KR20070022817A - Method for manufacturing multilayer electronic component - Google Patents

Abstract

The present invention provides a process of forming the electrode layer 12a on the first support sheet 20, and a green sheet 10a formed on the surface of the electrode layer 12a, and having the electrode layer 12a. The manufacturing method of the laminated electronic component which has the process of obtaining a process, the process of laminating | stacking the green sheet 10a which has the said electrode layer 12a, forming a green chip, and baking the said green chip, The said electrode layer 12a Before laminating the green sheet 10a having the C), an adhesive layer 28 is formed on the surface of the half electrode layer side of the green sheet 10a having the electrode layer 12a, and the adhesive layer 28 is sandwiched. The manufacturing method of the laminated electronic component characterized by laminating | stacking the green sheet (10a) which has an electrode layer (12a).

Description

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

This invention relates to the manufacturing method of laminated electronic components, such as a multilayer ceramic capacitor, for example, More specifically, even when the green sheet is made very thin, stackability (adhesiveness at the time of lamination) is high, and a coating material Manufacture of multilayered electronic parts that can effectively prevent sheet-attack caused by solvents in the solvent, reduce non-stick defects (non-lamination) and short defect rate, and are inexpensive It is about a method.

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, which is also required to be downsized and high in performance.

In order to advance the miniaturization and high capacity of this multilayer ceramic capacitor, the thickness of the dielectric layer is strongly demanded. 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 a dielectric green sheet, normally, the green sheet coating material which consists of a dielectric powder, a binder, a plasticizer, and an organic solvent (toluene, alcohol, MEK, etc.) is prepared first. Next, this green sheet coating material is apply | coated on carrier films, such as PET, by a doctor blade method, etc., and is manufactured by heating and drying.

Moreover, in recent years, the preparation of the ceramic suspension mixed with the dielectric powder and the binder in the solvent, and the biaxial stretching of the film-form molded object obtained by extrusion molding this suspension is also examined.

The method of manufacturing a multilayer ceramic capacitor using the above-described ceramic green sheet will be described in detail. On the dielectric green sheet, an internal electrode paste containing a metal powder and a binder is printed in a predetermined pattern, dried, and then internal electrode pattern. To form. Next, the carrier sheet is peeled from the ceramic green sheet, and a plurality of them are laminated and cut into chips to form a green chip. Next, after firing this green chip, an external electrode is formed and manufactured.

By the way, when the internal electrode paste is directly printed on the green sheet, the solvent in the internal electrode paste penetrates into the green sheet, causing a phenomenon called so-called sheet attack. The sheet attack caused by the permeation of this solvent causes pinholes in the green sheet and often causes short defects. In particular, when the dielectric green sheet is formed very thin, the influence of the sheet attack becomes remarkable, and thus, the thickness of the interlayer thickness of the sheet is difficult.

On the other hand, in following patent documents 1-4, after forming an internal electrode pattern in a support sheet, it dries and prepares a dry type electrode pattern separately. Then, an internal electrode pattern transfer method is proposed which transfers this dry type electrode pattern to the surface of each dielectric green sheet or the surface of the laminated body of the dielectric green sheet.

By the way, in the technique shown by these patent documents 1-4, especially when the thickness of a green sheet is thin, it is very difficult to adhere | attach an electrode pattern layer well to the surface of a green sheet, and to transfer with high precision, and also a transfer process In this case, there is a problem that the dielectric green sheet is partially broken and a short defect occurs. In addition, as in the above Patent Documents 1 to 4, when the green sheet on which the electrode pattern layer is formed is directly laminated, the adhesive force between the internal electrode formation surface and the green sheet surface becomes insufficient, resulting in poor adhesion. There is a problem.

In order to solve the problem of adhesion failure or short defect, for example, in Patent Documents 5 to 7, 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 form 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, since the green sheet layer needs to be about half of the desired thickness, that is, very thin, it is difficult to cope with further thinning of the green sheet.

Moreover, in patent documents 8-13, the method of laminating | stacking using the green sheet formed by superimposing 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 or interlayer separation can be suppressed. However, in the method described in these documents, in order to thin the green sheet itself, it is necessary to thin each green sheet layer further, so that it was difficult to cope with further thinning of the green sheet.

In particular, these documents use green sheets formed 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 or three layers of Patent Documents 9 and 10 in Patent Literatures 7, 8. A green sheet layer of about 3.4 μm and a green sheet layer of about 0.6 to 1 μm are formed by overlapping. For this reason, in these documents, it is difficult to respond to thinning.

Patent Document 1: Japanese Patent Application Laid-Open No. 63-51616

Patent Document 2: Japanese Patent Application Laid-Open No. 3-250612

Patent Document 3: Japanese Patent Application Laid-Open No. 5-159966

Patent Document 4: Japanese Patent Application Laid-Open No. 7-312326

Patent Document 5: Japanese Patent Application Laid-Open No. 7-297073

Patent Document 6: Japanese Patent Application Laid-Open No. 2004-103983

Patent Document 7: Japanese Patent Application Laid-Open No. 2004-119802

Patent Document 8: Japanese Patent Application Laid-Open No. 10-50552

Patent Document 9: Japanese Patent Application Laid-Open No. 11-144992

Patent Document 10: Japanese Patent Application Laid-Open No. 8-37128

Patent Document 11: Japanese Patent Application Laid-Open No. 5-101970

Patent Document 12: Japanese Patent Application Laid-Open No. 2003-264120

Patent Document 13: Japanese Patent Publication No. 2003-272947

Problems to be Solved by the Invention

The present invention is made in view of such a state, and even when the green sheet is made very thin, the stackability (adhesion at the time of lamination) is high, and sheet attack by the solvent contained in the paint is effectively prevented, and a non-bonding defect It is an object of the present invention to provide a method for producing a multilayered electronic component such as a multilayer ceramic capacitor, which can reduce (non-lamination) and short defective rate, and which is inexpensive.

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, the present inventor discovered that an adhesive layer is formed on the surface of the half electrode layer side of the green sheet which has an electrode layer, this adhesive layer is sandwiched, and the green sheet which has an electrode layer is laminated | stacked. It has been found that the object can be achieved, and have come to complete the present invention.

That is, the manufacturing method of the laminated electronic component of this invention is a process of forming an electrode layer on a 1st support sheet, the process of forming a green sheet on the surface of the said electrode layer, and obtaining a green sheet which has an electrode layer,

Stacking a green sheet having the electrode layer and forming a green chip;

As a manufacturing method of a laminated electronic component which has a process of baking the said green chip,

Before laminating the green sheet having the electrode layer, an adhesive layer is formed on the surface of the semi-electrode layer side (the surface opposite to the surface on which the electrode layer is formed) of the green sheet having the electrode layer,

The adhesive layer is sandwiched, and the green sheet having the electrode layer is laminated.

In the manufacturing method of this invention, an adhesive layer is formed in the surface of the semi-electrode layer side of the green sheet which has an electrode layer, the adhesive layer is sandwiched, and the green sheet which has an electrode layer is laminated | stacked, and a green chip is formed. By sandwiching and laminating the adhesive layer, the stackability (adhesiveness at the time of lamination) can be improved, and non-bonding defects (non-lamination) and poor adhesion can be prevented. Moreover, in this invention, the green sheet which has an electrode layer is manufactured by first forming an electrode layer on a 1st support sheet, and then forming a green sheet on the surface of this electrode layer. For this reason, when printing the internal electrode paste directly on a green sheet, the permeation (sheet attack) of the solvent in the green sheet which became a problem especially can be prevented effectively, and the short defective rate can be reduced. In addition, since permeation of the solvent can be prevented, there is no fear of adversely affecting the composition of the electrode layer or the green sheet.

Moreover, in this invention, since the adhesive layer is sandwiched and the green sheet which has an electrode layer is laminated | stacked, high pressure and heat are unnecessary at the time of lamination | stacking, 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 destroyed and can be laminated satisfactorily.

In the present invention, the green sheet can be formed on the surface of the electrode layer without using an adhesive layer. As the formation method of the said green sheet, thick film formation methods, such as the coating method using a dielectric paste, or thin film methods, such as vapor deposition and sputtering, etc. are mentioned, Especially die using a die coater is mentioned. It is preferable to form by a coating method. When the green sheet is formed on the surface of the electrode layer without using an adhesive layer, the manufacturing process can be simplified and the manufacturing cost can be reduced. In the present invention, even in such a case, lamination of the green sheet having the electrode layer is performed 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 contact bonding 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 an interlayer separation 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, a gap tends to occur in the interior of the element body after sintering depending on the thickness of the adhesive layer, which tends to be the origin of crack generation, or the capacitance of the volume tends to remarkably decrease. . 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 tends to significantly decrease. There is this.

Preferably, the thickness of the said green sheet is 1.5 micrometers or less, and the thickness of the said contact bonding layer is 1/10 or less of the thickness of the said green sheet. Further, preferably, the thickness of the electrode layer is 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 defective 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. This invention is especially effective when the thickness of the said green sheet and an electrode layer is made into the said range.

In addition, in this invention, the thickness of the said contact bonding layer, a green sheet, and an electrode layer means the thickness at the time of drying.

Preferably, the green sheet includes dielectric particles containing barium titanate as a main component, 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 includes, as a binder, an acrylic resin and / or a butyral resin. In the case of forming a thin green sheet, by using such a binder, a green sheet having sufficient strength can be formed even though it is thin.

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

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 contains a charging agent, the charging agent contains one of an imidazoline-based surfactant, and the weight-based addition amount of the charging agent is based on the amount of the organic polymer material. It is below a weight-based addition amount. By including this kind of charging agent in a predetermined amount, an antistatic effect 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 of the same kind as the dielectric composition included in the green sheet. A dielectric composition may be included. Since the adhesive layer becomes part of the element body after firing, it is preferable that dielectric particles of the same kind as the dielectric particles contained in the green sheet are included. In addition, since the thickness of an adhesive layer needs to be controlled, it is preferable that the average particle diameter of the dielectric particle is equal or small.

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 to maintain good adhesion of the adhesive layer.

Preferably, the electrode layer is formed on a surface of the first support sheet in a predetermined pattern, and a blank pattern layer having a thickness substantially the same as that of the electrode layer is formed on a surface of the first support sheet on which the electrode layer is not formed. The margin pattern layer is made of substantially the same material as the green sheet. That is, in the present invention, it is preferable that the electrode layer and the margin pattern layer are formed on the first support sheet in advance so that the electrode layer having a predetermined pattern and the margin pattern layer having a complementary pattern are formed on the surface of the green sheet. .

By forming a blank pattern layer in the part where an electrode layer is not formed, the level difference of the surface by the electrode layer of a predetermined pattern is eliminated. For this reason, even if it presses before baking after laminating | stacking a large number of green sheets, the outer surface of a laminated body is maintained in a plane, the electrode layer does not push in a planar direction, and the short circuit generate | occur | produces by the electrode layer penetrating a green sheet, It is also possible to prevent. In addition, in this invention, a blank pattern layer means the dielectric layer formed in the pattern complementary to an electrode layer.

Preferably, before laminating the green sheet having the electrode layer, the first supporting sheet is peeled from the green sheet having the electrode layer,

In the state which peeled the said 1st support sheet, the electrode layer side surface of the green sheet which has the said electrode layer is laminated | stacked on another green sheet.

Or in the state which has the said 1st support sheet, the semi-electrode layer side surface of the green sheet which has the said electrode layer is laminated | stacked on another green sheet,

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

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

When forming the said adhesive layer 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 and transferred to the surface of the semi-electrode layer side of the green sheet which has the said electrode layer. Do.

By forming the said contact bonding layer by a transfer method, permeation to the electrode layer and / or a green sheet of an adhesion layer component can be effectively prevented. For this reason, there is no possibility that it may adversely affect the composition of an electrode layer and / or a green sheet. In addition, even when the adhesive layer is formed thin, since the components of the adhesive layer do not penetrate the electrode layer and / or the green sheet, the adhesiveness can be maintained high.

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

It is preferable that the said adhesive layer is apply | coated and formed directly on the surface of the half electrode layer side of the green sheet which has the said electrode layer by the die-coating method.

By forming the adhesive layer by a die coating method using a die coater, the amount of PET film used can be reduced and the time required for forming the adhesive layer can be shortened as compared with the case of forming the adhesive layer by a transfer method. Therefore, the lead time and the tact of the process can be improved.

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.

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

2A is an essential part cross sectional view showing a method for forming an electrode layer according to an embodiment of the present invention.

FIG. 2B is an essential part cross-sectional view illustrating the continuous process of FIG. 2A.

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

3B is an essential part cross-sectional view illustrating the continuous process of FIG. 3A.

3C is an essential part cross-sectional view illustrating the continuous process of FIG. 3B.

4A is an essential part cross sectional view showing a laminating method for a green sheet having an electrode layer according to an embodiment of the present invention.

4B is an essential part cross-sectional view illustrating the continuous process of FIG. 4A.

FIG. 5A is an essential part cross sectional view of the continuous process of FIG. 4B. FIG.

FIG. 5B is an essential part cross sectional view of the continuous process of FIG. 5A. FIG.

It is a principal part sectional drawing which shows the lamination method of the green sheet which has an electrode layer which concerns on other embodiment of this invention.

FIG. 6B is an essential part cross sectional view of the continuous process of FIG. 6A. FIG.

6C is an essential part cross-sectional view illustrating the continuous process of FIG. 6B.

FIG. 7A is an essential part cross sectional view of the continuous process of FIG. 6C. FIG.

FIG. 7B is an essential part cross sectional view of the continuous process of FIG. 7A. FIG.

FIG. 7C is an essential part cross sectional view of the continuous process of FIG. 7B. FIG.

Best Mode for Carrying Out the Invention

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

First, the whole structure of a multilayer ceramic capacitor is demonstrated as one Embodiment of the electronic component manufactured by the method which concerns on this invention.

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 has 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. The other internal 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 manufactured by forming the electrode layer 12a in a predetermined pattern on the carrier sheet 20 as shown in Figs. 2A and 2B as described later in detail. do.

The material of the dielectric layer 10 is not specifically limited, For example, it is comprised from dielectric materials, such as calcium titanate, strontium titanate, and / 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. In particular, in the present embodiment, the thickness is preferably reduced to 3 µm or less, more preferably 1.5 µm or less.

Although the material of the terminal electrodes 6 and 8 is not specifically limited, Usually, although copper, a copper alloy, nickel, a nickel alloy, etc. are used, silver, silver, a palladium alloy, 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). -1.9 mm, Preferably it is about 0.3-1.6 mm).

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

First, in order to manufacture the electrode layer which comprises the internal electrode layer 12 shown in FIG. 1 after baking, 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, or the like, which become the above-described conductor materials after firing.

As a conductor material used when manufacturing an electrode paste, Ni, Ni alloy, and these mixtures are used. There is no restriction | limiting in particular in the shape, such as spherical shape and a flaky shape, such a conductor material may mix | blend these shapes. 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.

An 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, these copolymers, and the like. Among these, ethyl cellulose, Butyral systems, such as polyvinyl butyral, are preferable.

A binder becomes like this. Preferably, 4-10 mass parts is contained with respect to 100 mass parts of conductor materials (metal powder) in an electrode paste. As a solvent, any well-known thing, such as a terpineol, butyl carbitol, a kerosene, acetone, isobonyl 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 adhesiveness, the electrode paste preferably contains a plasticizer or an adhesive. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and benzyl butyl phthalate, adipic acid, phosphate esters and glycols. The amount of the plasticizer added is preferably 10 to 300 parts by mass, and more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the binder in the electrode paste. Moreover, when there is too much addition amount of a plasticizer or an adhesive, there exists a tendency for the intensity | strength of the electrode layer before baking to fall remarkably. Moreover, it is preferable to add a plasticizer and / or an adhesive in an electrode paste, and to improve adhesiveness and / or adhesiveness of an electrode paste.

And using this electrode paste, the electrode layer 12a is formed in the predetermined pattern on the surface of the carrier sheet 20 as a 1st support sheet. Examples of the method for forming the electrode layer 12a include a thick film forming method such as a printing method or a thin film method such as vapor deposition and sputtering. In the present embodiment, a screen printing method or a gravure printing method, which is a kind of a thick film method, is used. Thus, the electrode layer 12a is formed. It is preferable that the thickness of the electrode layer 12a shall be 1.5 micrometers or less.

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

As shown in FIG. 2A, after or before the electrode paste layer of a predetermined pattern is formed on the surface of the carrier sheet 20 by the printing method, the carrier sheet 20 in which the electrode layer 12a is not formed is formed. On the surface, a blank pattern layer 24 having a thickness substantially the same as that of the electrode layer 12a is formed. The margin pattern layer 24 is made of the same material as the green sheet 10a described later. In addition, the margin pattern layer 24 can be formed by the same method as the electrode layer 12a or the green sheet 10a mentioned later. 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 a drying time becomes like this. Preferably it is 5-15 minutes.

Next, as shown in FIG. 2B, the green sheet 10a is formed on the surfaces of the electrode layer 12a and the margin pattern layer 24 formed on the carrier sheet 20. The green sheet 10a forms the dielectric layer 10 shown in FIG. 1 after baking. In addition, in this embodiment, the green sheet 10a can be formed in the surface of the electrode layer 12a and the margin pattern layer 24, without using an adhesive layer. By forming the green sheet 10a on the electrode layer 12a and the margin pattern layer 24 without using an adhesive layer, the adhesive force at the time of lamination is kept high, and the manufacturing process is simplified and the manufacturing cost is reduced. Can be planned.

The green sheet 10a is formed on the surface of the electrode layer 12a and the margin pattern layer 24 by a die coating method or the like using a dielectric paste containing a dielectric material. The green sheet 10a is preferably formed to a thickness of about 0.5 to 30 µm, more preferably about 0.5 to 10 µm, and is formed on the electrode layer 12a and the margin pattern layer 24 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 shrinks to a thickness of 5 to 25% compared with before drying. The thickness of the green sheet after drying is preferably 1.5 µm or less, and the green sheet 10a is preferably formed such that the total thickness of the green sheet 10a and the electrode layer 12a becomes 3.0 µm or less. .

The dielectric paste for manufacturing the green sheet 10a is usually composed of an organic solvent paste or an aqueous paste obtained by kneading a dielectric material and an organic vehicle.

As the dielectric material, various compounds which are complex oxides or oxides, for example, carbonates, nitrates, hydroxides, organometallic compounds and the like can be appropriately selected and mixed. 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 addition, in order to form a very thin green sheet, it is preferable to use powder finer than the green sheet thickness.

The organic vehicle is obtained by dissolving a binder in an organic solvent. The binder used for the organic vehicle is not particularly limited, and various conventional binders such as ethyl cellulose, polyvinyl butyral and acrylic resin are used. Preferably, butyral series such as acrylic resin or polyvinyl butyral is used. Resin is used.

Moreover, the organic solvent used for an organic vehicle is not specifically limited, either terpineol, alcohol, butyl carbitol, acetone, methyl ethyl ketone (MEK), toluene, xylene, ethyl acetate, butyl stearate, isobornyl acetate, etc. 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, hydroxy ethyl cellulose, water-soluble acrylic resin, emulsion 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-type 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. When there are too few plasticizers, a green sheet will tend to weaken, and when too many, a plasticizer will leak and handling will be difficult.

Next, apart from the carrier sheet 20 described above, 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. In addition, the thickness of the carrier sheet 26 may be the same thickness as the carrier sheet 20, and may be another thickness.

The adhesive layer 28 contains a binder and a plasticizer. The adhesive layer 28 may contain 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 dielectric particles may not be included. In the case where the dielectric particles are included in the adhesive layer 28, the particle diameter of the dielectric particles is preferably smaller than the particle diameter of the dielectric particles contained in the green sheet.

As the binder for the adhesive layer 28, for example, butyral resin such as acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or an organic substance composed of these copolymers Or emulsions. 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 the same as 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, glycol, 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 the adhesive layer 28 with respect to 100 mass parts of binders at 0-200 mass parts, Preferably it is 20-200 mass parts, More preferably, it is 30-70 mass parts. It is preferable that the adhesive layer 28 also 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 based on the weight of the binder (organic polymer material). It is preferable that it is the addition amount or less. It is preferable that content of a charging agent is contained in the adhesive layer 28 with respect to 100 mass parts of binders, 0-200 mass parts, Preferably it is 20-200 mass parts, More preferably, it is contained in 50-100 mass parts.

Preferably the thickness of the contact bonding layer 28 is 0.02-0.3 micrometer, More preferably, it is 0.05-0.1 micrometer, and it is preferable that it is thinner than the average particle diameter of the dielectric particle contained in a green sheet. Moreover, it is preferable that the thickness of the contact bonding layer 28 is 1/10 or less of the thickness of the green sheet 10a.

If the thickness of the adhesive layer 28 is too thin, the adhesive force is lowered, and if it 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 volumetric capacitance tends to significantly decrease. There is this.

The adhesive layer 28 is formed on the surface of the carrier sheet 26 as the second support sheet by a method such as a bar coater method, a die coater method, a reverse coater method, a dip coater method, a kiss coater method, or the like. 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, an adhesive layer 28 is formed on the surface of the green sheet 10a formed on the electrode layer 12a and the blank pattern layer 24 shown in FIG. 2B, and the laminate unit U1a shown in FIG. 3C is formed. Get In this embodiment, a transfer method is employed as a method of forming the adhesive layer 28. That is, as shown to FIG. 3A and FIG. 3B, the adhesive layer 28 of the carrier sheet 26 is pressed to the surface of the green sheet 10a, it heat-presses, and peels off the carrier sheet 26 after that. As shown in FIG. 3C, the adhesive layer 28 is transferred onto the surface of the green sheet 10a to obtain a laminate unit U1a.

By forming the adhesive layer 28 by the transfer method, permeation to the green sheet 10a, the electrode layer 12a, or the margin pattern layer 24 of the component of the adhesive layer can be effectively prevented. For this reason, there is no possibility that it will adversely affect the composition of the green sheet 10a, the electrode layer 12a, or the margin pattern layer 24. FIG. Moreover, even when the adhesive layer 28 is formed thin, since the component of an adhesive layer does not penetrate into the green sheet 10a, the electrode layer 12a, or the margin pattern layer 24, adhesiveness can be maintained high.

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

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

Hereinafter, the lamination method will be described.

First, as shown to FIG. 4A, the 1st support sheet 20 is peeled off from the laminated body unit U1a produced above, and the green sheet 30 for outer layers (10-30 micrometers in which an electrode layer is not formed) is carried out. The green sheet of thickness is laminated | stacked on the laminated body of thickness 100-200 micrometers which laminated | stacked multilayer. Next, another laminated unit U1b produced by the same method as the laminated unit U1a is prepared. In the prepared laminated unit U1b, the 1st support sheet 20 is peeled off and the laminated unit U1b is made into the state in which the 1st support sheet 20 peeled. And as shown in FIG. 4B, the laminated body unit U1b and laminated body unit U1a which the 1st support sheet 20 peeled are sandwiched, and the adhesive layer 28 of the laminated body unit U1a is sandwiched, Adhesion and lamination.

Next, as shown in FIG. 5A and FIG. 5B, another laminate unit U1c is sandwiched and laminated on the laminate unit U1b by attaching the adhesive layer 28 of the laminate unit U1b. , Laminated. And a some laminated body unit 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, it presses finally, and a laminated body is cut | disconnected to a predetermined size after that, and a green chip is formed. In addition, 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 a binder removal treatment and a baking treatment, and heat treatment is performed because the dielectric layer is reoxidized.

Although the binder removal process 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, the following conditions are particularly preferable.

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

As for baking conditions, the following conditions are preferable.

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,

Atmospheric gas: wet N ₂ and H ₂ with a mixed gas.

However, it is preferable to carry out oxygen partial pressure in the air atmosphere at the time of baking at 10 <^-2> Pa or less, especially 10 <^{-2> -10 <-10>} Pa. When it exceeds the said range, there exists a tendency for an internal electrode layer to oxidize, and when oxygen partial pressure is too low, the electrode material of an internal electrode layer will abnormally sinter and will tend to be cut off in the middle.

The heat treatment after such sintering is preferably performed at a holding temperature or a maximum temperature at 1000 ° C or higher, more preferably at 1000 to 1100 ° C. If the holding temperature or the maximum temperature during the heat treatment is less than the above range, the dielectric resistance life will tend to be shortened because oxidation of the dielectric material is insufficient, and if the above range is exceeded, Ni of the internal electrode will oxidize and the capacity will decrease. Rather, it tends to react with the dielectric substrate and reduce its lifetime. The oxygen partial pressure at the time of heat processing 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. Below the above range, the reoxidation of the dielectric layer 2 is difficult, and when the above range is exceeded, the internal electrode layer 12 tends to oxidize.

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.

In addition, in order to wet the N ₂ gas and mixed gas, such as, for example, and passing the gas to the heated water, and the like using a bubbling apparatus. In this case, about 0-75 degreeC of water temperature is preferable.

In addition, you may perform a binder removal process, baking, and a heat processing in succession, respectively, or independently. In the case of carrying out these continuously, after debinding, the atmosphere is changed without cooling, the temperature is subsequently raised to the holding temperature at the time of baking, firing is performed, and then the cooling is performed to change the atmosphere when the holding temperature of the heat treatment is reached. It is preferable to perform heat treatment. On the other hand, when carried out by them independently, and after standing in the firing, the temperature was raised under a holding temperature N ₂ gas or a wet N ₂ gas atmosphere up to the time of binder removal, by changing the atmosphere is preferable to keep the temperature rise again, the column after cooling to the holding temperature at the time of the process, it is desirable to change back to N ₂ gas or a wet N ₂ gas atmosphere, to continue the cooling. Further, in the heat-treatment, N _2, and then also raised to the holding temperature under the gas atmosphere, changing the atmosphere, it may be a N ₂ gas atmosphere in a wet the entire process of the heat treatment.

The sintered compact (element body 4) thus obtained is subjected to cross-sectional polishing, for example, by barrel polishing, sand blasting, 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, is preferably about 10 minutes in a mixed gas of wet N ₂ and H ₂ to 600~800 ℃ ~1 hour. Then, as necessary, the pad layer is formed by plating or the like on the terminal electrodes 6 and 8. The terminal electrode paste may be prepared in the same manner as the above 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 is used in various electronic devices and the like.

In this embodiment, lamination | stacking is performed without using an adhesive layer in the process where a non-adhesion defect (non lamination) does not become a problem relatively. In addition, in a process in which non-bonding defects (non-lamination) are likely to occur, lamination is performed by sandwiching the adhesive layer. That is, since the adhesive layer is not used when the green sheet 10a is formed on the electrode layer 12a, the manufacturing process can be simplified and the manufacturing cost can be reduced. In addition, when laminating | stacking the green sheet 10a which has the electrode layer 12a, since the adhesive layer 28 is pinched | interposed, lamination | stacking can be improved and non-adhesion defect (non lamination) can be aimed at. For this reason, according to the manufacturing method of this embodiment, even when the green sheet is made very thin, non-adhesive defects (non-lamination) can be reduced, maintaining adhesiveness high, and also simplification and manufacture of a manufacturing process The cost can be reduced.

In the present embodiment, first, the electrode layer 12a and the margin pattern layer 24 are formed on the carrier sheet 20, and then the green sheet 10a is formed thereon, thereby forming the electrode layer 12a and the margin. The green sheet 10a having the pattern layer 24 is manufactured. For this reason, the permeation (sheet attack) of the solvent contained in a coating material can be prevented effectively, and the short defective rate can be reduced. In addition, since permeation of the solvent can be prevented, there is no fear of adversely affecting the composition of the electrode layer or the green sheet.

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

For example, the method of this invention is not limited to the manufacturing method of a multilayer ceramic capacitor, It is applicable also as a 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, you may form the adhesive layer 28 by apply | coating directly on the green sheet 10a by the die-coating method etc., for example. .

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

That is, as shown to FIG. 6A and FIG. 6B, on the green sheet 30 for outer layers, the adhesive layer 28 is pinched | interposed with the laminated body U1a which did not peel off the carrier sheet 20 first. It adhere | attaches, and laminates. Next, as shown to FIG. 6C, the carrier sheet 20 is peeled from the laminated body U1a.

Subsequently, as shown to FIG. 7A-7C, similarly, on the laminated unit U1a, the other laminated unit U1b is sandwiched and the adhesive layer 28 of the laminated unit U1b is sandwiched. It adhere | attaches, and laminates. Subsequently, a plurality of laminate units are laminated by repeating the steps shown in FIGS. 7A to 7C. And the green sheet for outer layers is laminated | stacked on the upper surface of this laminated body, it can press finally, and a laminated body can be cut | disconnected to a predetermined size after that, and a green chip can be formed.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated based on a more 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, 4.3 weight part of additive raw material mixtures obtained above, 3.11 weight part of ethanol, 3.11 weight part of propanol, 1.11 weight part of xylene, 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 250 cc polyethylene resin container, 450g of ₂ mm square ZrO2 media, and it carried out on 45 m / min of circumferential speeds, and 16 hours. Moreover, the median diameter of the particle size of the additive raw material after grinding | pulverization was 0.1 micrometer.

Subsequently, the additive slurry obtained above: 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 spirit: 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. In addition, mixing by a ball mill was carried out on the conditions of 45 m / min and 20 hours of circumferential speeds, using the 500-cc polyethylene resin container, injecting 900 g of ₂ mm square ZrO2 media. In addition, said organic vehicle is a polyvinyl butyral resin (made by Sekisui Chemical Co., Ltd.) of polymerization degree 1450 and 69% butyralization: 15 weight part, ethanol: 42.5 weight part, and propanol: 42.5 weight part It produced by stirring and melt | dissolving at the temperature of 50 degreeC. That is, resin content (amount of polyvinyl butyral resin) in an organic vehicle was 15 weight%.

Paste for Internal Electrode

First, the additive raw material mixture was produced similarly to the above-mentioned 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 tarpineol, and 1.5 parts by weight of polyethylene glycol dispersant were mixed and slurried, and the resulting slurry was pulverized. -It grind | pulverized by Finetec Co., Ltd. model LMZ0.6), and obtained the additive slurry.

In addition, the grinding | pulverization of the additive in a slurry was performed by rotating a rotor on the conditions of 14 m / min of circumferential speeds, and circulating a slurry between a coordinate value (bessel) and a slurry tank. The coordinate value was filled with ZrO ₂ beads having a diameter of 0.1 mm so as to be 80% with respect to the coordinate value capacity, and the grinding was performed so that the residence time in the coordinate value of the entire slurry was 5 minutes. In addition, the median diameter of the additive after grinding | pulverization was 0.1 micrometer.

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. In addition, the additive raw material concentration in the additive slurry after removing acetone was 49.3 weight%.

Subsequently, a nickel powder (particle size 0.2㎛ / Kawagoe Railway 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, polyethyleneglycol dispersant: 1.19 parts by weight, dioctyl phthalate (plasticizer): 2.25 parts by weight, isobonyl acetate: 32.19 parts by weight, and acetone: 56 parts by weight using a ball mill to mix and paste. 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.

In addition, mixing by the ball mill was performed by filling 30 volume% of ₂ mm-diameter ZrO2 media and 60 volume% of said mixtures of each 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 using a viscometer (HAAKE Corporation), 25 ℃, the shear rate viscosity 8sec ^-1 V ₅₀ according to the viscosity V _8, and 50sec ^-1 in each Measured. As a result of the measurement, it is confirmed that V ₈ = 15.5 cps, V ₅₀ = 8.5 cps, V ₈ / V ₅₀ = 1.72, and the viscosity can be favorably used 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-based 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 (preparative preparation): 0.4 part 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 blank pattern paste was obtained. As the organic vehicle, the same organic vehicle as the paste for internal electrodes was used. That is, it was set as the 8 weight% isobornyl acetate solution of ethyl cellulose resin.

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

For adhesive layer  Paste

Butyral resin (polymerization degree 800, 83% butyralization degree, 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 melt | dissolving 50 weight part.

inside Electrode layer , Margin patterns and green sheet formation

First, the said internal electrode paste was printed by the screen printing machine on the PET film (1st support sheet) which performed the peeling process on the surface by silicone resin. Next, the internal electrode layer having a predetermined pattern was formed by drying under the condition of 90 ° C. and 5 minutes. 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 on the part in which the internal electrode layer of PET film was not formed, and then it dried by the conditions of 90 degreeC and 5 minutes, and formed the margin pattern. For printing of 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.

Subsequently, on the internal electrode layer and the blank pattern formed above, the green sheet paste was applied by a die coater and then dried to form a green sheet. The application rate 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.

Formation of the adhesive layer, transfer of the adhesive layer

First, the adhesive layer was formed by apply | coating said adhesive layer paste with a die coater on another PET film (2nd support sheet), and then drying. The coating speed was 70 m / min., And the drying set the temperature in a drying furnace to 80 degreeC. The adhesive layer was formed so that the film thickness at the time of drying might be 0.1 micrometer. In addition, as a PET film used as a 2nd support sheet, the PET film which peeled and treated with the silicone resin on the surface was used similarly to a 1st support sheet.

Next, on the green sheet 10a which has the electrode layer 12a and the blank pattern 24 produced above, the adhesive layer 28 is transferred by the method shown to FIGS. 3A-3C, and a laminated unit ( U1a) was formed. At the time of transfer, a pair of rolls are used, the pressing force is 5 MPa, the temperature is 100 degreeC, and it can confirm that transfer can be performed favorably.

Fabrication of Green Chips

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. Lamination was carried out under the conditions of a press pressure of 200 MPa and a press temperature of 50 ° C. In addition, the green sheet for outer layers is the green sheet formed so that the thickness after drying may be 10 micrometers using the coating material for green sheets manufactured above.

Subsequently, 100 laminated units were laminated thereon by the method shown in FIG. 4A, 4B, 5A, and 5B. Subsequently, a plurality of outer layer green sheets molded to a thickness of 10 μm were laminated so that the thickness at the time of lamination was about 50 μm, and after firing, an outer layer serving as a cover part (cover layer) of the multilayer capacitor was formed. did. Subsequently, the obtained laminated body was press-molded on condition of 100 MPa and 70 degreeC, and after that, it cut | disconnected with the dicing machine and obtained the green chip before baking. In addition, 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 into a predetermined size, subjected to binder removal treatment, firing and annealing (heat treatment) to prepare a chip-shaped sintered body.

Debinding binder,

Temperature rise rate: 50 ℃ / hour,

Holding temperature: 240 ℃

Retention time: 8 hours

Atmosphere gas: performed in air.

Firing

Temperature rising rate: 300 ℃ / hour,

Holding temperature: 1200 ℃

Retention time: 2 hours

Cooling rate: 300 ℃ / hour,

Atmosphere gas: mixed gas was carried out as in the N ₂ gas and H ₂ (5%) controlled by a dew point 20 ℃.

Annealing (reproduction),

Retention time: 3 hours,

Cooling rate: 300 ℃ / hour,

Gas atmosphere: was performed in a N ₂ gas controlled to a dew point 20 ℃. In addition, humidification of atmospheric gas was performed at water temperature 0-75 degreeC using the wet.

Subsequently, after grind | polishing the cross section of a chip-shaped sintered compact with sand blast, the external electrode was formed by apply | coating an In-Ga alloy paste to the edge part, and the sample of the laminated ceramic capacitor of the structure shown in FIG. 1 was obtained.

Non-adhesive  Defect 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, and then the two-liquid curable epoxy resin was cured so that the side surfaces of the dielectric layer and the internal electrode layer were exposed. Next, the green chip sample embedded in the epoxy resin was polished to a depth of 1.6 mm using sand paper. In addition, grinding by sand paper was performed by using sand paper of # 400, sand paper of # 800, sand paper of # 1000, and sand paper of # 2000 in this order. Subsequently, mirror polishing was performed on the polishing surface by sand paper using the diamond paste. And using the optical microscope, the polished surface which performed the mirror-polishing process was observed at 400 magnification, 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 a non-sticking defect generate | occur | produced with respect to the whole measurement sample was made into the non-sticking defect ratio. The results are shown in Table 1.

short Defective  Measure

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), and the ratio of the short defective sample to the total measured samples is determined by using the sample having a resistance value of 100 m or less as the short defective sample. It was set as the short defective rate. The results are shown in Table 1.

Example  2

A sample of the green chip and the multilayer ceramic capacitor before firing was produced in the same manner as in Example 1, except that the formation of the adhesive layer was performed by the coating method, not by the transfer method, and in the same manner as in Example 1, the non-bonding defect ratio And the short defective rate were measured.

That is, in Example 2, the adhesive layer is applied by directly applying the adhesive layer paste onto the surface of the semi-electrode layer side of the green sheet 10a having the electrode layer 12a and the margin pattern 24 using a die coater. Formed.

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-adhesion 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.

TABLE 1

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 which has an electrode layer, sandwiched the adhesive layer, and laminated | stacked each laminated unit were 0% of non-bonding defect ratios, and the favorable result was obtained. It became. In addition, in Example 1, the short defective rate was 12%, which was better than that in Example 2, which, in Example 1, permeated the electrode layer or the green sheet of the component of the adhesive layer at the time of forming the adhesive layer (adhesive layer). Sheet attack) is considered to be effectively preventable.

On the other hand, in Comparative Example 1 in which a laminate unit was laminated without forming an adhesive layer, the non-adhesive defect ratio was 100%, that is, sufficient adhesive force could not be obtained at the time of lamination, resulting in non-stick defects occurring in all samples. It became. In addition, in Comparative Example 1, since non-stick defects occurred in all samples, the short defective rate could not be measured.

As a result, by forming an adhesive layer on the green sheet having the electrode layer, sandwiching the adhesive layer, and laminating the green sheet having the electrode layer, the stackability (adhesiveness at the time of lamination) is improved, and non-bonding defects and poor adhesion are prevented. It can confirm that it can prevent. In addition, it can be confirmed that the short defective rate can be further reduced by forming the adhesive layer by the transfer method.

Example  3

As a binder for the green sheet, a sample of the green chip and the multilayer ceramic capacitor before firing was produced by the same method as in Example 1, except that acrylic resin was used instead of the polyvinyl butyral resin. In the same manner, the non-bonding defect ratio and the short defective rate were measured.

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

Green Sheet Paste of Acrylic Resin

First, the additive raw material mixture was produced similarly to 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 square ZrO2 media, and it carried out on the conditions of 45 m / min and 16 hours of circumferential speeds. In addition, the median diameter of the particle size of the additive raw material after grinding | pulverization was 0.1 micrometer.

Subsequently, the additive slurry obtained above: 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 preparation): 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: 6.68 parts by weight and organic vehicle: 34.77 parts by weight It mixed using the ball mill and the paste for green sheets was obtained. In addition, mixing by a ball mill was carried out on the conditions of 45 m / min and 20 hours of circumferential speeds, inject | pouring 900 g of ₂ mm diameter ZrO2 media using the 500 cc polyethylene resin container. In addition, said organic vehicle was produced by stirring and melt | dissolving 15 weight part of acrylic resins at the temperature of 50 degreeC in 85 weight part of ethyl acetate. That is, the resin content (amount of acrylic resin) in the organic vehicle was 15% by weight. As the acrylic resin, a copolymer (MMA / BA = 82/18: weight ratio) of a molecular weight of 450,000, an acid value of 5 mgKOH / g, and a methyl methacrylate (MMA) having a Tg of 70 ° C (MMA) and butyl acrylate (BA) was used. did.

Evaluation 2

As a binder for green sheets, Example 3 using acrylic resin instead of polyvinyl butyral resin, as in Example 1, had a low non-bonding defect ratio and a short defective rate, resulting in good results. That is, in Example 3, the non-adhesive defect ratio was 0% and the short defective rate was 10%. From this result, even when acrylic resin is used as a binder for green sheets, it can confirm that the effect of this invention is fully exhibited.

According to the present invention, since the adhesive layer is formed on the surface of the semi-electrode layer side of the green sheet having the electrode layer, the adhesive layer is sandwiched, and the green sheet having the electrode layer is laminated, even when the green sheet is formed very thinly. The adhesiveness at the time of lamination | stacking is high, a non-bonding defect (non lamination) can be reduced, and the manufacturing method of laminated electronic components, such as a laminated ceramic capacitor with low cost, can be provided. Moreover, in this invention, since the green sheet which has an electrode layer is manufactured by forming an electrode layer on a 1st support sheet, and then forming a green sheet on the surface of this electrode layer, the solvent contained in a coating material into the green sheet Sink (sheet attack) can be effectively prevented, and the short defective rate can be reduced.

Claims (12)

Forming an electrode layer on the first support sheet; Forming a green sheet on the surface of the electrode layer to obtain a green sheet having an electrode layer; Laminating a green sheet having the electrode layer to form a green chip; As a manufacturing method of a laminated electronic component which has a process of baking the said green chip, Before laminating the green sheet having the electrode layer, an adhesive layer is formed on the surface of the half electrode layer side of the green sheet having the electrode layer, The manufacturing method of the laminated electronic component characterized by sandwiching the said adhesive layer and laminating | stacking the green sheet which has the said electrode layers. The method of claim 1, wherein the green sheet is formed on the surface of the electrode layer without using an adhesive layer. 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. The manufacturing method of the laminated electronic component of any one of Claims 1-3 whose thickness of the said green sheet is 1.5 micrometers or less. The manufacturing method of the laminated electronic component in any one of Claims 1-4 whose thickness of the said electrode layer is 1.5 micrometers or less. The manufacturing method of the laminated electronic component of any one of Claims 1-5 whose thickness of the sum total of the said green sheet and the said electrode layer is 3.0 micrometers or less. The said electrode layer is formed in the surface of the said 1st support sheet in a predetermined pattern, The thickness of the said 1st support sheet in which the said electrode layer is not formed is substantially the same thickness as the said electrode layer in any one of Claims 1-6. The blank pattern layer of this invention is formed, The manufacturing method of the laminated electronic component of which the said blank pattern layer is comprised from the material substantially the same as the said green sheet. The said 1st support sheet is peeled from the green sheet which has the said electrode layer, before laminating | stacking the green sheet which has the said electrode layer, The manufacturing method of the laminated electronic component which laminates on the other green sheet the electrode layer side surface of the green sheet which has the said electrode layer in the state which peeled the said 1st support sheet. The surface of the semi-electrode layer side of the green sheet having the electrode layer is laminated on another green sheet according to any one of claims 1 to 7, After laminating | stacking the green sheet which has the said electrode layer, the manufacturing method of the laminated electronic component which peels the said 1st support sheet from the green sheet which has the said electrode layer. The manufacturing method of the laminated electronic component of any one of Claims 1-9 in which the said contact bonding layer is formed by the transfer method. The method of manufacturing a laminated electronic component according to claim 10, wherein the adhesive layer is first formed on the surface of the second support sheet so as to be peeled off, and is pressed on the surface of the half electrode layer side of the green sheet having the electrode layer. The manufacturing method of the laminated electronic component of any one of Claims 1-9 which forms the said contact bonding layer by the apply | coating method.

Images