JP2000076930A - Conductive paste for internal electrode of laminated ceramic capacitor and manufacture of laminated ceramic capacitor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide conductive paste for internal electrodes of a laminated ceramic capacitor which realizes good transcription from an intaglio plate to a transcription body, when printing a thin film internal electrode pattern, and to provide a manufacturing method for the laminated ceramic capacitor using the conductive paste. SOLUTION: In this conductive paste for internal electrodes of a laminated ceramic capacitor, when a shear rate is changed isokinetically from 0 sec-1 to 12 sec-1, viscosity represented by a ratio S/D of a shear stress S to a shear rate D is in the range of 800-2,300 poise, for the shear rate in the range of 8-12 sec-1. At the same time, a thixotropy index represented by a ratio v1/v2 of the viscosity v1 in the time of the shear rate of 1 sec-1 to the viscosity v2 in the time of the shear rate of 10 sec-1 is in the range of 3-13. Furthermore, the manufacturing method of the laminated ceramic capacitor includes a process of printing patterns for the internal electrodes with intaglio offset printing using the conductive paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive paste for internal electrodes of a multilayer ceramic capacitor and a method for manufacturing a multilayer ceramic capacitor using the same.

[0002]

2. Description of the Related Art Conventionally, a multilayer ceramic component such as a multilayer ceramic capacitor is manufactured by forming an internal electrode pattern on a ceramic green sheet by a screen printing method using a conductive paste containing a metal powder and a binder resin. It is manufactured by a so-called sheet lamination method in which a plurality of the ceramic green sheets are laminated and fired (Japanese Patent Application Laid-Open No. 6-203628).

[0003] The above ceramic green sheet is one type.
Generally, electrical and thermal characteristics required for substrate materials
Alumina (Al_TwoO_Three), Mullite (3Al
_TwoO _Three・ 2SiO_Two), Aluminum nitride (AlN),
Barium titanate (BaTiO_ThreeVarious ceramics
Vine consisting of organic additives and solvents
To prepare the ceramic slurry,
Strip the sludge with a doctor blade method.
After continuous application on carrier film, it is dried
ing.

In recent years, small-sized ceramic components have been
The demand for higher capacitance has become severer.For example, in multilayer ceramic capacitors, in order to achieve this small size and high capacitance, use a dielectric material with a high dielectric constant or reduce the thickness of the ceramic green sheet to increase the number of layers. And so on. However, the demands for the above-mentioned multilayer ceramic capacitors to be smaller and larger in capacity have become more and more severe, and the use of dielectric materials having a high dielectric constant and the thinning of the ceramic green sheets alone have not been sufficient to meet the demands. For internal electrode patterns formed on thinned ceramic green sheets, studies have been made to reduce the thickness of the printed coating film.

However, when printing a thin film internal electrode pattern using the above screen printing method, a large amount of a vehicle (referred to as a solvent and a binder resin) is added to the conductive paste to cure shrinkage during firing. Must be increased, and as a result, the following problems (1) to (4) occur, and there is a limit to a reduction in the thickness of the print film. Since the content of the metal powder in the conductive paste is reduced, there is a possibility that the characteristics as an internal electrode may be impaired or the capacitance of the multilayer ceramic capacitor may vary.

The solvent contained in the conductive paste dissolves the ceramic green sheet (so-called sheet attack by the solvent), which may impair the characteristics of the multilayer ceramic capacitor. In addition to the above-mentioned problems, in the screen printing method, since the screen plate is stretched at the time of printing, the mesh expands and contracts, which may cause a variation of about ± 20 μm in printing dimensions and printing position.

Therefore, recently, instead of the screen printing method,
The formation of internal electrode patterns by a printing method such as an offset printing method (see JP-A-9-237737) and a gravure printing method (see JP-A-8-250370) has been studied. Above all, the intaglio offset printing method has excellent printing shape and does not impair the properties as an internal electrode (that is, without reducing the content of metal powder in the conductive paste used). Is expected as an effective printing method.

In the intaglio offset printing method, a step of filling a concave portion of the intaglio plate with a conductive paste, temporarily transferring the conductive paste to the surface of a transfer body, and transferring the conductive paste onto a ceramic green sheet is employed. I have. In particular, if the transfer body surface is formed of silicone rubber,
Since the conductive paste on the surface of the transfer body is completely transferred to the ceramic green sheet, it is possible to form a pattern for an internal electrode having a good printed shape such as a sharp edge of a printed pattern.

[0009]

However, the intaglio used in the intaglio offset printing method is usually glass or metal, and the surface free energy of the intaglio is 40 to 6 inclusive.
Since the conductive paste disclosed in the above publication is used since the conductive paste is about 0 dyn / cm, which is larger than that of the transfer body, the conductive paste is split when the conductive paste is transferred from the intaglio to the transfer body. As a result, there is a possibility that a phenomenon in which a part of the conductive paste remains in the concave portions of the intaglio (hereinafter, referred to as paste separation) may occur.

As a result, the separation of the paste causes irregularities (irregularities) in the shape (smoothness, uniformity, etc.) of the coating film surface of the internal electrode pattern, and in a multilayer ceramic component such as a multilayer ceramic capacitor, FIG. As shown in (1), structural defects such as a short defect 61, a delamination 62, and a break 63 in an internal electrode pattern occur, resulting in variations in capacitance, shortening of life in an accelerated life test, and reliability. There is a possibility that a problem that reproducibility is reduced may occur.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to achieve a good transition from an intaglio plate to a transfer body when printing a thin film internal electrode pattern. It is to provide a conductive paste. Another object of the present invention is to provide a method for manufacturing a multilayer ceramic capacitor using the conductive paste.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the flow characteristics of the conductive paste used for printing the internal electrode pattern (specifically, Focusing on viscoelasticity), we thought that the flow properties of such conductive paste might affect the transferability of conductive paste from intaglio to blanket, and continued our research. By setting the viscosity and thixotropy of the paste within a predetermined range, a good transfer of the conductive paste from the intaglio to the blanket can be realized (that is, the separation of the paste can be prevented), and the inside of the thin film having a smooth coating film surface can be realized. High reliability and reproducibility, with little variation in electrode pattern, and thus capacitance
The present inventors have found that a small, thin and large-capacity high-capacity ceramic capacitor can be manufactured, and have completed the present invention.

That is, the conductive paste for internal electrodes of the multilayer ceramic capacitor of the present invention has a shear rate of 0 seconds.
from c ^-1 at the time of constant speed to changing to 12 sec ^-1, shear rate in the range of 8~12sec ^-1, the viscosity represented by the ratio S / D of the shear stress S and the shear rate D 800-230
Within the scope of 0Poise, and a viscosity v ₁ at a shear rate 1 sec ^-1, the viscosity at a shear rate of 10 sec ^-1 v
The ratio v ₁ / v thixotropy represented by ₂ and _2, characterized in that in the range of 3 to 13.

The conductive paste for internal electrodes (hereinafter simply referred to as conductive paste) of the multilayer ceramic capacitor of the present invention, when filling the conductive paste into the intaglio recess with a doctor blade or the like, exerts a shear force on the conductive paste. Works to increase the shear rate and decrease the viscosity, so that the intaglio plate can be easily filled into the concave portions. Further, in the concave portion of the intaglio and on the transfer member, the shear force does not act on the conductive paste (that is, the shear rate decreases), the viscosity increases, and the internal cohesive force of the conductive paste increases. The transfer of the conductive paste from the transfer member to the transfer member and from the transfer member to the ceramic green sheet can be performed without causing the separation of the paste.

Therefore, if the conductive paste is pattern-printed on a ceramic green sheet using an intaglio offset printing method, the printed shape (particularly, the surface roughness of the printed coating film) is good, and the pattern for the internal electrode of a thin film is formed. Can be formed with high accuracy, and the reliability of the electrical characteristics of the multilayer ceramic capacitor can be improved. In order to prepare the conductive paste having the predetermined thixotropic property and viscosity, for example, as a binder resin, a butyral resin B or an acrylic resin A and a cellulose resin C are used.
And (A or B / C =) in a range of 1/1 to 6/1 by weight. Among such resins, the cellulosic resin imparts an appropriate thixotropic property to the conductive paste.

The method of manufacturing a multilayer ceramic capacitor according to the present invention comprises the steps of (1) printing an internal electrode pattern on a ceramic green sheet by using an intaglio offset printing method using the conductive paste having the predetermined viscosity and thixotropy. And (2) repeating the step (1) to form a multilayer body in which a plurality of ceramic green sheets having internal electrode patterns are laminated; and
And (b) firing the laminate.

According to the manufacturing method of the present invention, since the internal electrode pattern is formed by intaglio offset printing,
Compared to the case of using the conventional screen printing method, it is possible to print a thin film, and it is easy to adjust the thickness of the coating film,
Moreover, it is possible to form a pattern for an internal electrode having excellent pattern shape and printing position accuracy. Also, in the intaglio offset printing method, since the above-mentioned specific conductive paste is used, the transfer of the conductive paste from the intaglio to the transfer body and from the transfer body to the ceramic green sheet can be performed favorably without causing the separation of the paste. As a result, it is possible to form an internal electrode pattern having a smooth coating film surface.

Therefore, as shown in FIG. 6B, a pattern of the internal electrode of a thin film having a smooth coating film surface can be laminated, so that a structural defect such as a short-circuit failure does not occur in the dielectric layer, and the reliability is improved. Thus, it is possible to manufacture a multilayer ceramic component such as a multilayer ceramic capacitor having high cost, and having a small size, a small thickness, and a large capacity. In addition, JP-A-9-237737 describes that a cellulose resin, a rosin resin, a butyral resin, an acrylic resin, an epoxy resin, or the like may be used alone or in combination as a binder resin for the conductive paste. However, when using a plurality of these resins, no specific combination of the resins and no compounding ratio is disclosed. Of course, neither the viscosity nor the thixotropy of the conductive paste is suggested or taught.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the conductive paste of the present invention will be described. (Conductive paste) Examples of the metal powder used for the conductive paste of the present invention include copper powder, silver powder, powder obtained by coating the surface of copper powder with silver, gold powder, platinum powder, palladium powder, iron powder, and nickel powder. Powders or powders of these alloys are used, and these are used alone or in combination.

The shape of the metal powder may be, for example, a sphere or a scale, but a sphere is preferred in consideration of the viscoelasticity of the obtained conductive paste. The average particle size of the metal powder is preferably several μm to submicron. However, considering the viscoelasticity of the obtained conductive paste, the average particle size is 0.1 to 0.5μ
m is preferred.

In the present invention, in order to improve the dispersibility of the metal powder in the conductive paste, it is preferable that the surface of the metal powder is modified to a high molecular weight organic material using a coupling agent such as a silane coupling agent. Used for Further, in the present invention, in order to enhance the adhesion to the ceramic green sheet, the same metal powder as the ceramic green sheet (aluminum-based metal, titanium, etc.) is used as a co-material.
May be added to the conductive paste in a desired amount.

The amount of the metal powder used is preferably 500 to 2000 parts by weight, more preferably 700 to 1300 parts by weight, based on 100 parts by weight of the binder resin. If the amount of the metal powder is less than the above range, the electrical characteristics of the multilayer ceramic capacitor may be impaired, for example, when a thin film internal electrode pattern is formed, a sufficient capacitance may not be obtained.

Conversely, if the amount of the metal powder exceeds the above range, the proportion of the binder resin used in the conductive paste is reduced, and the internal cohesive force of the conductive paste is weakened, so that the paste may be divided. Alternatively, there is a possibility that transferability to a transfer member is extremely poor. The aggregation or poor dispersion of the metal powder in the conductive paste may cause a short circuit between the internal electrodes. Therefore, in order to sufficiently disperse the metal powder in the paste, a binder resin, a dispersant, and the like may be added.

Examples of the dispersant include various surfactants usually used for preparing a conductive paste. Among them, it is preferable to use a polymer surfactant from the viewpoint of stabilizing the conductive paste. Examples of the binder resin include a cellulose resin, a rosin resin, a polyvinyl resin, a butyral resin, an acrylic resin, a phenol resin, an epoxy resin, a polyester resin, a polyamide resin, and a polyurethane resin. And these may be used alone or in combination.

However, when manufacturing a multilayer ceramic capacitor, it is common to simultaneously fire a ceramic green sheet and a pattern for an internal electrode made of a conductive paste. It is good to select and use. Also, among the above resins,
Since the cellulosic resin can impart an appropriate thixotropic property to the conductive paste, it is preferable to use, as a binder resin, a mixed resin obtained by mixing the cellulosic resin in an appropriate amount.

More specifically, as a binder resin used for preparing a conductive paste having an excellent debinding property and a suitable thixotropic property, for example, a butyral resin B or an acrylic resin A and a cellulose resin C And (A or B / C =) 1/1 to 6/1 in a weight ratio. Examples of the butyral-based resin include polyvinyl butyral, polyvinyl butyral which is a copolymer of vinyl acetate and vinyl alcohol.

Examples of the acrylic resin include polymers and copolymers of acrylic acid and its esters, acrylamide, acrylonitrile, methacrylic acid and its esters, and the like. Examples of the cellulosic resin include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose, cellulose nitrate, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate. These are used alone or in combination of two or more.

The amount of the binder resin used is 3 to 15% by weight, preferably 5 to 9% by weight based on the total amount of the conductive paste.
% By weight. If the amount of the binder resin is below the above range, the properties as a binder are not satisfied,
The internal cohesive force of the conductive paste may be weakened.
Conversely, if the amount of binder resin used exceeds the above range,
In order to adjust the viscosity to the above-mentioned predetermined range, a large amount of a solvent must be used, and the use ratio of the metal powder in the conductive paste is reduced. There is a possibility that the characteristics as a ceramic capacitor may not be satisfied.

The solvent used in the conductive paste of the present invention is not particularly limited as long as it is compatible with the above-mentioned binder resin and dispersant.
The above is preferred. If the boiling point of the solvent does not satisfy the above range, the solvent is likely to evaporate during printing,
The conductive paste may change over time, and the printing characteristics may deteriorate.

The above-mentioned solvent is specifically described, for example, hexanol, octanol, nonanol, decanol,
Alcohols such as undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, ceryl alcohol, cyclohexanol and terpineol; ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbyl) Tol), cellosolve acetate, butyl cellosolve acetate, carbitol acetate, alkyl ethers such as butyl carbitol acetate, etc., which are appropriately selected and used in consideration of printability and workability.

When a higher alcohol is used as the solvent, the drying and fluidity of the paste may be inferior. Therefore, butyl carbitol, butyl cellosolve, ethyl carbitol, butyl cellosolve acetate, which have better drying properties than these, are used. And butyl carbitol acetate may be used in combination. The solvent may be used so that the viscosity and thixotropy of the obtained conductive paste fall within predetermined ranges.

More specifically, for example, as a binder resin for the conductive paste, a butyral resin B or an acrylic resin A and a cellulose resin C are used in a weight ratio (A or B / C =) 1/1 to 6 When a mixed resin blended so as to be in the range of / 1, 100 to 500 parts by weight, preferably 200 to 300 parts by weight, of the solvent is added to 100 parts by weight of the mixed resin.

The conductive paste of the present invention comprises the above-mentioned metal powder.
In addition to the vehicle (binder resin and solvent),
Plasticizer, antistatic agent, defoamer, antioxidant as required
Auxiliaries such as lubricants, lubricants, and curing agents, and
Prepared by kneading and dispersing using a mixer such as
It is. The conductive paste thus prepared has a shear rate of
0 sec^-1From 12 sec ^-1Changed at a constant speed
The shear rate is 8 to 12 seconds^-1In the range of
A viscosity represented by a ratio S / D between the force S and the shear rate D is 800.
Within the range of ~ 2300 poise and shear rate
1 sec^-1Viscosity v₁And shear speed 10 sec^-1
Viscosity v_TwoRatio v₁/ V_TwoThixotropy represented by
Is in the range of 3 to 13.

Here, the flow characteristics (viscoelasticity) of the conductive paste of the present invention will be described with reference to FIG. The conductive paste of the present invention has a shear rate of 0 sec ^-1 to 12 sec.
Fluidity is increased by changing at a constant speed to c- ¹ ,
The viscosity gradually decreases and a loop is drawn as shown by a solid line A in FIG. Such a phenomenon is called thixotropic.

Similar to the solid line A in FIG. 7, the solid line B in FIG.
-E are also conductive pastes having thixotropic properties. In the case of conductive pastes exhibiting the flow characteristics indicated by the solid line B, the viscosity at a shear rate of 1 sec ^-1 and the shear rate of 1
Thixotropicity represented by the ratio to the viscosity at ⁰ sec ^-1 is 13
Not only is it difficult to prepare the conductive paste, but also when the conductive paste is filled into the recesses of the intaglio with a doctor blade or the like, the viscosity increases in the initial stage until a shear force acts on the paste. Therefore, the filling of the conductive paste into the recesses of the intaglio may become difficult (hereinafter referred to as paste filling failure).

In the case of the conductive paste exhibiting the flow characteristics indicated by the solid line C, the thixotropic property is smaller than 3 in contrast to the conductive paste indicated by the solid line B. (A state in which no shear force acts on the conductive paste), there is a possibility that the paste will be divided. Also,
In the case of a conductive paste exhibiting the flow characteristics of the solid line D, the viscosity is higher than 800 to 2300 poise when the shear rate is 8 to 12 sec ^-1 (D _{a in} FIG. 7), so that the thixotropic property is not reduced. There is a risk that the conductive paste may not be able to be filled well in the recesses of the intaglio and that the paste may be broken when the conductive paste is transferred from the intaglio to the transfer body, or the transfer from the intaglio to the transfer body Properties may be very poor.

In the case of the conductive paste having the flow characteristics indicated by the solid line E, the viscosity at _a shear rate of 8 to 12 sec ^-1 (D _{a in} FIG. 7) is opposite to the conductive paste indicated by the solid line D. Is lower than 800 to 2300 poise, there is a possibility that the paste may be broken at the time of transfer from the intaglio to the transfer body even if the conductive paste is given an appropriate thixotropy. Further, the conductive paste showing the flow characteristics of the solid line E is as follows:
Since the amount of the solvent in the conductive paste increases, there is a possibility that sheet attack by the solvent may occur or the internal cohesive force of the conductive paste may be weakened.

On the other hand, the conductive paste of the present invention, suitable viscosity (viscosity at D _a in FIG. 7 800～2300P
Since oise) and thixotropy (the ratio of the viscosity v ₁ and v ₂ in Figure 7 having 3 to 13), not to cause the observed on solid B~E conductive paste problem, doctor It is possible to sufficiently fill the concave portion of the intaglio with a blade or the like, and to prevent separation of the paste when transferring from the intaglio to the transfer body and from the transfer body to the ceramic green sheet.

The terms indicating the flow characteristics of the fluid include:
In addition to the above thixotropic properties, there is a Newtonian fluidity. The Newtonian fluidity is a phenomenon that does not change even if the shear rate is changed, shows fluidity with a constant viscosity, and is observed in fluids such as water and alcohol. When the conductive paste having such a Newtonian fluidity is used, unlike the conductive paste having the thixotropic property, when the conductive paste is filled into the recesses of the intaglio, the conductive paste on the transfer body is used. Since the viscosity of the conductive paste is constant, there is a possibility that defective filling of the paste or separation of the paste may occur.

Next, a method for manufacturing the multilayer ceramic capacitor of the present invention will be described. In the multilayer ceramic capacitor, (1) a step of printing an internal electrode pattern on a ceramic green sheet by the intaglio offset printing method using the conductive paste described above, and (2) a step of (1) above are repeated. Then, a step of forming a laminated body in which a plurality of ceramic green sheets each having an internal electrode pattern are laminated, and (3) a step of firing the laminated body of the above (2) are employed. You.

First, various members used in the step (1) of printing the internal electrode pattern will be described. (Transfer Body) As the transfer body used in the present invention, a transfer body having excellent receptivity of the conductive paste from the concave portion of the intaglio plate and having excellent transferability of the conductive paste to the ceramic green sheet is used. This is preferable in that a thin film coating having a smooth surface can be reproduced with high accuracy.

As the transfer member, for example, a transfer member whose surface rubber layer is made of silicone rubber is preferably used. The silicone rubber includes a millable type and a room temperature curing type (R
Various silicone rubbers such as a TV) type and an electron beam curing type are used. Above all, room-temperature-curable addition-type silicone rubber is preferably used because it can reproduce a thin printed coating film with high accuracy without generating any by-products at the time of curing.

The surface rubber layer made of these silicone rubbers preferably has a smooth surface, and more specifically, preferably has a surface roughness of 0.5 μm or less as a 10-point average roughness, more preferably 0.3 μm or less. The hardness (JIS-A) of the silicone rubber is preferably 20 to 80 degrees, more preferably 40 to 70 degrees.
In order to adjust the hardness of silicone rubber to this range,
Silicone oil or silicone gel may be appropriately blended.

The support of the blanket may be any as long as it has a flat surface, such as polyethylene terephthalate (PET), polyether sulfone (PES),
Plastics such as polyester and polycarbonate (PC), and metal plates such as aluminum and stainless steel can be used. Further, the transfer body may have a porous layer formed between the surface rubber layer and the support.

The shape of the transfer member used in the present invention is as follows.
Examples include a sheet-shaped blanket wound around a cylindrical body (roller), and a roller-shaped one. Also,
As long as no displacement occurs during printing, a curved elastic body used for pad printing or the like, or a sheet-like blanket attached to the elastic body may be used. (Intaglio) As the intaglio used in the present invention, for example, a flat plate having a concave portion corresponding to the internal electrode pattern formed on the surface of the substrate, or a flat plate wound,
A cylindrical one or a columnar one may be used.

As the substrate, for example, soda lime glass, non-alkali glass, quartz, low alkali glass,
In addition to glass plates such as low expansion glass, fluorine resin, polycarbonate (PC), polyether sulfone (PE
S), a resin plate of polyester, polymethacrylic resin, etc.
Metal plates such as stainless steel, copper, and low expansion alloy invar can be used. Among them, it is particularly preferable to use a glass plate such as soda lime glass, which can form the edge shape of the pattern very sharply.

The concave portion of the intaglio plate can be formed by a photolithography method, an etching method, an electroforming method or the like, as in the prior art. The depth of the concave portion of the intaglio plate is set such that the depth of the concave portion is approximately 1 to 10 μm, preferably 3 to 7 μm so that the thickness of the internal electrode pattern is usually approximately 0.5 to 5 μm in thickness after drying. Is set in the range.

Further, the intaglio may have a doctor blade for scraping the conductive paste according to the type of the intaglio. At this time, as the blade blade, for example, metal such as stainless steel, rubber, resin, ceramic, or the like is used. (Ceramic Green Sheet) The ceramic green sheet used in the present invention is, for example, alumina (Al).
₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), aluminum nitride (AlN), barium titanate (BaT)
A ceramic slurry is prepared by adding a binder made of an organic additive and a solvent to various ceramic raw material powders such as iO ₃ ), and then the ceramic slurry is pulled up, a doctor blade method, a reverse roll coater method, and the like. It is manufactured by continuously applying the composition on a carrier film in a belt shape by a conventionally known method such as a gravure coater method and then drying.

Examples of the shape of the ceramic green sheet include a long one wound on a roll and a strip-like one cut to a predetermined length. Further, in the present invention, a ceramic green sheet produced by printing a predetermined size on a carrier film by a printing method such as a screen printing method or a gravure printing method may be used.

When a multilayer ceramic capacitor is manufactured by the manufacturing method of the present invention, an off-the-shelf ceramic green sheet that has been manufactured in advance by a doctor blade method or the like may be used, or when a pattern for an internal electrode is printed. In addition, those produced as needed by a screen printing method, a flexographic printing method, a spray coat, a curtain coat, or the like may be used.

The thickness of the ceramic green sheet is as follows:
It is preferable that the thickness of the multilayer ceramic component is as small as possible for the reason of miniaturization and large capacity of the multilayer ceramic component. In the present invention, a thin-film internal electrode pattern is formed on the surface of the thin ceramic green sheet, and a ceramic green sheet is laminated on the pattern. The laminating step of the internal electrode pattern and the ceramic green sheet is alternately performed. When a multilayer ceramic capacitor is manufactured repeatedly, the thickness of the dielectric layer (specifically, ceramic green sheet) can be reduced, so that a higher stacking (multilayering) than before can be achieved, and a large capacity can be realized. It has the advantage of being able to.

Next, the step (1) of printing an internal electrode pattern using the above members will be described with reference to the drawings. The step (1) of printing the internal electrode pattern is performed, for example, by an intaglio offset printing machine shown in FIG.
This is performed by transferring the conductive paste from the intaglio to the transfer body and from the transfer body to the ceramic green sheet through the steps shown in FIGS. 2A to 2C.

The intaglio offset printing press shown in FIG. 1 is an example of an offset printing press using a plate-shaped intaglio, and reference numeral 1 in the figure denotes a transfer member in which a blanket is wound around a roller in a sheet shape. (Alternatively, a roller-shaped transfer body may be used.) Reference numeral 2 denotes a ceramic green sheet,
Reference numeral 3 denotes an intaglio, reference numeral 4 denotes a concave portion of the intaglio, reference numeral 5 denotes a doctor blade, and reference numeral 6 denotes a ceramic green sheet support.

As shown in FIG. 2A, a necessary amount of conductive paste is first filled in the concave portion 4 of the intaglio 3 by using a doctor blade 5. This conductive paste may be filled by supplying a sufficient amount of the conductive paste to the concave portion 4 of the intaglio 3 in advance, and scraping off the excess conductive paste with a doctor blade. Next, as shown in FIG. 2B, the transfer body 1 is rotated while being pressed against the intaglio 3 at a predetermined pressure, and the conductive paste 7 in the indentation 4 of the intaglio is transferred without causing the paste to be divided. Transfer around body 1.

At this time, the transfer body 1 is usually placed on the intaglio 3 in a state of 0.1 mm.
1-5 kg / cm ^2, and it is preferably is pressed in the range of 1-2 kg / cm ^2. Then, as shown in FIG. 2C, the transfer body 1 is rotated while pressing the transfer body 1 against the ceramic green sheet 2 at a predetermined pressure, and the conductive paste 7 transferred around the transfer body 1 is completely separated without being separated. Is transferred onto the ceramic green sheet 2.

The transfer body 1 is applied to the ceramic green sheet 2 usually at 0.1 to 5 kg / cm ² , preferably at 1 to ² k / cm ² .
It is sufficient that the pressure is applied in the range of g / cm ² . Further, in the present invention, in a printing method using a flat intaglio, a curved elastic body 11 used for pad printing or the like is used as shown in FIG. 3 instead of the transfer body 1 shown in FIGS. Alternatively, as shown in FIG. 4, a transfer member 12 having a large curvature and a sheet-like blanket 13 attached thereto may be used.

Next, a process of printing an internal electrode pattern on a ceramic green sheet 2 using a conductive paste by an offset printing machine using a cylindrical intaglio will be described with reference to FIG. In the offset printing press using the columnar intaglio, a transfer body 1 composed of a roller is arranged near the columnar intaglio 9 so as to be able to contact the columnar intaglio 9. A ceramic green sheet 2 is disposed near the transfer body 1. The cylindrical intaglio plate 9 is provided with a blade 5 for filling the concave portion with a conductive paste, and the blade 5 has a paste reservoir.

As shown in this figure, first, the conductive paste 7 is filled in the concave portion 4 of the cylindrical intaglio 9 on which the doctor blade 5 is installed. The printing pressure in the transfer step from the intaglio 9 to the transfer body 1 and the transfer step from the surface of the transfer body 1 to the ceramic green sheet 2 is not particularly limited, but is usually printed at about 0.1 to 5 kg / cm ^2. do it.

The transfer speed of the conductive paste from the intaglio 9 to the transfer body 1 is usually preferably set to about 50 to 200 mm / s from the viewpoint of improving the acceptability of the conductive paste of the transfer body 1. The transfer speed of the conductive paste from the transfer body 1 to the ceramic green sheet 2 is usually 5
It is good to set it in the range of about 0 to 200 mm / s.

Under these conditions, the conductive paste 7 filled in the intaglio recesses 4 is transferred to the transfer member 1 without causing the paste to be separated, and is then transferred well from the transfer member 1 to the ceramic green sheet 2. Is done. Reference numeral 10 in FIG. 5 denotes a thick body, and the transfer body 1 of the conductive paste 7 is used.
This is for adjusting the pressure at the time of transfer from the substrate to the ceramic green sheet 2.

The thickness of the internal electrode pattern formed in the step (1) is usually 3 μm or less in order to reduce the size of the multilayer ceramic capacitor and obtain high reliability.
It is preferably 2 μm or less, more preferably 1 μm or less. The printing method for forming the internal electrode pattern on the ceramic green sheet is not limited to the above-described method, and once the conductive paste filled in the intaglio recess is transferred to the transfer member surface, In the intaglio offset printing method in which the conductive paste transferred to the surface of the transfer body is transferred onto a ceramic green sheet, the conductive paste has a viscosity of 800-2.
By using a paste having a thickness of 300 poise and a thixotropy of 3 to 13, a printing method in which the paste does not break when the conductive paste is transferred from the intaglio to the transfer body and from the transfer body to the ceramic green sheet. I just need.

Next, the step (2) of forming the laminate will be described. In the manufacturing method of the present invention, in order to form a laminate by laminating a plurality of ceramic green sheets each having a pattern for an internal electrode, (A) the above (1) using a conductive paste on the ceramic green sheets. The step of printing the pattern for the internal electrode by the step of) and the step of forming the ceramic green sheet on the pattern for the internal electrode are repeated a plurality of times, and the ceramic green sheet, the pattern for the internal electrode, and the ceramic green sheet are stacked in this order. Method, or (B) preparing a long ceramic green sheet wound on a roll, and using a conductive paste on the ceramic green sheet, using an intaglio offset printing method (repetition of the above step (1)) to form the internal electrodes. Pattern is printed at the same pitch,
Then, the ceramic green sheet having the internal electrode pattern is cut to produce a plurality of ceramic green sheets having the internal electrode pattern, and then the plurality of ceramic green sheets are sequentially stacked.

At this time, a plurality of ceramic green sheets each having an internal electrode pattern are stacked so that the side from which the internal electrode pattern is drawn out is staggered, as shown at A in FIG. Can be By this stacking method, one end of the laminate can be electrically connected to the anode of the external electrode, and the other end can be electrically connected to the cathode of the external electrode.

Since the laminate of the present invention is composed of the thin-film internal electrode patterns and the thin ceramic green sheets, it can be made thinner (ie, smaller and thinner) than conventional multilayer ceramic capacitors. That is, the multilayer can be formed in the same thickness as the conventional multilayer ceramic capacitor. Therefore, it is possible to manufacture a small-sized and large-capacity multilayer ceramic capacitor having a large number of layers.

Next, the step (3) of firing the laminate will be described. The firing of the formed laminate is performed by burning the binder resin at 500 to 800 ° C. in the air or in a nitrogen atmosphere, and then in the air or in a reducing atmosphere at 1000 to 1000 ° C.
It is performed by firing at 1800 ° C. and further heat-treating at 600-900 ° C. In this case, when a metal powder having a reducing property (such as a palladium powder or a copper powder) is used as the metal powder of the conductive paste, the calcination is not necessarily performed in a nitrogen atmosphere or a reducing atmosphere. When a metal powder having no property (for example, nickel powder) is used, it is preferable to perform firing in a nitrogen atmosphere or a reducing atmosphere.

Then, as shown in FIG. 8, the laminated body obtained by this sintering is coated with, for example, indium-gallium paste on each end face thereof to form an external electrode electrically connected to the internal electrode layer. By forming 81, a multilayer ceramic capacitor is formed.

[0067]

The present invention will be specifically described below with reference to examples and comparative examples. The intaglio, transfer member, and ceramic green sheet used in Examples and Comparative Examples described below are as follows. (Intaglio) Chrome (C)
After vapor deposition of r), a predetermined pattern was drawn using a laser. Then, a conventional etching process was performed to produce a glass intaglio having a depth of 6 μm. The surface free energy of this intaglio is 45 dyn / cm. (Transfer Body) A sheet-shaped blanket is mounted on a cylindrical blank cylinder. The blanket is 0.35 thick
A 0.55 mm thick room-temperature-curable addition-type silicone rubber (hardness: JIS-A, 60 °, surface roughness: 0.2 μm) layer formed on a 0.5 mm-thick polyethylene terephthalate support was used. (Ceramic green sheet) 97.5 mol% of BaTiO ₃ on a band-shaped carrier film made of synthetic resin
2.0 mol% of CaZrO ₃ and 0.5 mol% of MnO were mixed with Y ₂ O _{3 with} respect to 100 mol parts of the ceramic raw material powder.
A ceramic slurry was prepared by adding 0.5 mol part, and adding 5.4% by weight of butyral resin as a binder to the total amount of the obtained mixture, and then applying the ceramic slurry by a doctor blade method. By drying, a belt-shaped ceramic green sheet having a thickness of 7.5 μm was produced. Then, a ceramic green sheet punched into a size of 100 mm × 100 mm was used. Example 1 (Preparation of conductive paste) Binder resin (ethyl cellulose: polyvinyl butyral (weight ratio) = 1: 2) 1
Butylcarbitol acetate as a solvent having a viscosity of 830 p.
The mixture was blended so that the oil and thixotropic properties became 10.8, and the mixture was uniformly dispersed using a three-roll mill to prepare a paste.

The viscosity (poi) of the conductive paste was
se) is a rheological viscoelasticity measuring device “MR-50”
This is a measured value when the shear rate is 10 sec ⁻¹ , which is calculated from the following measurement conditions using “0”. Measurement conditions: using a cone plate with a cone diameter of 20 mm and a cone angle of 5 deg, a maximum rotation speed of 10 rpm, and a measurement time of 5
The rotation was moved up and down at a constant speed in 0 seconds, and the torque acting on the cone was detected.

[0069] In addition to the thixotropy, a viscosity v ₁ at a shear rate 1 sec ^-1, the ratio v ₁ / v ₂ of the viscosity v ₂ at a shear rate of 10 sec ^-1. (Preparation of Multilayer Ceramic Capacitor) A ceramic green sheet was fixed on the support of the intaglio offset printing press shown in FIG. Then, the conductive paste prepared above is filled in the recesses of the intaglio by a doctor blade, and the transfer body is rotated while pressing the intaglio at a pressure of 2 kg / cm ² to transfer the conductive paste in the intaglio recesses. Transferred onto the body. Subsequently, the conductive paste on the transfer member was transferred onto one surface of the ceramic green sheet by rotating the ceramic green sheet while pressing the transfer member at a pressure of 2 kg / cm ² , and a pattern for an internal electrode was printed.

At this time, the transfer speed of the conductive paste from the intaglio to the transfer member (the relative movement speed between the intaglio and the transfer member) and the transfer speed of the conductive paste from the transfer member to the ceramic green sheet (the transfer member and the ceramic) The relative movement speed with respect to the green sheet is 100 mm / s.
Next, a ceramic green sheet having an internal electrode pattern, obtained by repeating the above steps, is laminated by stacking 20 layers so that the side from which the internal electrode pattern is drawn out is alternated. Was formed.

After heating the obtained laminate at 800 ° C. in a nitrogen atmosphere to burn out the binder,
It was fired at 1250 ° C. for 2 hours in a reducing atmosphere, and further heat-treated at 900 ° C. in a nitrogen atmosphere to obtain a ceramic sintered body. After firing, an indium-gallium paste was applied to each end face of the obtained sintered body to form an external electrode electrically connected to the internal electrode, thereby producing a multilayer ceramic capacitor in which the internal electrode was made of Ni.

The external dimensions of this multilayer ceramic capacitor were 1.6 mm in width and 3.2 mm in length, and the thickness of the dielectric layer interposed between the internal electrodes was 5 μm. The total number of dielectric layers is 20, and the area of the counter electrode per layer is 2.
It was 1 mm ² . Examples 2 to 6, Comparative Examples 1 to 5 A pattern for an internal electrode was formed in the same manner as in Example 1 except that a conductive paste having a viscosity and a thixotropy shown in Table 1 below was used. Produced. (Separation of Paste) The transferability of the conductive paste from the intaglio to the transfer body when printing the internal electrode pattern in the above Examples and Comparative Examples was observed with a microscope for the paste remaining in the intaglio recess after printing. Then, it was confirmed whether or not the conductive paste was divided in the intaglio.

Further, the transferability of the paste from the transfer body to the ceramic green sheet was measured by rolling the adhesive roller on the surface of the transfer body after printing, observing the surface of the adhesive roller with a microscope, and determining the separation of the paste on the transfer body surface. The presence or absence was checked. (Surface Roughness of Printed Coating Film) A coating film (electrode layer) printed on a ceramic green sheet using a conductive paste
After drying at 0 ° C. for 5 minutes, the 10-point average roughness (Rz) of the coating film surface was measured using a surface / step profile measuring device P-10 manufactured by Tencor Corporation. (Thickness of Electrode Layer) One hundred prototype multilayer ceramic capacitors were observed using a fracture surface electron microscope, and the average thickness of the internal electrode layers was measured. (Measurement of Capacitance, Coefficient of Variation (CV Value) and Accelerated Life) The capacitance was measured using an LCR meter under the conditions of 1 kHz, 1 Vrm, and a temperature of 25 ° C. In addition, the variation coefficient (CV value) of the capacitance was calculated. The variation coefficient (CV value) is a value obtained by dividing the standard deviation of the capacitance by the thickness of the dielectric layer. In addition, the temperature 140
The accelerated life (min) was measured under the conditions of 15 ° C. and 15 V / μm.

The evaluation results are shown in Table 1 below, together with the viscosity and thixotropy of the conductive paste used.

[0075]

[Table 1] Examples 7 to 12 and Comparative Examples 6 to 10 As a binder resin, a mixture of ethyl cellulose and polyvinyl butyral in a weight ratio (former: latter =) of 1: 4 was used, and nickel powder was used as a metal powder. A conductive paste having the viscosity and thixotropic properties shown in Table 2 below was prepared in the same manner as in Example 1 except that 1100 parts by weight was added to the parts by weight. Then, a pattern for an internal electrode was formed in the same manner as in Example 1 except that a conductive paste having a viscosity and a thixotropy shown in Table 2 below was used, and a multilayer ceramic capacitor was produced.

For Examples 7 to 12 and Comparative Examples 6 to 10, in the same manner as in Example 1 (cutting of the paste),
The items of (surface roughness of printed coating film), (thickness of electrode layer) and (measurement of capacitance, its variation coefficient (CV value) and accelerated life) were evaluated. These evaluation results,
The viscosity and thixotropy of the conductive paste used are shown in Table 2 below.

[0077]

[Table 2] Comparative Examples 11 to 20 Using polyvinyl butyral as a binder resin,
And nickel powder as a metal powder in a binder resin 10
A conductive paste having the viscosity and thixotropic properties shown in Table 3 below was prepared in the same manner as in Example 1 except that 1300 parts by weight was added to 0 parts by weight. Next, an internal electrode pattern was formed in the same manner as in Example 1 except that a conductive paste having the viscosity and thixotropy shown in Table 3 below was used, and a multilayer ceramic capacitor was produced.

With respect to Comparative Examples 11 to 20, the above Example 1 was used.
In the same manner as in the above, items of (partition of paste), (surface roughness of printed coating film), (thickness of electrode layer) and (measurement of capacitance, its variation coefficient (CV value) and accelerated life) Was evaluated. These evaluation results are shown in Table 3 below together with the viscosity and thixotropic properties of the conductive paste used.

[0079]

[Table 3] Comparative Examples 21 to 30 An acrylic resin (methyl methacrylate) was used as a binder resin, and nickel powder was used as a metal powder in an amount of 110 parts by weight per 100 parts by weight of the binder resin.
Table 4 below was prepared in the same manner as in Example 1 except that 0 part by weight was added.
A conductive paste having the viscosity and thixotropy shown in Table 1 was prepared. Then, an internal electrode pattern was formed in the same manner as in Example 1 except that a conductive paste having the viscosity and thixotropic properties shown in Table 4 below was used, and a multilayer ceramic capacitor was produced.

For Comparative Examples 21 to 30, the above Example 1 was used.
In the same manner as in the above, items of (partition of paste), (surface roughness of printed coating film), (thickness of electrode layer) and (measurement of capacitance, its variation coefficient (CV value) and accelerated life) Was evaluated. These evaluation results are shown in Table 4 below together with the viscosity and thixotropic properties of the conductive paste used.

[0081]

[Table 4] Examples 13 to 18 and Comparative Examples 31 to 35 A mixture of ethyl cellulose and an acrylic resin in a weight ratio of 1: 3 (former: latter =) was used as the binder resin, and nickel powder was used as the metal powder. A conductive paste having the viscosity and thixotropic properties shown in Table 5 below was prepared in the same manner as in Example 1 except that 900 parts by weight was added to the parts by weight. Next, an internal electrode pattern was formed in the same manner as in Example 1 except that a conductive paste having a viscosity and a thixotropy shown in Table 5 below was used, and a multilayer ceramic capacitor was produced.

Examples 13 to 18 and Comparative Examples 31 to 35
In the same manner as in Example 1 (cutting of the paste), (surface roughness of the printed coating film), (thickness of the electrode layer), (capacitance, its variation count (CV value), and acceleration). Lifetime measurement) was evaluated. These evaluation results are shown in Table 5 below together with the viscosity and thixotropic properties of the conductive paste used.

[0083]

[Table 5] As is evident from Tables 1 to 5, in the examples, the transfer of the paste from the intaglio plate to the transfer member and the transfer of the conductive paste from the transfer member to the ceramic green sheet did not cause any separation of the paste. Further, the coating film surface roughness Rz is very smooth, 0.5 μm or less. Furthermore, in the obtained multilayer ceramic capacitor, the variation in the capacitance was less than 3%, the variation in the capacitance was small, and the accelerated life was long, indicating that the reliability was high.

On the other hand, the viscoelasticity (viscosity and thixotropy) of the conductive paste used did not satisfy the constituent requirements of the present invention, that is, Comparative Examples 1 to 3 using the conductive paste having a viscosity of less than 800 poise. 6-8, 11-
In Nos. 15, 21 to 25, and 31 to 33, when the conductive paste is transferred from the intaglio plate to the transfer body, the paste is separated, and an internal electrode pattern with extremely poor surface roughness is formed. As a result, in the obtained multilayer capacitor, the variation in the capacitance was found to be 3% or more, and the variation in the capacitance was recognized, indicating that the accelerated life was very short.

Comparative Examples 4 to 5, 9 to 10 using conductive paste having a viscosity of more than 2300 poise
In 20, 30, and 34 to 35, the transfer ratio of the conductive paste from the intaglio to the transfer body is poor because the proportion of the solvent in the conductive paste is too small, and the internal electrode pattern is printed. Has become difficult. Also,
Although the viscosity satisfies the range of the present invention, in Comparative Examples 16 to 19 and 26 to 29 in which the thixotropy is less than 3, since the thixotropy is small, the viscosity of the paste is low even in the concave portion of the intaglio where the shearing force does not work. Since the conductive paste does not increase, the internal cohesive force of the conductive paste is small, and when the conductive paste is transferred from the intaglio to the transfer body, the paste is divided and the surface roughness Rz of the coating film is deteriorated.

The multilayer ceramic capacitor obtained from the conductive paste of the comparative example has a capacitance variation count of 3
% Or more, the variation in capacitance is recognized, and it can be seen that the accelerated life is very short. Next, for the conductive paste prepared using the binder resin shown in Table 6 below, in the same manner as in Example 1 (cutting of the paste),
The items of (surface roughness of printed coating film), (thickness of electrode layer) and (measurement of capacitance, its variation coefficient (CV value) and accelerated life) were evaluated. Example 19 5 parts by weight of a binder resin (ethyl cellulose: polyvinyl butyral (weight ratio) = 1: 1), nickel fine powder 7
5 parts by weight and solvent (butyl carbitol acetate)
A conductive paste was prepared in the same manner as in Example 1 except that 20 parts by weight was blended, and a pattern for an internal electrode was formed using the conductive paste in the same manner as in Example 1 to produce a multilayer ceramic capacitor. . The conductive paste has a viscosity of 1780 poise and a thixotropic property of 8.5. Examples 20 to 24, Comparative Examples 36 to 42 Conductive pastes were prepared in the same manner as in Example 19 except that the binder resins shown in Table 6 below were used, and the patterns for internal electrodes were formed using the conductive pastes. Then, a multilayer ceramic capacitor was manufactured.

The results of the evaluation are shown in Table 6 below, together with the mixing ratio of the binder resin, the viscosity of the conductive paste, and the thixotropy.

[0088]

[Table 6] As is clear from Table 6, a resin in which polyvinyl butyral (butyral resin) or an acrylic resin (acrylic resin) is blended in a weight ratio of 1 to 6 times with respect to ethyl cellulose (cellulose resin) as a binder resin (Example) 19 to 24), no fragmentation of the paste occurs, the coating film surface is very smooth, and in the obtained multilayer ceramic capacitor, the variation coefficient of the capacitance is within 3%. It can be seen that there is little variation in capacity and the acceleration life is long.

[0089]

As described above in detail, by forming an internal electrode pattern for a multilayer ceramic capacitor by intaglio offset printing using a conductive paste having a predetermined viscoelasticity (viscosity and thixotropy). Transfer of the conductive paste from the intaglio to the transfer body and from the transfer body to the ceramic green sheet is realized without causing the paste to be separated, and the coating film surface is formed with extremely high precision with a very smooth thin film internal electrode pattern. can do.

Accordingly, the variation in the capacitance is reduced, and a small-sized, large-capacity, highly reliable, highly laminated ceramic capacitor can be manufactured.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an offset printing press using a plate-shaped intaglio.

FIG. 2 is an explanatory view showing a step of printing a conductive paste on a ceramic green sheet by the intaglio offset printing machine of FIG. 1;

FIG. 3 is an explanatory diagram showing another example of an offset printing press using a plate-shaped intaglio.

FIG. 4 is an explanatory view showing another example of an offset printing press using a plate-shaped intaglio.

FIG. 5 is an explanatory view showing a step of printing a conductive paste on a ceramic green sheet by an offset printing machine using a cylindrical intaglio.

FIG. 6 is a cross-sectional view of a multilayer ceramic capacitor when an internal electrode pattern is formed by intaglio offset printing using a conventional conductive paste (FIG. 6a), and an internal electrode pattern is formed by the manufacturing method of the present invention. FIG. 6B is a cross-sectional view (FIG. 6B) of the multilayer ceramic capacitor in the case of the above.

FIG. 7 is a graph showing a relationship between a shear rate and a viscosity in a conductive paste for an internal electrode of a multilayer ceramic capacitor.

FIG. 8 is a cross-sectional view of the multilayer ceramic capacitor of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiichi Inuzuka 2-2-1 4-207 Izumidai, Kita-ku, Kobe-shi, Hyogo F-term (reference) 5E001 AB03 AC09 AC10 AF00 AF06 AH01 AH05 AH09 AJ01 5E082 AA01 AB03 BC38 BC39 BC40 EE04 EE23 EE26 EE35 FG06 FG26 FG54 GG10 GG11 GG28 JJ03 JJ12 JJ23 LL01 LL02 LL35 MM11 MM22 MM24 PP10 5G301 DA10 DA42 DD01

Claims (5)

[Claims] When the shear speed is changed from 0 sec ^-1 to 12 sec ^-1 at a constant speed, the shear speed is from 8 to 12 sec.
In the range of ^-1, in a viscosity range that is represented by the ratio S / D of the shear stress S and the shear rate D is 800～2300Poise, and a viscosity v ₁ at a shear rate 1 sec ^-1, shear rate A conductive paste for an internal electrode of a multilayer ceramic capacitor, wherein the thixotropy represented by the ratio v ₁ / v ₂ to the viscosity v _{2 at 10} sec ⁻¹ is in the range of 3 to 13. 2. A butyral resin B or an acrylic resin A and a cellulose resin C are blended as a binder resin in a weight ratio of (A or B / C =) 1/1 to 6/1. 2. The conductive paste for internal electrodes of a multilayer ceramic capacitor according to claim 1, wherein the conductive paste contains a mixed resin. 3. A step of (1) printing an internal electrode pattern on the ceramic green sheet by the intaglio offset printing method using the conductive paste according to claim 1 or (2). Repeating the steps to form a laminate in which a plurality of ceramic green sheets having internal electrode patterns are laminated, and (3) a step of firing the laminate of (2) above. Method for manufacturing a multilayer ceramic capacitor. 4. The method for manufacturing a multilayer ceramic capacitor according to claim 3, wherein said laminate is formed by laminating a plurality of ceramic green sheets on which an internal electrode pattern has been printed in advance. 5. The method according to claim 3, wherein the laminate is formed by alternately laminating ceramic green sheets and patterns for internal electrodes.