KR100863398B1 - Method for manufacturing multilayer electronic component - Google Patents

Abstract

Forming a green chip by stacking the green sheet 10a, forming the electrode layer 12a on the surface of the green sheet 10a, and laminating the green sheet 10a on which the electrode layer 12a is formed. A method of manufacturing a laminated electronic component having a step and a step of firing the green chip, wherein the green sheet 10a having the electrode layer 12a is formed before the green sheet 10a having the electrode layer 12a is laminated. An adhesive layer (28) is formed on an electrode layer side surface, and the green sheet (10a) in which the electrode layer (12a) is formed is laminated with the adhesive layer (28) interposed therebetween.

Description

Manufacturing method of laminated electronic component {METHOD FOR MANUFACTURING MULTILAYER ELECTRONIC COMPONENT}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a multilayered electronic component such as, for example, a multilayer ceramic capacitor, and more particularly, even when the green sheet is made very thin, the stackability (adhesiveness at the time of lamination) is high and non-adhesive The present invention relates to a method for manufacturing a laminated electronic component that can reduce defects (non-lamination) and short defect rate and which is inexpensive.

In recent years, with the miniaturization of various electronic apparatuses, miniaturization and high performance of electronic components mounted in the electronic apparatuses have been advanced. As one of the electronic components, there is a multilayer ceramic capacitor, and this multilayer ceramic capacitor is also required to be downsized and high in performance.

In order to advance miniaturization and high capacity of this multilayer ceramic capacitor, the thickness of the dielectric layer is strongly demanded, and in recent years, the thickness of the dielectric green sheet to form the dielectric layer after firing has also been reduced to several micrometers or less.

In order to manufacture the dielectric green sheet, first, a paint for green sheet made of a dielectric powder, a binder, a plasticizer, and an organic solvent (toluene, alcohol, MEK, etc.) is first prepared. Next, this green sheet coating material is apply | coated on carrier films, such as PET, using a doctor blade method, etc., and is manufactured by heat-drying.

In addition, recently, a ceramic suspension in which a dielectric powder and a binder are mixed with a solvent is prepared, and a biaxial stretching of the film-form molded product obtained by extrusion molding the suspension has also been studied.

A method of manufacturing a multilayer ceramic capacitor using the above-described dielectric green sheet will be described in detail. First, an internal electrode layer is formed on a dielectric green sheet in a predetermined pattern by a printing method or a transfer method. Subsequently, the carrier film is peeled from the green sheet on which the internal electrode pattern is formed, and a plurality of layers of these are cut into chips to form a green chip, and after firing the green chip, an external electrode is formed (for example, manufactured). , Patent Document 1).

However, as in Patent Document 1, when the green sheet having the internal electrode pattern is directly laminated, the adhesive force between the internal electrode formation surface and the green sheet surface is insufficient, resulting in a problem of poor adhesion. Moreover, when the internal electrode was thinned, there also existed a problem that a short defective rate became high.

In order to solve the problem of adhesion failure and short defect, for example, in Patent Documents 2 to 4, as a green sheet having an internal electrode pattern, a green sheet having a structure in which upper and lower surfaces are sandwiched in the green sheet layer is formed. A method of laminating a green sheet is disclosed. In the methods described in these documents, for example, the green sheet layers, which are about half the desired thickness, are bonded to each other to have a desired thickness (thickness for one layer). According to this method, since the green sheet layers are bonded to each other during lamination, the adhesive force between the sheets can be improved and the short defects caused by the pinholes can be reduced. However, in this method, it is difficult to cope with further thinning of the green sheet because it is necessary to make the green sheet layer about half of the desired thickness, that is, very thin.

Moreover, in patent documents 5-10, the method of laminating | stacking using the green sheet which formed two or more layers of green sheet layers as a green sheet which has an internal electrode pattern is disclosed. According to these documents, it is described that the occurrence of short defects and delamination can be suppressed. However, in the methods described in these documents, in order to thin the green sheet itself, it is necessary to make each green sheet layer thinner than that, so that it is difficult to cope with further thinning of the green sheet.

In particular, these documents use green sheets obtained by superimposing two or more layers of green sheet layers having a thickness of about several μm. That is, in Patent Literatures 5 and 6, two to three layers of green sheet layers of about 2-3 μm, and 6 to 7 μm of Green Sheet layers of two and three layers of Patent Documents 9 and 10 in Patent Literatures 7, 8. The green sheet layer of about 3.4 micrometers and the green sheet layer of about 0.6-1 micrometer are overlapped and formed. Therefore, in these documents, it is difficult to cope with thinning.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-159966

Patent Document 2: Japanese Patent Application Laid-Open No. 7-297073

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-103983

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-119802

Patent Document 5: Japanese Unexamined Patent Publication No. 10-50552

Patent Document 6: Japanese Patent Application Laid-Open No. 11-144992

Patent Document 7: Japanese Patent Application Laid-Open No. 8-37128

Patent Document 8: Japanese Patent Application Laid-Open No. 5-101970

Patent Document 9: Japanese Patent Application Laid-Open No. 2003-264120

Patent Document 10: Japanese Patent Application Laid-Open No. 2003-272947

Disclosure of the Invention

Problems to be Solved by the Invention

The present invention has been made in view of such a situation, and even when the green sheet is made very thin, the stackability (adhesiveness at the time of lamination) is high, the short failure rate can be reduced, and the laminated type such as a low cost multilayer ceramic capacitor An object of the present invention is to provide a method for manufacturing an electronic component.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the objective of this invention is to form an adhesive layer on the electrode layer side surface of the green sheet in which the electrode layer was formed, and to laminate | stack the green sheet in which the electrode layer was formed through this adhesive layer. The inventors have found that they can achieve the present invention to complete the present invention.

That is, the manufacturing method of the laminated electronic component of the present invention,

Forming a green sheet,

Forming an electrode layer on a surface of the green sheet;

Stacking the green sheets on which the electrode layers are formed to form green chips;

A method of manufacturing a laminated electronic component having a process of firing the green chip,

Before laminating the green sheet on which the electrode layer is formed, an adhesive layer is formed on the electrode layer side surface of the green sheet on which the electrode layer is formed,

It is characterized by laminating the green sheet on which the electrode layer is formed with the adhesive layer therebetween.

In the manufacturing method of this invention, an adhesive layer is formed in the electrode layer side surface of the green sheet in which the electrode layer was formed, and the green sheet in which the electrode layer was formed is laminated | stacked, and the green chip is formed by laminating | stacking the adhesive layer. By laminating the adhesive layer therebetween, the stackability (adhesiveness at the time of lamination) can be improved to prevent non-bonding defects (non-lamination) and adhesion failure, and to reduce the short failure rate. Moreover, in this invention, since the green sheet in which the electrode layer was formed is laminated | stacked with the adhesive layer interposed, high pressure and heat are unnecessary at the time of lamination, and adhesion at low pressure and low temperature is attained. In addition, even when the green sheet is very thin, the green sheet is not broken and can be laminated satisfactorily.

In the present invention, the electrode layer can be formed on the surface of the green sheet without using an adhesive layer. As a formation method of the said electrode layer, thick film formation methods, such as the printing method using an electrode paste, or thin film methods, such as vapor deposition and sputtering, etc. are mentioned, for example. When the electrode layer is formed on the surface of the green sheet without using an adhesive layer, the manufacturing process can be simplified and the manufacturing cost can be reduced. In the present invention, when laminating the green sheets on which the electrode layers are formed, the lamination is carried out with the adhesive layer interposed therebetween, so that stackability (adhesiveness at the time of lamination) can be maintained high.

Preferably, the thickness of the said adhesive layer is 0.02-0.3 micrometer, More preferably, it is 0.05-0.1 micrometer.

In this invention, it is preferable to make thickness of the said contact bonding layer into the said range from a viewpoint of prevention of delamination and a crack. When the thickness of the adhesive layer is too thin, the thickness of the adhesive layer is smaller than the unevenness of the green sheet surface, and the adhesiveness tends to be remarkably lowered. In addition, when the thickness of the adhesive layer is too thick, depending on the thickness of the adhesive layer, a gap tends to occur in the interior of the element body after sintering, which tends to be the origin of cracking or the capacitance of the volume tends to be significantly lowered. In addition, when an adhesive layer thicker than the average particle diameter of the dielectric particles included in the green sheet is formed, a gap tends to occur in the interior of the element body after sintering, depending on the thickness of the adhesive layer, and the capacitance of the volume is considerably lowered. There is this.

Preferably, the green sheet is formed detachably on the surface of the first support sheet. As a 1st support sheet, PET film etc. are mentioned, for example, In order to improve peelability, it is preferable that silicone resin etc. are coated.

Preferably, the thickness of the green sheet is 1.5 μm or less, and the thickness of the adhesive layer is 1/10 or less of the thickness of the green sheet. Further, the thickness of the electrode layer is preferably 1.5 µm or less. According to the present invention, even when the green sheet and the electrode layer are thinned to the above-described thickness, the stackability is high, and non-bonding defects and short defect rates can be reduced.

Moreover, in this invention, it is preferable to make thickness of the sum total of the said green sheet and the said electrode layer into 3.0 micrometers or less. The present invention is particularly effective when the thickness of the green sheet and the electrode layer is in the above range.

In the present invention, the thickness of the adhesive layer, the green sheet and the electrode layer means a thickness at the time of drying.

Preferably, the green sheet includes dielectric particles mainly composed of barium titanate, and the average particle diameter of the dielectric particles is 0.3 µm or less. If the average particle diameter of the dielectric particles is too large, the formation of a thin green sheet tends to be difficult.

Preferably, the green sheet contains at least one of acrylic resin or butyral resin as a binder. In the case of forming a thin green sheet, by using such a binder, it is possible to form a green sheet having sufficient strength even if thin.

Preferably, the adhesive layer comprises an organic polymer material substantially the same as the binder included in the green sheet. This is because the binder is removed from the chip at the time of debinding the green chip by the debinding process under the same conditions.

Preferably, the adhesive layer contains a plasticizer, and the plasticizer is at least one of phthalic acid ester, glycol, adipic acid and phosphate ester. By including this kind of plasticizer in a predetermined amount, good adhesion can be exhibited.

Preferably, the adhesive layer comprises a charging agent, the charging agent comprises one of imidazoline-based surfactants, and the weight-based addition amount of the charging agent is equal to or less than the weight-based addition amount of the organic polymer material. By including this kind of charging agent in a predetermined amount, the effect of antistatic can be obtained.

The adhesive layer may include dielectric particles, the dielectric particles having an average particle diameter equal to or smaller than the average particle diameter of the dielectric particles included in the green sheet, and having a dielectric composition substantially the same as the dielectric composition included in the green sheet. It may be included. Since the adhesive layer becomes a part of the element body after firing, it is preferable that dielectric particles of substantially the same kind are contained as the dielectric particles included in the green sheet. Since the adhesive layer needs to control the thickness, the average particle diameter of the dielectric particles is preferably equal or smaller.

Preferably, the weight-based addition ratio of the dielectric particles included in the adhesive layer is less than the weight-based addition ratio of the dielectric particles included in the green sheet. This is because the adhesion of the adhesive layer is maintained satisfactorily.

Preferably, the electrode layer is formed in a predetermined pattern on the surface of the green sheet, a blank pattern layer having a thickness substantially the same as the electrode layer is formed on the surface of the green sheet in which the electrode layer is not formed, and the margin pattern layer The green sheet is made of substantially the same material.

By forming a blank pattern layer, the level difference of the surface by the electrode layer of a predetermined pattern is eliminated. Therefore, even when the green sheet is laminated and pressurized prior to firing before firing, the outer surface of the laminate is kept flat and the electrode layers are not shifted in the planar direction. Furthermore, the green sheet is torn and causes a short circuit. There is no case. In the present invention, the margin pattern layer means a dielectric layer formed in a pattern complementary to the electrode layer.

Preferably, before laminating the green sheet on which the electrode layer is formed, the first support sheet is peeled from the green sheet on which the electrode layer is formed,

In the state of peeling the said 1st support sheet, the surface of the semi-electrode layer side (surface opposite to the surface on which the electrode layer is formed) of the green sheet in which the said electrode layer was formed is laminated | stacked on another green sheet.

Alternatively, with the first supporting sheet, the electrode layer side surface of the green sheet on which the electrode layer is formed is laminated on another green sheet,

After laminating the green sheet on which the electrode layer is formed, it is preferable to peel the first support sheet from the green sheet on which the electrode layer is formed.

In this invention, it is preferable to form the said contact bonding layer by the transfer method or the coating method.

When the adhesive layer is formed by a transfer method,

It is preferable that the said adhesive layer is formed so that exfoliation is possible on the surface of a 2nd support sheet initially, and is pressed by the surface of the electrode layer side of the green sheet in which the said electrode layer was formed, and is transferred.

By forming the adhesive layer by a transfer method, the penetration of at least one of the electrode layer or the green sheet of the component of the adhesive layer, that is, the sheet attack can be effectively prevented. Therefore, there is no possibility of adversely affecting the composition of at least one of the electrode layer or the green sheet. In addition, even when the adhesive layer is formed thin, adhesiveness can be maintained high because the components of the adhesive layer do not penetrate into at least one of the electrode layer or the green sheet.

Or when forming the said contact bonding layer by the apply | coating method,

It is preferable that the said adhesive layer is formed by apply | coating directly to the electrode layer side surface of the green sheet in which the said electrode layer was formed by the die coating method.

By forming the said adhesive layer by the die-coating method using a die coater, compared with the case where an adhesive layer is formed by the transfer method, the usage-amount of PET film can be reduced and lead time can be shortened.

Although it does not specifically limit as a laminated electronic component manufactured by this invention, For example, a laminated ceramic capacitor, a laminated inductor element, etc. are illustrated.

In addition, in this invention, an electrode layer is used by the concept containing the electrode paste film used as an internal electrode layer after baking.

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on embodiment shown in drawing.

First, as an embodiment of an electronic component manufactured by the method according to the present invention, the entire structure of a multilayer ceramic capacitor will be described.

As shown in FIG. 1, the multilayer ceramic capacitor 2 according to the present embodiment includes a capacitor body 4, a first terminal electrode 6, and a second terminal electrode 8. The capacitor body 4 includes a dielectric layer 10 and an internal electrode layer 12, and these internal electrode layers 12 are alternately stacked between the dielectric layers 10. One of the inner electrode layers 12 alternately stacked is electrically connected to the inside of the first terminal electrode 6 formed outside the first end of the capacitor body 4. In addition, the other inner electrode layers 12 alternately stacked are electrically connected to the inside of the second terminal electrode 8 formed outside the second end of the capacitor body 4.

In the present embodiment, the internal electrode layer 12 is formed in a predetermined pattern on the surface of the ceramic green sheet 10a as shown in Figs. 2A and 2B, as will be described later in detail.

The material of the dielectric layer 10 is not specifically limited, For example, it is comprised from dielectric materials, such as at least one of calcium titanate, strontium titanate, or barium titanate. Although the thickness of each dielectric layer 10 is not specifically limited, It is common that they are several micrometers-several hundred micrometers. Especially in this embodiment, Preferably it is 3 micrometers or less, More preferably, it is thinned to 1.5 micrometers or less.

Although the material of the terminal electrodes 6 and 8 is not specifically limited, Usually, copper, a copper alloy, nickel, a nickel alloy, etc. are used, but silver, an alloy of silver, palladium, etc. can also be used. Although the thickness of the terminal electrodes 6 and 8 is not specifically limited, either, Usually, it is about 10-50 micrometers.

What is necessary is just to determine the shape and size of the multilayer ceramic capacitor 2 suitably according to an objective and a use. When the multilayer ceramic capacitor 2 has a rectangular parallelepiped shape, it is usually vertical (0.6 to 5.6 mm, preferably 0.6 to 3.2 mm) x horizontal (0.3 to 5.0 mm, preferably 0.3 to 1.6 mm) x thickness (0.1 to 1.9 mm, preferably 0.3 to 1.6 mm).

Next, an example of the manufacturing method of the multilayer ceramic capacitor 2 which concerns on this embodiment is demonstrated.

First, a dielectric paste is prepared in order to manufacture the ceramic green sheet which comprises the dielectric layer 10 shown in FIG. 1 after baking.

The dielectric paste is usually composed of an organic solvent paste or an aqueous paste obtained by kneading a dielectric material and an organic vehicle.

As a dielectric material, it is suitably selected from various compounds which become a complex oxide and an oxide, for example, carbonate, nitrate, hydroxide, an organometallic compound, etc., and can mix and use. The dielectric material is usually used as a powder having an average particle diameter of 0.3 m or less, preferably 0.2 m or less. In order to form a very thin green sheet, it is preferable to use a powder finer than the green sheet thickness.

The organic vehicle is obtained by dissolving a binder in an organic solvent. Although it does not specifically limit as a binder used for an organic vehicle, Although normal various binders, such as ethyl cellulose, polyvinyl butyral, and an acrylic resin, are used, Preferably, butyral system, such as an acrylic resin or polyvinyl butyral, is used. Resin is used.

In addition, the organic solvent used in the organic vehicle is not particularly limited, and terpineol, alcohol, butyl carbitol, acetone, methyl ethyl ketone (MEK), toluene, xylene, ethyl acetate, butyl stearate, isobornyl acetate, and the like. Organic solvents are used. In addition, the vehicle in an aqueous paste dissolves a water-soluble binder in water. The water-soluble binder is not particularly limited, and polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, water-soluble acrylic resins, emulsions and the like are used. Content of each component in a dielectric paste is not specifically limited, Usually, what is necessary is just about 1-5 mass% for a binder, and about 10-50 mass% of a solvent (or water).

The dielectric paste may contain additives selected from various dispersants, plasticizers, dielectrics, glass flits, insulators, charge aids, and the like, as necessary. However, it is preferable to make these total content into 10 mass% or less. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and benzyl butyl phthalate, adipic acid, phosphate esters and glycols. When using butyral resin as binder resin, it is preferable that a plasticizer is content of 25-100 mass parts with respect to 100 mass parts of binder resins. If the amount of plasticizer is too small, the green sheet tends to be weak, and if too much, the plasticizer bleeds out and handling is difficult.

Then, using this dielectric paste, as shown in Fig. 2A, by the doctor blade method, on the carrier sheet 20 as the first support sheet, preferably 0.5 to 30 m, more preferably 0.5 to 10 m The green sheet 10a is formed to a thickness of about enough. The green sheet 10a is formed on the carrier sheet 20 and then dried. The drying temperature of the green sheet 10a is preferably 50 to 100 ° C, and the drying time is preferably 1 to 20 minutes. The thickness of the green sheet 10a after drying is reduced to a thickness of 5 to 25% as compared with before drying. As for the thickness of the green sheet after drying, 1.5 micrometers or less are preferable.

As the carrier sheet 20, PET film etc. are used, for example, and it is preferable that silicone etc. are coated in order to improve peelability. Although the thickness of these carrier sheets 20 is not specifically limited, Preferably it is 5-100 micrometers.

2B, the electrode layer 12a of a predetermined pattern is formed on the surface of the green sheet 10a formed on the carrier sheet 20, and the electrode layer 12a is not formed before and after. On the surface of the green sheet 10a, a blank pattern layer 24 having a thickness substantially the same as that of the electrode layer 12a is formed. In this embodiment, it is preferable to form the electrode layer 12a and the blank pattern layer 24 on the surface of the green sheet 10a without using the adhesive layer mentioned later. By forming the electrode layer 12a and the margin pattern layer 24 on the green sheet 10a without using an adhesive layer, it is possible to simplify the manufacturing process and reduce the manufacturing cost while maintaining high adhesive strength at the time of lamination. have. It is preferable that the thickness of the electrode layer 12a is 1.5 micrometers or less, and it is preferable to form the electrode layer 12a so that the thickness of the sum total of the electrode layer 12a and the green sheet 10a may be 3.0 micrometers or less.

The electrode layer 12a can be formed on the surface of the green sheet 10a by, for example, a thick film forming method such as a printing method using an electrode paste, or a thin film method such as vapor deposition or sputtering. When the electrode layer 12a is formed on the surface of the green sheet 10a by the screen printing method or the gravure printing method, which is one of the thick film methods, it is performed as follows.

First, an electrode paste is prepared. The electrode paste is prepared by kneading an organic vehicle with a conductor material made of various conductive metals or alloys, or various oxides, organometallic compounds, resinates, etc., which become the conductor materials after firing.

Ni, a Ni alloy, and a mixture thereof are used as a conductor material used when manufacturing an electrode paste. There is no restriction | limiting in particular in the shape, such as a spherical shape and a flaky shape, such a conductor material may mix | blend these shapes. In addition, the average particle diameter of a conductor material is 0.1-2 micrometers normally, Preferably what is about 0.2-1 micrometer may be used.

The organic vehicle contains a binder and a solvent. Examples of the binder include ethyl cellulose, acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, copolymers thereof, and the like. Among them, ethyl cellulose, polyvinyl buty Butyral systems, such as Lal, are preferable.

The binder is preferably 4 to 10 parts by mass with respect to 100 parts by mass of the conductor material (metal powder) in the electrode paste. As a solvent, all well-known things, such as terpineol, butyl carbitol, a kerosene, acetone, isobornyl acetate, can be used, for example. Solvent content becomes like this. Preferably it is about 20-55 mass% with respect to the whole paste.

In order to improve the adhesion, the electrode paste preferably contains a plasticizer or an adhesive. As a plasticizer, the thing similar to a dielectric paste can be used, The addition amount of a plasticizer becomes like this. Preferably it is 10-300 mass parts, More preferably, it is 10-200 mass parts with respect to 100 mass parts of binders in an electrode paste. When the amount of the plasticizer or the pressure-sensitive adhesive added is too large, the strength of the electrode layer 12a tends to remarkably decrease. Moreover, it is preferable to add at least one of a plasticizer or an adhesive in an electrode paste, and to improve at least one of the adhesiveness or adhesiveness of an electrode paste.

After or before the electrode paste layer of a predetermined pattern is formed on the surface of the green sheet 10a by the printing method, the electrode layer 12a is substantially formed on the surface of the green sheet 10a on which the electrode layer 12a is not formed. By using the same thickness pattern layer 24 is formed. The margin pattern layer 24 is made of the same material as the green sheet 10a. In addition, what is necessary is just to make it the same method as the green sheet 10a or the electrode layer 12a as a formation method of the blank pattern layer 24. The electrode layer 12a and the margin pattern layer 24 are dried as necessary. Although drying temperature is not specifically limited, Preferably it is 70-120 degreeC, and drying time becomes like this. Preferably it is 5-15 minutes.

Apart from the carrier sheet 20, as shown in FIG. 3A, an adhesive layer transfer sheet having an adhesive layer 28 formed on the surface of the carrier sheet 26 as a second support sheet is prepared. The carrier sheet 26 is comprised from the same sheet as the carrier sheet 20. The thickness of the carrier sheet 26 may be the same thickness as the carrier sheet 20, and may be different thickness.

The adhesive layer 28 includes a binder and a plasticizer. The adhesive layer 28 may include the same dielectric particles as those of the dielectric constituting the green sheet 10a. However, when the adhesive layer having a thickness smaller than the particle diameter of the dielectric particles is formed, the adhesive particles 28 may not be included. In the case where the dielectric layer is included in the adhesive layer 28, the particle size of the dielectric particles is preferably smaller than the particle size of the dielectric particles included in the green sheet.

As the binder for the adhesive layer 28, for example, an organic or emulsion consisting of butyral resins such as acrylic resins, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefins, polyurethanes, polystyrenes or copolymers thereof It consists of. In this embodiment, it is especially preferable to use butyral resin, such as an acrylic resin or polyvinyl butyral, as said binder. In addition, although the binder contained in the adhesive layer 28 may be same or different from the binder contained in the green sheet 10a, the same thing is preferable.

Although it does not specifically limit as a plasticizer for the contact bonding layer 28, For example, phthalic acid esters, such as dioctyl phthalate and bis (2-ethylhexyl phthalate), adipic acid, phosphate ester, glycols, etc. are illustrated. The plasticizer contained in the adhesive layer 28 may be the same as or different from the plasticizer contained in the green sheet 10a.

It is preferable that a plasticizer is contained in 0-200 mass parts with respect to 100 mass parts of binders in the adhesive layer 28, Preferably it is 20-200 mass parts, More preferably, it is contained in 30-70 mass parts.

It is preferable that the adhesive layer 28 further contains a charging agent, and the charging agent contains one of the imidazoline-based surfactants, and the weight-based addition amount of the charging agent is equal to or less than the weight-based addition amount of the binder (organic polymer material). It is preferable. It is preferable that content of a charging agent is contained in 0-200 mass parts with respect to 100 mass parts of binders in the adhesive layer 28, Preferably it is 20-200 mass parts, More preferably, it is contained in 50-100 mass parts.

The thickness of the adhesive layer 28 is preferably 0.02 to 0.3 µm, more preferably 0.05 to 0.1 µm, and preferably thinner than the average particle diameter of the dielectric particles included in the green sheet. Moreover, it is preferable that the thickness of the contact bonding layer 28 is 1/5 or less of the thickness of the green sheet 10a.

If the thickness of the adhesive layer 28 is too thin, the adhesive strength is lowered. If the thickness of the adhesive layer 28 is too thick, a gap tends to occur in the interior of the element body after sintering, depending on the thickness of the adhesive layer, and the capacitance of the volume tends to be significantly lowered. have.

The adhesive layer 28 is formed on the surface of the carrier sheet 26 as the second supporting sheet by a method such as a bar coater method, a die coater method, a reverse coater method, a dip coater method, a key coater method, It is dried as needed. Although drying temperature is not specifically limited, Preferably it is room temperature to 80 degreeC, and drying time becomes like this. Preferably it is 1 to 5 minutes.

Subsequently, the adhesive layer 28 is formed on the surface of the electrode layer 12a and the blank pattern layer 24 formed on the green sheet 10a shown in FIG. 2B, and the laminated unit U1a shown in FIG. 3C is obtained. In this embodiment, the transfer method is adopted as a method of forming the adhesive layer 28. That is, as shown in FIGS. 3A and 3B, the adhesive sheet 28 of the carrier sheet 26 is pressed against the surface of the electrode layer 12a and the margin pattern layer 24 by heat and pressure, and then the carrier sheet 26 is peeled off. By doing so, as shown in Fig. 3C, the adhesive layer 28 is transferred to the surfaces of the electrode layer 12a and the margin pattern layer 24 to obtain the laminate unit U1a.

By forming the adhesive layer 28 by the transfer method, the penetration of the electrode layer 12a, the margin pattern layer 24, or the green sheet 10a of the component of the adhesive layer, that is, sheet attack can be effectively prevented. Therefore, there is no possibility of adversely affecting the composition of the electrode layer 12a, the margin pattern layer 24, or the green sheet 10a. In addition, even when the adhesive layer 28 is formed thin, since the components of the adhesive layer do not penetrate into the electrode layer 12a, the margin pattern layer 24 or the green sheet 10a, the adhesiveness can be maintained high.

40-100 degreeC is preferable and, as for the heating temperature at the time of transfer, 0.2-15 Mpa is preferable. Although pressurization by press and the pressurization by a calender roll may be sufficient, it is preferable to perform pressurization by a pair of rolls.

Subsequently, a green chip is formed by stacking a plurality of stacked units stacked in order of the green sheet 10a, the electrode layer 12a, the margin pattern layer 24, and the adhesive layer 28. Lamination | stacking of a laminated body unit is laminated | stacked by adhering each laminated body unit through the contact bonding layer 28 as shown to FIG. 4A, FIG. 4B and FIG. 5A, FIG. 5B.

Hereinafter, the lamination method will be described.

First, as shown in FIG. 4A, the 1st support sheet 20 is peeled from the laminated body unit U1a produced above, and the green sheet 30 for outer layers (10-30 micrometer thickness in which the electrode layer is not formed) is carried out. Layered green sheet is laminated on a multilayer body having a thickness of 100 to 200 탆). Next, the other laminated unit U1b produced by the method similar to laminated unit U1a is prepared. The 1st support sheet 20 is peeled from the prepared laminated unit U1b, and the laminated body U1b is made into the state in which the 1st support sheet 20 peeled. As shown in FIG. 4B, the laminate unit U1b and the laminate unit U1a from which the first support sheet 20 is peeled off are bonded together with the adhesive layer 28 of the laminate unit U1a interposed therebetween. By laminating.

Next, as shown to FIG. 5A and 5B, it adheres similarly on the laminated unit U1b with the separate laminated unit U1c, and the adhesive layer 28 of the laminated unit U1b. By laminating. And the laminated body unit of multiple layers is laminated | stacked by repeating the process shown to FIG. 5A and FIG. 5B. Subsequently, the green sheet 30 for outer layer is laminated | stacked on the upper surface of this laminated body, after final pressurization, a laminated body is cut | disconnected to predetermined size, and a green chip is formed. The pressure at the time of final pressurization becomes like this. Preferably it is 10-200 MPa, and heating temperature becomes like this. Preferably it is 40-100 degreeC.

The green chip is subjected to binder removal processing, firing treatment, and heat treatment to regenerate the dielectric layer.

Although the binder removal processing may be performed under normal conditions, in the case of using a non-metal such as Ni or a Ni alloy as the conductor material of the internal electrode layer, it is particularly preferable to carry out under the following conditions.

Temperature rise rate: 5 to 300 ° C / hour, especially 10 to 50 ° C / hour,

Holding temperature: 200-400 ° C., especially 250-350 ° C.,

Holding time: 0.5-20 hours, especially 1-10 hours,

Atmosphere: Mixed gas of humidified N ₂ and H ₂ .

The firing conditions are preferably the following conditions.

Temperature rising rate: 50 to 500 ° C / hour, especially 200 to 300 ° C / hour,

Holding temperature: 1100 to 1300 ° C, especially 1150 to 1250 ° C,

Holding time: 0.5 to 8 hours, especially 1 to 3 hours,

Cooling rate: 50-500 ° C./hour, especially 200-300 ° C./hour,

Atmosphere gas: A mixed gas of humidified N ₂ and H ₂ .

However, the oxygen partial pressure in an air atmosphere at firing is preferably carried out as a 10 ^-2 Pa or less, and particularly 10 ^-2 ~10 ^-8 Pa. If it exceeds the above range, the internal electrode layer tends to be oxidized, and if the oxygen partial pressure is too low, the electrode material of the internal electrode layer tends to abnormally sinter and break off in the middle.

The heat treatment after performing such firing is preferably performed at a holding temperature or a maximum temperature as 1000 ° C or higher, more preferably 1000 to 1100 ° C. If the holding temperature or maximum temperature during the heat treatment is less than the above range, the oxidation resistance of the dielectric material is insufficient, so that the insulating resistance life tends to be shortened. If the above range is exceeded, the Ni of the internal electrode is oxidized and the capacity is lowered. Reaction with the substrate tends to shorten its lifetime. The oxygen partial pressure at the time of heat treatment is an oxygen partial pressure higher than the reducing atmosphere at the time of baking, Preferably it is ^10-3 Pa ^- 1Pa, More preferably, it is 10-2 Pa ^- 1Pa. If it is less than the above range, the dielectric layer 2 is difficult to reoxidize, and if it exceeds the above range, the internal electrode layer 12 tends to be oxidized.

And as for other heat processing conditions, the following conditions are preferable.

Holding time: 0-6 hours, especially 2-5 hours,

Cooling rate: 50-500 ° C./hour, especially 100-300 ° C./hour,

Atmospheric gas: humidified N ₂ gas.

To wet the N ₂ gas and mixed gas, such as, for example, by passing the gas to the heating water is using a device such as bubbling. In this case, about 0-75 degreeC of water temperature is preferable. In addition, a binder removal process, baking, and heat processing may be performed continuously, respectively, and may be performed independently. In the case of performing these continuously, the atmosphere is changed without cooling after the debinding treatment, the temperature is subsequently raised to the holding temperature at the time of firing, the baking is carried out, and the cooling is performed. It is preferable. On the other hand, when performing these independently, after the firing, the temperature was raised under a maintained temperature to the N ₂ gas or a wet N ₂ gas atmosphere at the time of binder removal, by re-changing the atmosphere is preferable to keep the temperature increase, and at the time of heat treatment after cooling to the holding temperature, it is desirable to change back to the N ₂ gas or a wet N ₂ gas atmosphere, to continue the cooling. At the time of heat treatment, the atmosphere may be changed after the temperature is raised to the holding temperature under an N ₂ gas atmosphere, or the entire process of the heat treatment may be a humidified N ₂ gas atmosphere.

The sintered compact (element body 4) thus obtained is subjected to cross-sectional polishing, for example, by barrel polishing, sandblasting, or the like, and the terminal electrode pastes are baked to form terminal electrodes 6 and 8. The firing conditions of the terminal electrode paste is, for example, it is preferable that the mixed gas of wet N ₂ and H _2, which at 600~800 ℃ about 10-1 minutes. Then, a pad layer is formed by plating or the like on the terminal electrodes 6 and 8 as necessary. The terminal electrode paste may be prepared in the same manner as the above electrode paste.

The multilayer ceramic capacitor of the present invention produced in this way is mounted on a printed board or the like by soldering or the like and used in various electronic devices.

In this embodiment, lamination | stacking is carried out without using an adhesive layer in the process where a non-adhesion defect (non lamination) does not become a problem relatively. In addition, in the process in which a non-bonding defect (non lamination) is easy to produce, it laminates | stacks with an adhesive layer interposed. That is, since the adhesive layer is not used when forming the electrode layer 12a on the green sheet 10a, the manufacturing process can be simplified and the manufacturing cost can be reduced. In addition, when laminating | stacking the green sheet 10a in which the electrode layer 12a was formed, since the lamination | stacking is carried out with the contact bonding layer 28 interposed, adhesive improvement and non-adhesion defect (non lamination) can be aimed at. Therefore, according to the manufacturing method of this embodiment, even when the green sheet is made very thin, non-bonding defects (non-lamination) can be reduced while maintaining high adhesiveness, and the manufacturing process can be simplified and the manufacturing cost can be reduced. This becomes possible.

This invention is not limited to embodiment mentioned above, It can variously change within the scope of this invention.

For example, the method of the present invention can be applied not only to the manufacturing method of the multilayer ceramic capacitor but also to the manufacturing method of other laminated electronic components.

In addition, in the above-mentioned embodiment, although the adhesive layer 28 was formed by the transfer method, the adhesive layer 28 was formed by apply | coating directly on the electrode layer 12a and the margin pattern layer 24 by the die coater method etc., for example. You may also

In addition, in the above-mentioned embodiment, although the 1st support sheet 20 was peeled and laminated | stacked the laminated body unit from each laminated body unit before laminating each laminated body unit, For example, FIGS. 6A-6C, FIG. As shown to FIG. 7C, the process of peeling the 1st support sheet 20 after laminating | stacking a laminated body unit may be employ | adopted.

That is, as shown to FIG. 6A, 6B, the laminated unit U1a which did not peel off the 1st support sheet 20 on the green sheet 30 for outer layers first through the adhesive layer 28 is interposed. Adhesion and lamination. Next, as shown to FIG. 6C, the 1st support sheet 20 is peeled from laminated body U1a.

Subsequently, as shown in FIGS. 7A to 7C, in the same manner, a separate laminate unit U1b is bonded onto the laminate unit U1a with the adhesive layer 28 of the laminate unit U1b interposed therebetween. Laminated. Subsequently, a plurality of laminated unit is laminated by repeating the steps shown in FIGS. 7A to 7C. The green sheet for the outer layer is laminated on the upper surface of the laminate, and after the final pressing is performed, the laminate can be cut into a predetermined size to form a green chip.

1 is a schematic cross-sectional view of a multilayer ceramic capacitor according to one embodiment of the present invention.

2A is a sectional view showing the principal parts of the method for forming an electrode layer according to one embodiment of the present invention.

FIG. 2B is a sectional view showing the principal parts of the process following FIG. 2A. FIG.

3A is a sectional view showing the principal parts of the method for forming an adhesive layer according to the embodiment of the present invention.

3B is a sectional view showing the principal parts of the process following FIG. 3A.

FIG. 3C is a sectional view showing the principal parts of the process following FIG. 3B. FIG.

4A is a sectional view showing the principal parts of the method for laminating the green sheet with an electrode layer according to the embodiment of the present invention.

4B is a sectional view showing the principal parts of the process following FIG. 4A.

FIG. 5A is a sectional view showing the principal parts of the process following FIG. 4B. FIG.

FIG. 5B is a sectional view showing the principal parts of the process following FIG. 5A. FIG.

6A is a sectional view showing the principal parts of the method for laminating the green sheet with an electrode layer according to another embodiment of the present invention.

FIG. 6B is a sectional view showing the principal parts of the process following FIG. 6A. FIG.

FIG. 6C is a sectional view showing the principal parts of the process following FIG. 6B. FIG.

FIG. 7A is a sectional view showing the principal parts of the process following FIG. 6C. FIG.

FIG. 7B is a sectional view showing the principal parts of the process following FIG. 7A. FIG.

FIG. 7C is a sectional view showing the principal parts of the process following FIG. 7B. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated based on further detailed Example, this invention is not limited to these Examples.

Example  One

First, the following pastes were prepared.

Green Sheet Paste

First, as an additive (subcomponent) raw material, (Ba, Ca) SiO ₃ : 1.48 parts by weight, Y ₂ O ₃ : 1.01 parts by weight, MgCO ₃ : 0.72 parts by weight, MnO: 0.13 parts by weight, and V ₂ O ₅ : 0.045 weight I prepared for wealth. Next, these prepared additive (subcomponent) raw materials were mixed to obtain an additive (subcomponent) raw material mixture.

Subsequently, the additive raw material mixture obtained above was 4.3 parts by weight, ethanol: 3.11 parts by weight, propanol: 3.11 parts by weight, xylene: 1.11 parts by weight, and a dispersant: 0.04 parts by weight by mixing and grinding using a ball mill to obtain an additive slurry. The mixed grinding | pulverization was performed using the 250cc polyethylene resin container, 450g of ₂ mm diameter ZrO2 media, and it carried out on 45 m / min of circumferential speeds, and 16 hours. The median diameter of the additive raw material after grinding | pulverization was 0.1 micrometer.

Subsequently, the additive slurry obtained above was 11.65 parts by weight, BaTiO ₃ powder (BT-02 / Sakai Chemical Co., Ltd.): 100 parts by weight, ethanol: 35.32 parts by weight, propanol: 35.32 parts by weight, xylene: 16.32 parts by weight , Dioctyl phthalate (plasticizer): 2.61 parts by weight, mineral spirits: 7.3 parts by weight, dispersant: 2.36 parts by weight, charging aid: 0.42 parts by weight, organic vehicle: 33.74 parts by weight, MEK: 43.81 parts by weight and 2-butoxyethanol : 43.81 parts by weight was mixed using a ball mill to obtain a green sheet paste. Mixing by a ball mill was carried out under the conditions of a circumferential speed of 45 m / min and 20 hours by using a 500 cc polyethylene resin container and putting 900 g of ₂ mm phi ZrO ₂ media. In addition, said organic vehicle is 15 weight part of polyvinyl butyral resin (made by Sekisui Chemical Co., Ltd.) of polymerization degree 1450 and 69% butyralization degree, ethanol: 42.5 weight part, and propanol: 42.5 weight part, It produced by stirring and stirring at the temperature of 50 degreeC. That is, the resin content (amount of polyvinyl butyral resin) in the organic vehicle was 15% by weight.

Paste for Internal Electrode

First, the additive raw material mixture was produced in the same manner as the green sheet paste.

Subsequently, 100 parts by weight of the additive raw material mixture obtained above, 150 parts by weight of acetone, 104.3 parts by weight of tapineol, and 1.5 parts by weight of polyethylene glycol dispersant were mixed and slurried, and the resulting slurry was pulverized. It grind | pulverized with Finetec Co., Ltd. model LMZ0.6), and obtained the additive slurry.

Grinding of the additive in the slurry was performed by rotating the rotor under conditions of a circumferential speed of 14 m / min to circulate the slurry between the vessel and the slurry tank. The vessel was filled with ZrO ₂ beads having a diameter of 0.1 mm so as to be 80% with respect to the vessel capacity, and the grinding was carried out so that the residence time of the entire slurry in the vessel was 5 minutes. The median diameter of the additives after grinding was 0.1 µm.

Subsequently, the additive slurry after grinding was removed by evaporation of acetone in the slurry using an evaporator to prepare an additive slurry in which the additive raw material was dispersed in tapineol. The additive raw material concentration in the additive slurry after removing acetone was 49.3 wt%.

Subsequently, a nickel powder (particle size 0.2㎛ / Kawagoe tejjeu Industry Co., Ltd.): 100 parts by weight, additive slurry: 1.77 parts by weight, BaTiO ₃ powder (particle diameter 0.05㎛ / Sakai Chemical Industry Co., Ltd.): 19.14 parts by weight of an organic Vehicle: 56.25 parts by weight, polyethylene glycol dispersant: 1.19 parts by weight, dioctyl phthalate (plasticizer): 2.25 parts by weight, isobornyl acetate: 32.19 parts by weight, and acetone: 56 parts by weight were mixed and pasted using a ball mill. Subsequently, the obtained paste was removed by evaporating acetone using the stirring apparatus provided with the evaporator and the heating mechanism, and the paste for internal electrodes was obtained.

Mixing by a ball mill was performed by filling 30 volume% of ZrO2 media of ₂ mm diameter and 60 volume% of the mixtures of each said raw material in the ball mill on 45 m / min of circumferential speeds, and 16 hours. The organic vehicle was produced by stirring and dissolving 4 parts by weight of an ethyl cellulose resin: 40,000 parts by weight of molecular weight 130,000 and 4 parts by weight of an ethyl cellulose resin of 230,000 parts of molecular weight: 92 parts by weight of isobornyl acetate at a temperature of 70 ° C. That is, the resin content (amount of ethyl cellulose resin) in the organic vehicle was 8% by weight.

Then, the viscosity of the electrode paste thus obtained, a cone disc viscometer using (HAAKE Co., Ltd.), 25 ℃, 8sec ^-1 shear rate viscosity of the viscosity V ₅₀ V _8, and 50sec ^-1 in each Measured. As a result of the measurement, it was confirmed that V _{8 was} 15.5 cps, V ₅₀ = 8.5 cps, and V ₈ / V ₅₀ = 1.72, and the viscosity was good for the printing method.

Margin Pattern Paste

First, the additive slurry in which the additive raw material was disperse | distributed to tapineol was prepared like the paste for internal electrodes.

Subsequently, the additive slurry: 8.87 parts by weight, BaTiO ₃ powder (BT-02 / Sakai Chemical Co., Ltd.): 95.70 parts by weight, organic vehicle: 104.36 parts by weight, polyethylene glycol dispersant: 1.0 part by weight, dioctyl phthalate (plasticizer ): 2.61 parts by weight, isobonyl acetate: 19.60 parts by weight, acetone: 57.20 parts by weight, and imidazoline-based surfactant (charge aid): 0.4 parts by weight was mixed and pasted using a ball mill. Subsequently, the obtained paste was removed by evaporating acetone using the stirring apparatus provided with the evaporator and the heating mechanism, and the blank pattern paste was obtained. As the organic vehicle, the same organic vehicle as the internal electrode paste was used. That is, it was set as the 8 weight% isobornyl acetate solution of ethyl cellulose resin.

Next, the viscosity of the obtained blank pattern paste was measured similarly to the paste for internal electrodes. As a result of the measurement, it was confirmed that V ₈ = 19.9 cps, V ₅₀ = 10.6 cps, V ₈ / V ₅₀ = 1.88, and the viscosity can be satisfactorily used for the printing method.

For adhesive layer  Paste

Butyral resin (polymerization degree 800, butyralization degree 83%, Sekisui Chemical Co., Ltd. BM-SH): 1.5 parts by weight, MEK: 98.5 parts by weight and DOP (dioctyl phthalate and bis phthalate (2-ethylhexyl) Mixed solvent): The adhesive layer paste was produced by stirring and dissolving 50 weight part.

Green sheet, interior Electrode layer  And formation of margin patterns

First, the said green sheet paste was apply | coated with the die coater on the PET film (1st support sheet) which performed the peeling process with the silicone resin on the surface, and then green sheet was formed by drying. The coating speed was 50 m / min., And the drying made the temperature in a drying furnace 80 degreeC. The green sheet was formed so that the film thickness at the time of drying might be 1 micrometer.

Subsequently, the internal electrode paste was printed on a green sheet by a screen printing machine, and then dried under the condition of 90 ° C. and 5 minutes, thereby forming an internal electrode layer having a predetermined pattern. The internal electrode layer was formed so that the film thickness at the time of drying might be 1 micrometer.

Next, the said margin pattern paste was printed by the screen printing machine in the part in which the internal electrode layer of the green sheet in which the internal electrode layer was formed was not formed, and it dried under the conditions of 90 degreeC and 5 minutes, and formed the margin pattern. For printing the blank pattern, a screen plate forming a pattern complementary to the pattern used when printing the internal electrode paste was used. The blank pattern was formed so that the film thickness at the time of drying might be the same thickness as an internal electrode layer.

Formation of the adhesive layer, transfer of the adhesive layer

First, the said adhesive layer paste was apply | coated with the die coater on another PET film (2nd support sheet), and then the adhesive layer was formed by drying. The application rate was 70 m / min., And the drying temperature was 80 degreeC in the drying furnace. The adhesive layer was formed so that the film thickness at the time of drying might be 0.1 micrometer. As a PET film used as a 2nd support sheet, the PET film which performed the peeling process with silicone resin on the surface like the 1st support sheet was used.

Next, on the green sheet 10a on which the electrode layer 12a and the margin pattern 24 were formed, the adhesive layer 28 was transferred by the method shown in FIGS. 3A to 3C to stack the laminate unit U1a. Formed. At the time of transfer, a pair of rolls were used, the pressing force was 5 MPa and the temperature was 100 ° C, and it was confirmed that the transfer could be performed satisfactorily.

Green chip  making

First, a plurality of outer layer green sheets molded to a thickness of 10 mu m were laminated so that the thickness at the time of lamination was about 50 mu m, and after firing, an outer layer serving as a cover portion (cover layer) of the multilayer capacitor was formed. The green sheet for outer layer is a green sheet formed to have a thickness of 10 占 퐉 after drying, using the green sheet paint prepared above.

Next, 100 laminated body units were laminated | stacked on it by the method shown to FIG. 4A, FIG. 4B, FIG. 5A, and FIG. 5B. Subsequently, a plurality of outer layer green sheets molded to a thickness of 10 mu m were laminated thereon so that the thickness at the time of lamination was about 50 mu m, and after firing, an outer layer serving as a cover portion (cover layer) of the multilayer capacitor was formed. Subsequently, after pressing-molding the obtained laminated body on 100 MPa and 70 degreeC conditions, the green chip before baking was obtained by cutting | disconnecting with a dicing machine. In the present Example, the non-bonding defect (non-lamination) ratio was measured about the green chip before baking by the method demonstrated later.

Fabrication of Sintered Body

Subsequently, the final laminate was cut to a predetermined size, and subjected to binder removal, firing, and annealing (heat treatment) to prepare a chip-shaped sintered body.

The binder removes,

Temperature rise rate: 50 ℃ / hour,

Holding temperature: 240 ℃

Retention time: 8 hours

Atmosphere gas: in the air,

Done.

Firing

Temperature rising rate: 300 ℃ / hour,

Holding temperature: 1200 ℃

Retention time: 2 hours

Cooling rate: 300 ℃ / hour,

Atmosphere gas: mixed gas of N ₂ gas and H ₂ (5%) controlled at dew point 20 ° C.,

Done.

Annealing (reproduction),

Retention time: 3 hours

Cooling rate: 300 ℃ / hour,

Atmospheric gas: N ₂ gas controlled at dew point 20 ° C.,

Done. The humidification of the atmospheric gas was carried out at a water temperature of 0 to 75 ° C using a wet.

Subsequently, the cross section of the chip-like sintered body was polished by sandblasting, and then an In-Ga alloy paste was applied to the end portion and then fired to form an external electrode, thereby obtaining a sample of the multilayer ceramic capacitor having the configuration shown in FIG. 1.

Non-adhesive  flaw( Non Lamination Measurement of the ratio

About the sample of the green chip before baking obtained above, the generation | occurrence | production degree of a non-bonding defect (non lamination) was measured. In the measurement, 50 green chip samples were first embedded in a two-liquid curable epoxy resin so that the side surfaces of the dielectric layer and the inner electrode layer were exposed, and then the two-liquid curable epoxy resin was cured. Next, the green chip sample embedded in the epoxy resin was polished to a depth of 1.6 mm using sandpaper. Grinding by sandpaper was performed by using sandpaper of # 400, sandpaper of # 800, sandpaper of # 1000, and sandpaper of # 2000 in this order. Next, the polishing surface by sand paper was mirror-polished using the diamond paste. And the mirror surface polished polishing surface was observed by the magnification of 400 times using the optical microscope, and the presence or absence of a non-adhesive defect was investigated. As a result of observation by an optical microscope, the ratio of the sample which the non-adhesive defect generate | occur | produced with respect to the whole measurement sample was made into the non-adhesive defect ratio. The results are shown in Table 1.

Measurement of short defective rate

The short defective rate prepared 50 capacitor samples, and measured and measured the number which the short defect generate | occur | produced.

Specifically, the resistance value is measured using an insulation ohmmeter (E2377A multimeter manufactured by HEWLETT PACKARD), the sample having the resistance value of 100 kΩ or less is used as the short defective sample, and the ratio of the short defective sample to the total measurement sample is the short defective rate. I did it. The results are shown in Table 1.

Example  2

A sample of the green chip and the multilayer ceramic capacitor before firing was prepared in the same manner as in Example 1, except that the adhesive layer was formed by a coating method instead of a transfer method. The short defective rate was measured.

That is, in Example 2, the adhesive layer was formed by directly apply | coating the adhesive layer paste to the electrode layer side surface of the green sheet 10a in which the electrode layer 12a and the margin pattern 24 were formed using the die coater.

Comparative example  One

Except not forming an adhesive layer, the sample of the green chip and laminated ceramic capacitor before baking was produced like Example 1, and it carried out similarly to Example 1, and measured the non-bonding defect ratio and the short defective rate.

That is, in the comparative example 1, the laminated body unit was laminated | stacked without interposing an adhesive layer.

Formation method of adhesive layer % Of non-bonded defects Short defective rate (%) Example 1 Transcription 0 5 Example 2 Application method 0 18 Comparative Example 1 Not forming 100 Not measurable

Rating 1

In Table 1, the non-bonding defect ratio and the short defective rate of Example 1, 2, and Comparative Example 1 are shown, respectively.

In Table 1, Example 1 and Example 2 which formed the adhesive layer on the green sheet in which the electrode layer was formed, laminated | stacked each laminated unit with the adhesive layer interposed, all the non-bonding defect ratios are 0%, and also the short The defective rate was 5% and 18%, respectively, and the result was good. In Example 1, the short defective rate was 5%, which resulted in better results than in Example 2. However, in Example 1, this effectively prevents the penetration of the components of the adhesive layer into the electrode layer or the green sheet (sheet attack) in forming the adhesive layer. It seems to be due to what was prevented.

On the other hand, the comparative example 1 which laminated | stacked the laminated body unit without forming an adhesive layer had a non-bonding defect ratio 100%, ie, sufficient adhesive force was not obtained at the time of lamination, and the result which a non-sticking defect generate | occur | produced in all the samples. In Comparative Example 1, since the non-stick defects occurred in all the samples, the short defective rate could not be measured.

As a result, by forming an adhesive layer on the green sheet on which the electrode layer was formed, laminating the green sheet on which the electrode layer was formed, and improving the stackability (adhesiveness at the time of lamination), non-bonding defects and poor adhesion It was confirmed that it was possible to prevent the damage and reduce the short failure rate. Moreover, it was confirmed that the short defect rate can be further reduced by forming the adhesive layer by the transfer method.

Example  3

As a binder for the green sheet, except that an acrylic resin was used instead of the polyvinyl butyral resin, a sample of the green chip and the multilayer ceramic capacitor before firing was prepared in the same manner as in Example 1, and the same procedure as in Example 1 was performed, without adhesive. The defect ratio and the short defective rate were measured.

That is, in Example 3, as a green sheet paste, the green sheet paste of acrylic resin manufactured by the following method was used.

Green Sheet Paste of Acrylic Resin

First, the additive raw material mixture was produced in the same manner as the green sheet paste of Example 1.

Subsequently, 4.3 weight part of additive raw material mixtures obtained above, 6.85 weight part of ethyl acetate, and 0.04 weight part of a dispersing agent were mixed and grind | pulverized using the ball mill, and the additive slurry was obtained. The mixed grinding | pulverization was performed using the 250cc polyethylene resin container, 450g of ₂ mm diameter ZrO2 media, and it carried out on 45 m / min of circumferential speeds, and 16 hours. The median diameter of the additive raw material after grinding | pulverization was 0.1 micrometer.

Subsequently, the additive slurry obtained above was 11.2 parts by weight, BaTiO ₃ powder (BT-02 / Sakai Chemical Co., Ltd.): 100 parts by weight, ethyl acetate: 163.76 parts by weight, toluene: 21.48 parts by weight, dispersant: 1.04 parts by weight. , PEG400 (charge aid): 0.83 parts by weight, diacetone alcohol: 1.04 parts by weight, benzyl butyl phthalate (plasticizer): 2.61 parts by weight, butyl stearate: 0.52 parts by weight, mineral spirit: 6.78 parts by weight and organic vehicle: 34.77 weight The part was mixed using a ball mill to obtain a green sheet paste. Mixing by a ball mill was carried out under the conditions of a circumferential speed of 45 m / min and 20 hours by using a 500 cc polyethylene resin container and putting 900 g of ₂ mm phi ZrO ₂ media. The organic vehicle was produced by stirring and dissolving 15 parts by weight of acrylic resin in 85 parts by weight of ethyl acetate at 50 ° C. That is, the resin content (amount of acrylic resin) in the organic vehicle was 15% by weight. As acrylic resin, the copolymer (MMA / BA = 82/18: weight ratio) of the molecular weight 450,000, acid value 5 mgKOH / g, and methyl methacrylate (MMA) of Tg = 70 degreeC and butyl acrylate (BA) was used.

Evaluation 2

Example 3 which used acrylic resin instead of polyvinyl butyral resin as a binder for green sheets had the low non-bonding defect ratio and the short defect rate similarly to Example 1, and brought a favorable result. That is, in Example 3, the non-adhesive defect ratio was 0% and the short defective rate was 6%. From this result, even when acrylic resin was used as a binder for green sheets, it was confirmed that the effect of the present invention is sufficiently exhibited.

According to the present invention, since the adhesive layer is formed on the electrode layer side surface of the green sheet on which the electrode layer is formed, and the green sheet on which the electrode layer is formed is laminated with the adhesive layer therebetween, even when the green sheet is made very thin, stackability (lamination) Adhesiveness at the time), a short failure rate can be reduced, and a low-cost manufacturing method of a multilayer electronic component such as a multilayer ceramic capacitor can be provided.

Claims (15)

Forming a green sheet, Forming an electrode layer on a surface of the green sheet; Stacking the green sheets on which the electrode layers are formed to form green chips; A method of manufacturing a laminated electronic component having a process of firing the green chip, Before laminating the green sheet on which the electrode layer is formed, an adhesive layer is formed on the electrode layer side surface of the green sheet on which the electrode layer is formed, Laminating the green sheet on which the electrode layer is formed with the adhesive layer interposed therebetween, The green sheet is formed on the surface of the first support sheet to be peeled, manufacturing method of the laminated electronic component. The method of claim 1, wherein the electrode layer is directly formed on a surface of the green sheet. The manufacturing method of the laminated electronic component of Claim 1 or 2 whose thickness of the said contact bonding layer is 0.02-0.3 micrometer. delete The manufacturing method of the laminated electronic component of Claim 1 or 2 whose thickness of the said green sheet is 1.5 micrometers or less. The manufacturing method of the laminated electronic component of Claim 1 or 2 whose thickness of the said electrode layer is 1.5 micrometers or less. The manufacturing method of the laminated electronic component of Claim 1 or 2 whose thickness of the sum total of the said green sheet and the said electrode layer is 3.0 micrometers or less. The method according to claim 1 or 2, wherein the electrode layer is formed in a predetermined pattern on the surface of the green sheet, a blank pattern layer of the same thickness as the electrode layer is formed on the surface of the green sheet is not formed, the margin pattern A layer is made of the same material as that of the green sheet. The method according to claim 1 or 2, before laminating the green sheet on which the electrode layer is formed, the first support sheet is peeled from the green sheet on which the electrode layer is formed, The semi-electrode layer side surface of the green sheet on which the electrode layer is formed is laminated on another green sheet while the first supporting sheet is peeled off. The electrode layer side surface of the green sheet in which the said electrode layer was formed is laminated | stacked on the other green sheet in Claim 1 or 2 with the said 1st support sheet, After laminating the green sheet on which the electrode layer is formed, the first supporting sheet is peeled from the green sheet on which the electrode layer is formed. delete The method of manufacturing a laminated electronic component according to claim 1 or 2, wherein the adhesive layer is initially formed on the surface of the second support sheet so as to be peeled off, and is pressed onto the electrode layer side surface of the green sheet on which the electrode layer is formed. The manufacturing method of the laminated electronic component of Claim 1 or 2 formed by apply | coating the said adhesive layer directly to the electrode layer side surface of the said green sheet. The manufacturing method of the laminated electronic component of Claim 13 in which the said contact bonding layer is formed by apply | coating directly to the electrode layer side surface of the green sheet in which the said electrode layer was formed by the die-coating method. The dielectric layer of claim 1 or 2, wherein the adhesive layer comprises dielectric particles, wherein the dielectric particles have an average particle diameter equal to or smaller than the average particle diameter of the dielectric particles included in the green sheet, and the dielectric composition included in the green sheet. A method for manufacturing a laminated electronic component having the same kind of dielectric composition.

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