a conductor paste for an electrode layer was prepared.

Formation of spacer layer

The dielectric paste thus prepared was printed in a predetermined pattern on a ceramic green sheet using a screen printing machine, and dried at 90 ° C. for 5 minutes to form a spacer layer on the ceramic green sheet.

Subsequently, KOSAKA LABORATORY LTD. It was 0.070 micrometer when the surface roughness Ra of the spacer layer was measured in the same manner as in Example 1 using Manufacture "Surcoder (SE-30D)" (brand name).

In addition, when the surface of the spacer layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed on the surface of the spacer layer.

Formation of electrode layer and fabrication of laminate unit

Further, the conductor paste is printed on the ceramic green sheet in a pattern complementary to the pattern of the spacer layer using a screen printing machine, dried at 90 ° C. for 5 minutes to form an electrode layer having a thickness of 1 μm, and polyethylene tere. The laminated unit in which the ceramic green sheet, the electrode layer, and the spacer layer were laminated | stacked on the surface of the phthalate film was produced.

The surface roughness Ra of the electrode layer formed in this way was determined by KOSAKA LABORATORY LTD. It measured by the same method as Example 1 using the preparation "Surf coder (SE-30D)" (brand name), and it was 0.070 micrometer.

In addition, when the surface of the electrode layer was observed at a magnification of 400 times using a metal microscope, no cracking or wrinkles were observed on the surface of the electrode layer.

Fabrication of Ceramic Green Chips

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

The ceramic green sheet having a thickness of 10 μm thus produced was peeled off from the polyethylene terephthalate film, and cut. Then, the cut five ceramic green sheets were laminated to form a cover layer having a thickness of 50 μm. It peeled and cut | disconnected from the polyethylene terephthalate film, and cut | disconnected 50 laminated body units were laminated | stacked on the cover layer.

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

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

Fabrication of Multilayer Ceramic Capacitor Samples

Using the ceramic green chip thus produced, a multilayer ceramic capacitor sample was produced in the same manner as in Example 1.

A total of 50 multilayer ceramic capacitor samples were produced in the same manner.

Short ratio

In the same manner as in Example 1, the resistance values of the 50 multilayer ceramic capacitor samples thus produced were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured.

As a result, the short rate was 16%.

Example 9

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that α-terpinyl acetate was used instead of limonene as a solvent when preparing the electrode paste conductor paste and the spacer paste dielectric paste. The surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were 0.069 µm and 0.069 µm, respectively.

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

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 14%.

Example 10

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that I-dihydrocarbyl acetate was used instead of limonene as a solvent for preparing the electrode paste conductor paste and the spacer layer dielectric paste. The surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were measured to be 0.070 µm and 0.070 µm, respectively.

In addition, when the surface of the electrode layer and the spacer layer was observed by magnification 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 18%.

Example 11

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that I-mentone was used instead of limonene as a solvent when preparing the electrode paste conductor paste and the spacer paste dielectric paste. The surface roughness Ra of the layer and the surface roughness Ra of the electrode layer were measured to be 0.066 μm and 0.066 μm, respectively.

 In addition, when the surface of the electrode layer and the spacer layer was observed by magnification 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 10%.

Example 12

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that I-peryl acetate was used instead of limonene as a solvent when preparing the electrode paste conductor paste and the spacer paste dielectric paste. The surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were measured to be 0.074 µm and 0.074 µm, respectively.

In addition, when the surface of the electrode layer and the spacer layer was observed by magnification 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. The short rate was 16%.

Example 13

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that I-carbyl acetate was used instead of limonene as a solvent for preparing the electrode paste conductor paste and the spacer layer dielectric paste. The surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were 0.076 µm and 0.076 µm, respectively.

In addition, when the surface of the electrode layer and the spacer layer was observed by magnification 400 times using a metal microscope, no cracking or wrinkles were observed.

 In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 8%.

Example 14

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that d-dihydrocarbyl acetate was used instead of limonene as a solvent when preparing the electrode paste conductor paste and the spacer paste dielectric paste. The surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were measured to be 0.076 µm and 0.076 µm, respectively.

In addition, when the surface of the electrode layer and the spacer layer was observed by magnification 400 times using a metal microscope, no cracking or wrinkles were observed.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 10%.

Comparative Example 3

The same method as in Example 8, except that a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) was used instead of limonene as a solvent when 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, and were 0.102 µm and 0.102 µm, respectively.

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

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 90%.

Comparative Example 4

A spacer layer and an electrode layer were formed on the ceramic green sheet in the same manner as in Example 8 except that terpionel was used instead of limonene as a solvent when preparing the conductive paste for the electrode layer and the dielectric paste for the spacer layer. The surface roughness Ra of the layer and the surface roughness Ra of the electrode layer were measured 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 by magnification 400 times using a metal microscope, cracks and wrinkles were observed on the surface of the electrode layer and the spacer layer.

In addition, 50 multilayer ceramic capacitor samples were produced in the same manner as in Example 8, the resistance values of the 50 multilayer ceramic capacitor samples were measured by a multimeter, and the short ratio of the multilayer ceramic capacitor samples was measured. Was 88%.

From Examples 8 to 14 and Comparative Examples 3 and 4, meta with a weight average 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. A dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio 50:50)) as a solvent was printed to form a spacer layer. A conductive paste containing a copolymer of methyl methacrylate and butyl acrylate having an average molecular weight of 700,000 as a binder and a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) as a solvent is printed Is formed on the ceramic green sheet formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A dielectric paste containing a copolymer of methyl methacrylate and butyl acrylate having an average molecular weight of 700,000 as a binder and terpionel as a solvent was printed to form a spacer layer, and methyl methacrylate and acrylic acid having a weight average molecular weight of 700,000 When an electrode layer is formed by printing a conductor paste containing a copolymer of butyl as a binder and terpionel as a solvent, the surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer deteriorate. Voids are likely to form in the multilayer ceramic capacitors produced by laminating the laminated unit, whereas ceramic green formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder A copolymer containing a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder And printing a dielectric paste containing limonene as a solvent to form a spacer layer, a conductor paste comprising a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder, and limonene as a solvent. When the electrode layer was formed by printing, methyl methacrylate and acrylic acid having a weight average molecular weight of 700,000 on a ceramic green sheet formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1456, butyralization degree 69%) as a binder. A dielectric paste containing a copolymer of butyl as a binder and α-terpinyl acetate as a solvent is printed to form a spacer layer, and a copolymer of a copolymer of methyl methacrylate and butyl acrylate having a weight average molecular weight of 700,000 as a binder And printing a conductor paste containing? -Terpinyl acetate as a solvent. In the case of forming the electrode layer, methyl methacrylate and butyl acrylate were obtained on a ceramic green sheet formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A dielectric paste containing a copolymer of copolymer as a binder, and containing I-dihydrocarbyl acetate as a solvent to form a spacer layer, and comprising a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder. In the case where an electrode layer is formed by printing a conductor paste containing I-dihydrocarbyl acetate as a solvent, a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) is formed as a binder. The nose of methyl methacrylate and butyl acrylate with a weight average molecular weight of 700,000 on one ceramic green sheet A dielectric paste containing a reamer as a binder and I-mentone as a solvent is printed to form a spacer layer, and a copolymer of methyl methacrylate methyl and butyl acrylate as a binder is included, and I-mentone In the case where the electrode layer was formed by printing a conductor paste containing a solvent as a solvent, the weight average was measured 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 containing a copolymer of a molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and containing I-peryl acetate as a solvent was printed to form a spacer layer, and a weight average molecular weight of 700,000 methyl methacrylate and A copolymer of butyl acrylate as a binder and I-peryl acetate as a solvent When the entire paste was printed to form the electrode layer, methacrylic acid having a weight average 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. A dielectric paste containing a copolymer of methyl and butyl acrylate as a binder and containing I-carbyl acetate as a solvent was printed to form a spacer layer, and copolymerized with a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate. When a conductive paste containing as a binder and containing I-carbyl acetate as a solvent was printed to form an electrode layer, and a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder was used. Methyl methacrylate and acrylic acid moiety with a weight average molecular weight of 700,000 on the formed ceramic green sheet A dielectric paste containing a copolymer of as a binder and d-dihydrocarbyl acetate as a solvent to form a spacer layer, and containing a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder. When the electrode paste was formed by printing a conductor paste containing d-dihydrocarbyl acetate as a solvent, it was found that the surface roughness Ra of the spacer layer and the surface roughness Ra of the electrode layer were improved.

Further, from Examples 8 to 14 and Comparative Examples 3 and 4, a weight average 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 A laminate unit is printed by printing a dielectric paste and a conductor paste containing a copolymer of methyl methacrylate and butyl acrylate as a binder and a mixed solvent of terpionel and kerosene (mixing ratio (mass ratio) 50:50) as a solvent. On the ceramic green sheet formed by laminating 50 laminate units and manufacturing a multilayer ceramic capacitor and using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A dielectric comprising a copolymer of methyl methacrylate and butyl acrylate as a binder and terpionel as a solvent When the paste and the conductor paste are printed to produce a laminate uni sheet, and 50 laminate units are laminated to produce a multilayer ceramic capacitor, the short ratio of the multilayer ceramic capacitor is significantly increased. A copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate is included as a binder on a ceramic green sheet formed by using a dielectric paste containing Ral (polymerization degree 1450, butyralization degree 69%), and limonene is used as a binder. A polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) was used as a binder when a laminate unit was produced by printing a dielectric paste and a conductor paste included as a laminate, and a laminated ceramic capacitor was prepared by laminating 50 laminate units. Weight average molecules on a ceramic green sheet formed using a dielectric paste comprising A laminate unit was prepared by printing a dielectric paste and a conductor paste containing a copolymer of 700,000 methyl methacrylate and butyl acrylate as a binder, and containing? -Terpinyl acetate as a solvent, to prepare 50 laminate units. When the laminated ceramic capacitor was laminated to produce a multilayer ceramic capacitor, methyl methacrylate having a weight average 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. A laminate unit is prepared by printing a dielectric paste and a conductor paste containing a copolymer of butyl acrylate and a butyl acrylate as a binder, and containing I-dihydrocarbyl acetate as a solvent, and stacking 50 laminate units to form a multilayer ceramic capacitor. In the case of preparing a polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder A dielectric paste and a conductor paste containing a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and containing I-mentone as a solvent were printed on a ceramic green sheet formed using the dielectric paste. When a laminate unit was fabricated and 50 laminate units were laminated to produce a multilayer ceramic capacitor, a ceramic formed by using a dielectric paste containing polyvinyl butyral (polymerization degree 1450, butyralization degree 69%) as a binder. A laminate unit was produced by printing a dielectric paste and a conductor paste containing a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder and containing I-peryl acetate as a solvent on the green sheet. In the case of manufacturing a multilayer ceramic capacitor by laminating 50 laminate units, A copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate is contained as a binder on a ceramic green sheet formed using a dielectric paste containing rivinylbutyral (polymerization degree 1450, butyralization degree 69%), A laminate unit was prepared by printing a dielectric paste and a conductor paste containing I-carbyl acetate as a solvent, a laminated ceramic capacitor was laminated by stacking 50 laminate units, and polyvinyl butyral (polymerization degree 1450). And a copolymer of a weight average molecular weight of 700,000 methyl methacrylate and butyl acrylate as a binder on a ceramic green sheet formed using a dielectric paste containing butyralization degree (69%), and d-dihydrocarbyl acetate 50 sheets of laminated unit were formed by printing the dielectric paste and the conductor paste which are included as a solvent. In the case where a multilayer ceramic capacitor is produced by stacking the laminated unit of the above, it has been found that the short rate of the multilayer ceramic capacitor can be greatly reduced.

This is because the mixed solvent (mixing ratio (mass ratio) 50:50) of terpionel and kerosene used as the solvent of the dielectric paste for the spacer layer and the conductor paste in Comparative Examples 3 and 4 and the terpionel form the 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 roughness Ra of the electrode layer are deteriorated. While sufficient to cause pinholes or cracks in the ceramic green sheet, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, used as solvents for the dielectric paste and conductor paste for spacer layers in Examples 8 to 14, I-mentone, I-peryl acetate, I-carbyl acetate and d-dihydrocarbyl acetate are used to form ceramic green sheets. Since the polyvinyl butyral contained in the dielectric paste used is hardly dissolved, cracking and wrinkles are effectively prevented from occurring on the surfaces of the spacer layer and the electrode layer, thereby preventing pinholes or cracks from occurring in the ceramic green sheet. I think because.

The present invention is not limited to the above embodiments and examples, and various changes are possible within the scope of the invention described in the claims, and needless to say that they are also included within the scope of the present invention.

According to the present invention, it is possible to provide a conductive paste for an electrode layer that can reliably prevent short defects from occurring in a multilayer ceramic electronic component without dissolving a binder contained in a layer adjacent to the electrode layer of the multilayer ceramic electronic component. It becomes possible.

Moreover, according to this invention, it becomes possible to provide the manufacturing method of the laminated unit for laminated ceramic electronic components which can reliably prevent a short defect from generating in a laminated ceramic electronic component.

Claims (10)

Acrylic resins are included as binders and are selected from the group consisting of limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-perylyl acetate, I-carbyl acetate and d-dihydrocarbyl acetate Including one kind of solvent, The weight average molecular weights of the said acrylic resin are 450,000 or more and 900,000 or less, The acid value of the said acrylic resin is 5 mgKOH / g or more and 25 mgKOH / g or less, The conductor paste characterized by the above-mentioned. delete delete An acrylic resin is included as a binder on a ceramic green sheet containing butyral resin as a binder, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-peryl acetate, I-carbyl acetate And a conductive paste containing one solvent selected from the group consisting of d-dihydrocarbyl acetate in a predetermined pattern to form an electrode layer, The weight average molecular weights of the said acrylic resin are 450,000 or more and 900,000 or less, The acid value of the said acrylic resin is 5 mgKOH / g or more and 25 mgKOH / g or less, The degree of polymerization of the butyral resin is 1000 or more, A butyralization degree of said butyral resin is 64 mol% or more and 78 mol% or less, The manufacturing method of the laminated unit for laminated ceramic electronic components characterized by the above-mentioned. The method of claim 4, wherein After drying the electrode layer, the acrylic resin is included on the ceramic green sheet as a binder, limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-peryl acetate, I-carbyl acetate and A laminate for multilayer ceramic electronic parts, further comprising a spacer layer formed by printing a dielectric paste containing one solvent selected from the group consisting of d-dihydrocarbyl acetate in a pattern complementary to the pattern of the electrode layer. Method of manufacturing the unit. The method of claim 4, wherein Prior to forming the electrode layer, the acrylic resin is included as a binder on the ceramic green sheet, and limonene, α-terpinyl acetate, I-dihydrocarbyl acetate, I-mentone, I-peryl acetate, I-carbyl A multilayer ceramic, characterized in that a spacer layer is formed by printing a dielectric paste comprising a solvent selected from the group consisting of acetate and d-dihydrocarbyl acetate in a pattern complementary to the pattern of the electrode layer to be formed. The manufacturing method of the laminated body unit for components. delete delete delete delete