JP4720245B2 - Manufacturing method of multilayer ceramic electronic component - Google Patents

Description

  The present invention relates to a method for manufacturing a multilayer ceramic electronic component, and more particularly to a method for manufacturing a multilayer ceramic electronic component that suppresses stacking deviation, has excellent stackability, and has low delamination.

  For example, the manufacture of a multilayer ceramic capacitor as an example of a multilayer ceramic electronic component is performed according to the following procedure.

  First, a dielectric slurry in which a ceramic dielectric pigment powder is dispersed in a solvent containing a nonvolatile organic component such as a dispersant, a polymer resin, and a plasticizer is prepared. Next, this dielectric slurry is applied and dried on a plastic support film by means such as a doctor blade method or a nozzle method to obtain a dielectric green sheet.

  Next, an internal electrode pattern layer is formed on the dielectric green sheet. The internal electrode pattern layer is generally formed by screen printing a conductive paste.

  Next, after peeling the dielectric green sheet containing the internal electrode pattern layer from the support base film and cutting it to a predetermined size, while performing the pattern alignment of the internal electrode pattern layer, after laminating a plurality of times, The ceramic green laminate is formed by pressurization and pressure bonding. Next, this multilayer body is cut into a predetermined size to obtain a chip, and then fired at a predetermined atmosphere and temperature, and an external electrode is applied and baked onto the end of the obtained fired body chip to thereby obtain a multilayer ceramic capacitor. Is completed.

  In the manufacturing process of such a multilayer ceramic capacitor, when the internal electrode pattern layer is formed in a predetermined pattern on the dielectric green sheet, the internal electrode pattern layer has a step gap portion (blank pattern) where no electrode pattern layer exists. ) Exists. A step is formed on the surface of the internal electrode pattern layer due to the stepped gap portion. A large number of internal electrode pattern layers are stacked via green sheets in a state where the step is formed. Thereafter, since the laminated body is pressed and pressure-bonded, the step gap portion is crushed. Therefore, as the number of stacked layers increases and the thickness of the green sheet decreases, the effect of accumulated steps increases.

  As a result, the green sheet sandwiched between the internal electrode pattern layers where there is no stepped gap portion is more strongly pressed and the density is increased, but the density of the green sheet sandwiched between the portions where the stepped gap portion is present is Compared with other portions, the density is lowered, and a density difference is generated in the laminate. Moreover, in the green sheet pinched | interposed into the part in which a step-shaped clearance gap part exists, the problem that the adhesiveness of an upper and lower green sheet falls arises.

  The laminate is then cut into chips and then fired, but there is a problem that when the laminate having the above-mentioned problems is fired, it is easily cracked between the layers. There is also a problem that structural defects such as chip deformation, short circuit failure, cracks, and delamination frequently occur after the laminate is fired.

  In order to solve such a problem, for example, as shown in the following Patent Document 1 to Patent Document 5, etc., by printing a dielectric paste, a step gap portion generated between the internal electrode patterns of a predetermined pattern is blanked. A method of filling with a pattern layer has been proposed. According to these methods, the surface including the internal electrode layer can be flattened, and various problems of the ceramic capacitor due to the above-described step can be improved.

However, in recent years, with the increase in capacitance and integration, the number of stacked green sheets has increased, and even if a blank pattern layer is formed, delamination between green sheets becomes a problem. It is coming. In addition, stacking misalignment between green sheets has become a problem.
JP 56-94719 A JP-A-3-74820 JP-A-9-106925 JP 2001-126951 A JP-A-2001-358036.

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a method for manufacturing a multilayer ceramic electronic component that suppresses stacking misalignment, has excellent stackability, and has low delamination. .

In order to achieve the above object, a method for producing a multilayer ceramic electronic component according to the present invention comprises:
A step of stacking a predetermined number of green sheets to obtain a preliminary laminate,
Drying the preliminary laminate,
Stacking the dried pre-laminated body to obtain a final laminated body;
Cutting the final laminate to form a green chip;
Firing the green chip.

  As a result of intensive studies on the cause of delamination, the present inventors, as a result of the green chip undergoing a solidification / drying process and a binder removal process, residual solvent and residual plasticizer remaining inside the green chip It was thought that delamination was caused by volatilization. That is, as the number of stacked green sheets increases, the residual solvent and residual plasticizer inside the green chip are less likely to volatilize, and these solvents or plasticizers volatilize at a time in the solidification / drying process and binder removal process. Therefore, we thought that delamination is likely to occur.

  Therefore, the present inventors considered that a predetermined number of green sheets are stacked to form a preliminary laminate, and then the preliminary laminate is dried, and the dried preliminary laminate is stacked to obtain a final laminate. It was. By doing so, it was confirmed by experiments that residual solvents, plasticizers, and the like are less likely to volatilize at a time in the solidification / drying step and the binder removal step of the final laminate, and delamination can be suppressed.

  Preferably, the reduction rate of the weight of the pre-laminated body after drying with respect to the weight of the pre-laminated body before drying is 0.2 to 1.0%, more preferably 0.2 to 0.6%. When the rate of decrease is small, drying is not sufficient, and residual solvent or plasticizer remains in the green sheet, making it difficult to effectively suppress delamination. On the other hand, when the reduction rate is too large, the layer will be dried too much, the stacking property will be lowered, and when the final laminate is obtained by pressing, there is a tendency that stacking misalignment tends to occur between the preliminary laminates.

  Although the drying temperature at the time of drying of a preliminary | backup laminated body is not specifically limited, Preferably it is 80-150 degreeC. If the drying temperature is too low, it takes time for drying and is not efficient, and if the drying temperature is too high, the support sheet holding the preliminary laminate tends to be deformed.

  Preferably, when the pre-laminated body after drying is stacked, it is pressed against the pre-stacked pre-laminated body at a pressure of 0.1 MPa or more, more preferably 0.15 MP, particularly preferably 0.5 MPa or more. If this pressure is too low, stacking deviation tends to occur.

  Preferably, when stacking the pre-laminated body after drying, the pre-laminated body already stacked is pressed under a temperature condition of 50 to 85 ° C. If this temperature is too low, stacking misalignment tends to occur.

  Preferably, the preliminary laminated body is formed by stacking 10 to 100 sheets of green sheets. If the number of laminated green sheets is too small, the number of times the preliminary laminated body is laminated tends to increase in order to obtain a final laminated body having the required number of laminated layers, and the number of manufacturing steps tends to increase. Moreover, when there are too many green sheets laminated | stacked, there exists a tendency for a residual solvent and a residual plasticizer to increase, and it exists in the tendency for the effect of this invention to decrease.

  Preferably, 10 to 100 preliminary laminates are stacked to form a final laminate. When the number of stacked preliminary laminates is too small, the number of green sheets stacked in the final laminate decreases, and when the number of stacked layers is too large, the number of man-hours increases.

  An electrode layer having a predetermined pattern is formed on the surface of the green sheet. As the multilayer ceramic electronic component manufactured by the method of the present invention, for example, a multilayer ceramic capacitor is exemplified, and in that case, a large number of electrode layers are stacked.

  Preferably, the dried preliminary laminated body is conveyed by a conveying plate, and the preliminary laminated body is pressed against the already laminated preliminary laminated body with a pressure of 0.1 MPa or more by using the conveying plate.

  Preferably, the final laminate is temporarily pressed with a pressure of 5 MPa or more by a temporary pressing device. Or when the press pressure capacity of the transport plate is high, the preliminary laminated body is used at a pressure of 5 MPa or more with respect to the pre-laminated body already stacked using the transport plate without using a temporary pressing device. It may be pressed.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor manufactured by a method for manufacturing a multilayer ceramic electronic component according to an embodiment of the present invention.
2 (A) to 2 (C) are main part cross-sectional views showing an example of a lamination process of a green sheet and an electrode layer,
3 (A) to 3 (C) are main part cross-sectional views showing a continuation process of FIG. 2 (C),
4 (A) to 4 (C) are main part cross-sectional views showing a continuation process of FIG. 3 (C),
5 (A) to 5 (C) are main part cross-sectional views showing a continuation process of FIG. 4 (C),
6 (A) to 6 (C) are main part cross-sectional views showing a continuation process of FIG. 5 (C),
FIG. 7 is a cross-sectional view of an essential part showing a step subsequent to FIG.
8A, FIG. 8A, and FIG. 8B are schematic views showing the subsequent steps of FIG.
FIG. 9 is a schematic view showing stacking deviation.

Overall Configuration of Multilayer Ceramic Capacitor First, the overall configuration of a multilayer ceramic capacitor will be described as an embodiment of an electronic component according to the present invention.

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

  In the present embodiment, the internal electrode layer 12 is formed by a transfer method, as will be described in detail later.

  The material of the dielectric layer 10 is not particularly limited, and is made of a dielectric material such as calcium titanate, strontium titanate and / or barium titanate. The thickness of each dielectric layer 10 is not particularly limited, but is generally several μm to several hundred μm. In particular, in this embodiment, the thickness is preferably 5 μm or less, more preferably 3 μm or less, and particularly preferably 1.5 μm or less.

  Although the material of the terminal electrodes 6 and 8 is not particularly limited, copper, a copper alloy, nickel, a nickel alloy, or the like is usually used, but silver, an alloy of silver and palladium, or the like can also be used. The thickness of the terminal electrodes 6 and 8 is not particularly limited, but is usually about 10 to 50 μm.

  The shape and size of the multilayer ceramic capacitor 2 may be appropriately determined according to the purpose and application. 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) × horizontal (0.3 to 5.0 mm, preferably 0.3 to 1.6 mm) × thickness (0.1 to 1.9 mm, preferably 0.3 to 1.6 mm).

Method for Manufacturing Multilayer Ceramic Capacitor Next, an example of a method for manufacturing the multilayer ceramic capacitor 2 according to this embodiment will be described.

(1) First, a dielectric paste (green sheet paste) is prepared in order to manufacture a ceramic green sheet that will form the dielectric layer 10 shown in FIG. 1 after firing.

  The dielectric paste is composed of an organic solvent-based paste obtained by kneading a dielectric material (ceramic powder) and an organic vehicle.

  As the dielectric material, various compounds to be complex oxides and oxides, for example, carbonates, nitrates, hydroxides, organometallic compounds, and the like are appropriately selected and used by mixing. The dielectric material is usually used as a powder having an average particle size of 0.4 μm or less, preferably about 0.1 to 3.0 μm. In order to form a very thin green sheet, it is desirable to use a powder finer than the thickness of the green sheet.

  An organic vehicle is obtained by dissolving a binder resin in an organic solvent. In this embodiment, polyvinyl butyral resin is used as the binder resin used in the organic vehicle. The polymerization degree of the polyvinyl butyral resin is 1000 or more and 1700 or less, preferably 1400 to 1700. The degree of butyralization of the resin is greater than 64% and less than 78%, preferably greater than 64% and 70% or less, and the residual acetyl group content is less than 6%, preferably 3% or less.

  The degree of polymerization of the polyvinyl butyral resin can be measured by, for example, the degree of polymerization of the raw material polyvinyl acetal resin. Further, the degree of butyralization can be measured in accordance with, for example, JISK6728. Furthermore, the amount of residual acetyl groups can be measured according to JISK6728.

  The organic solvent used for the organic vehicle is not particularly limited, and for example, organic solvents such as terpineol, alcohol, butyl carbitol, acetone, and toluene are used. In the present embodiment, the organic solvent preferably includes an alcohol solvent and an aromatic solvent, and the total mass of the alcohol solvent and the aromatic solvent is 100 parts by mass. More than 20 parts by mass. When the content of the aromatic solvent is too small, the sheet surface roughness tends to increase. When the content is too large, paste filtration characteristics deteriorate, and the sheet surface roughness also increases and deteriorates.

  Examples of alcohol solvents include methanol, ethanol, propanol, butanol and the like. Examples of the aromatic solvent include toluene, xylene, benzyl acetate and the like.

  Binder resin should be dissolved and filtered in advance in at least one alcohol solvent of methanol, ethanol, propanol, or butanol, and a dielectric powder and other components should be added to the solution. Is preferred. A binder resin having a high degree of polymerization is difficult to dissolve in a solvent, and the dispersibility of the paste tends to be deteriorated by an ordinary method. In the method of the present embodiment, the paste dispersibility can be improved in order to add the ceramic powder and other components to the solution after dissolving the binder resin having a high degree of polymerization in the above-mentioned good solvent, Generation | occurrence | production of undissolved resin can be suppressed. In addition, in solvents other than the above-mentioned solvents, the solid content concentration cannot be increased, and the change in lacquer viscosity with time tends to increase.

  The dielectric paste may contain additives selected from various dispersants, plasticizers, antistatic agents, dielectrics, glass frit, insulators, and the like as necessary.

  Using this dielectric paste, by a doctor blade method or the like, for example, as shown in FIG. 3 (A), the carrier sheet 30 as the second support sheet is preferably 0.5 to 30 μm, more preferably 0.00. The green sheet 10a is formed with a thickness of about 5 to 10 μm. The green sheet 10 a is dried after being formed on the carrier sheet 30. 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% as compared with that before drying. The thickness of the green sheet after drying is preferably 3 μm or less.

  (2) Separately from the carrier sheet 30 described above, as shown in FIG. 2A, a carrier sheet 20 as a first support sheet is prepared, and a release layer 22 is formed thereon, on which An electrode layer 12a having a predetermined pattern is formed, and before and after that, a blank pattern layer 24 having substantially the same thickness as the electrode layer 12a is formed on the surface of the release layer 22 where the electrode layer 12a is not formed.

  As the carrier sheets 20 and 30, for example, a PET (polyethylene terephthalate) film or the like is used, and a film coated with silicon or the like is preferable in order to improve peelability. Although the thickness of these carrier sheets 20 and 30 is not specifically limited, Preferably, it is 5-100 micrometers. The thicknesses of these carrier sheets 20 and 30 may be the same or different.

  The release layer 22 preferably includes the same dielectric particles as the dielectric that constitutes the green sheet 10a shown in FIG. In addition to the dielectric particles, the release layer 22 includes a binder, a plasticizer, and a release agent. The particle size of the dielectric particles may be the same as the particle size of the dielectric particles contained in the green sheet, but is preferably smaller.

  The method for applying the release layer 22 is not particularly limited. However, since it is necessary to form the release layer 22 very thinly, for example, an application method using a wire bar coater or a die coater is preferable.

  The binder for the release layer 22 is made of, for example, an organic material or an emulsion made of acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a copolymer thereof. The binder contained in the release layer 22 may be the same as or different from the binder contained in the green sheet 10a, but is preferably the same.

  Although it does not specifically limit as a plasticizer for the peeling layer 22, For example, a phthalate ester, dioctyl phthalate, adipic acid, phosphate ester, glycols etc. are illustrated. The plasticizer contained in the release layer 22 may be the same as or different from the plasticizer contained in the green sheet 10a.

  The release agent for the release layer 22 is not particularly limited, and examples thereof include paraffin, wax, silicone oil, and the like. The release agent contained in the release layer 22 may be the same as or different from the release agent contained in the green sheet 10a.

  The binder is contained in the release layer 22 in an amount of preferably 2.5 to 200 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably about 8 to 30 parts by weight with respect to 100 parts by weight of the dielectric particles. .

  The plasticizer is preferably contained in the release layer 22 in an amount of 0 to 200 parts by mass, preferably 20 to 200 parts by mass, and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the binder.

  The release agent is preferably contained in the release layer 22 at 0 to 100 parts by mass, preferably 2 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the binder.

  After the release layer 22 is formed on the surface of the carrier sheet 30, as shown in FIG. 2A, an electrode layer 12a that will constitute the internal electrode layer 12 after firing is formed on the surface of the release layer 22 in a predetermined pattern. Form. The thickness of the electrode layer 12a is preferably about 0.1 to 2 μm, more preferably about 0.1 to 1.0 μm. The electrode layer 12a may be composed of a single layer, or may be composed of a plurality of layers having two or more different compositions.

  The electrode layer 12a is formed on the surface of the release layer 22 by a thick film forming method using an electrode paste. In order to form the electrode layer 12a on the surface of the release layer 22 by a screen printing method or a gravure printing method which is a kind of thick film method, the following is performed.

  First, an electrode paste is prepared. The electrode paste is prepared by kneading a conductive material made of various conductive metals or alloys, or various oxides, organometallic compounds, resinates, or the like, which become the conductive material described above after firing, and an organic vehicle.

  As a conductive material used when manufacturing the electrode paste, Ni, Ni alloy, or a mixture thereof is used. There are no particular restrictions on the shape of such a conductive material, such as a spherical shape or a flake shape, or a mixture of these shapes may be used. The average particle diameter of the conductor material is usually 0.1 to 2 μm, preferably about 0.2 to 1 μm.

  The organic vehicle contains a binder and a solvent. Examples of the binder include ethyl cellulose, acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, and copolymers thereof, but a butyral system such as polyvinyl butyral is particularly preferable.

  The binder is preferably included in the electrode paste in an amount of 8 to 20 parts by mass with respect to 100 parts by mass of the conductive material (metal powder). As the solvent, any known solvents such as terpineol, butyl carbitol, and kerosene can be used. The solvent content is preferably about 20 to 55% by mass with respect to the entire paste.

  In order to improve adhesion, the electrode paste preferably contains a plasticizer. Examples of the plasticizer include phthalic acid esters such as benzylbutyl phthalate (BBP), adipic acid, phosphoric acid esters, glycols, and the like. The plasticizer is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the binder in the electrode paste. In addition, 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 12a to fall remarkably. In order to improve the transferability of the electrode layer 12a, it is preferable to add a plasticizer and / or a pressure-sensitive adhesive to the electrode paste to improve the adhesion and / or the pressure-sensitive adhesiveness of the electrode paste.

  After or before the electrode paste layer having a predetermined pattern is formed on the surface of the release layer 22 by the printing method, the surface of the release layer 22 on which the electrode layer 12a is not formed is substantially the same thickness as the electrode layer 12a. The blank pattern layer 24 is formed.

  The blank pattern layer 24 shown in FIG. 2A can be formed on the surface of the release layer 22 by a thick film forming method such as a printing method using an electrode level difference absorbing printing paste. When a blank pattern layer (FIG. 2 (A)) is formed on the surface of the release layer 22 by screen printing, which is one type of thick film method, it is performed as follows.

  First, an electrode level difference absorbing printing paste is prepared. The electrode level difference absorbing printing paste is composed of an organic solvent-based paste obtained by kneading a dielectric material (ceramic powder) and an organic vehicle.

  As the dielectric material used when manufacturing the electrode level difference absorbing printing paste, the dielectric material having the same average particle diameter as the dielectric material constituting the green sheet 10a is used. In the electrode level difference absorbing printing paste, dielectric particles (ceramic powder) are contained in an amount of 30 to 50 parts by mass, more preferably 40 to 50 parts by mass with respect to the entire paste. If the content of the ceramic powder is too small, the paste viscosity becomes small and printing is difficult. Moreover, when there is too much content rate of ceramic powder, it exists in the tendency for it to become difficult to make printing thickness thin.

  The organic vehicle contains a binder and a solvent. Examples of the binder include ethyl cellulose, acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, and copolymers thereof, but a butyral system such as polyvinyl butyral is particularly preferable.

  The degree of polymerization of the butyral binder contained in this electrode level difference absorbing printing paste is set to be equal to or higher than the degree of polymerization of the binder contained in the paste for forming the green sheet 10a, and preferably high. For example, when the degree of polymerization of polyvinyl butyral as a binder contained in the green sheet paste is 1000 to 1700, the binder contained in the electrode level difference absorbing print paste is 1400 or more, more preferably 1700 or more, particularly preferably Polyvinyl butyral or polyvinyl acetal having a degree of polymerization of 2400 or more. Of these, polyvinyl acetal having a polymerization degree of 2000 or more is preferable.

  When the binder of the electrode level difference absorbing printing paste is polyvinyl butyral, it is preferable that the degree of butyralization is in the range of 64 to 74 mol%. Moreover, when it is a polyvinyl acetal, it is preferable that the acetalization degree is 66-74 mol%.

  The binder is preferably contained in the electrode paste absorbing print paste in an amount of 3 to 10 parts by mass with respect to 100 parts by mass of the dielectric material. More preferably, 4 to 8 parts by mass are included.

  Examples of the solvent include known ones such as terpineol, butyl carbitol, and kerosene. Either can be used. As for the solvent content, about 50-70 mass parts is preferable with respect to the whole paste.

  In addition, the electrode level difference absorbing printing paste may contain various additives such as a dispersant, a plasticizer and / or an adhesive and an antistatic agent.

  Although there is no limitation in particular as a dispersing agent, For example, polymeric materials, such as ester polymer and carboxylic acid, are used, Preferably the content is 0.25-1. 5 parts by mass, more preferably 0.5 to 1.0 parts by mass is preferably contained.

  The plasticizer is not particularly limited, and for example, phthalic acid esters such as benzylbutyl phthalate (BBP), adipic acid, phosphoric acid esters, glycols, and the like are used. The content thereof is preferably 10 to 200 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the binder.

  The antistatic agent is not particularly limited. For example, an imidazoline-based antistatic agent is used, and the content thereof is 0.1 to 0.75 parts by mass, more preferably 100 parts by mass of the ceramic powder. It is preferable to contain by 0.25-0.5 mass part.

  As shown in FIG. 2A, this electrode level difference absorbing print paste is printed on the blank pattern portion between the electrode layers 12a. Thereafter, the electrode layer 12a and the blank pattern layer 12a are dried as necessary. The drying temperature is not particularly limited, but is preferably 70 to 120 ° C, and the drying time is preferably 5 to 15 minutes.

  (3) Separately from the carrier sheets 20 and 30, the adhesive layer transfer sheet in which the adhesive layer 28 is formed on the surface of the carrier sheet 26 as the third support sheet, as shown in FIG. prepare. The carrier sheet 26 is composed of a sheet similar to the carrier sheets 20 and 30.

  The composition of the adhesive layer 28 is the same as that of the release layer 22 except that it does not contain a release agent. That is, the adhesive layer 28 includes a binder, a plasticizer, and a release agent. The adhesive layer 28 may contain the same dielectric particles as the dielectric constituting the green sheet 10a. However, when forming an adhesive layer having a thickness smaller than the particle diameter of the dielectric particles, the dielectric particles It is better not to include. In addition, when dielectric particles are included in the adhesive layer 28, the particle size of the dielectric particles is preferably smaller than the particle size of the dielectric particles included in the green sheet.

  The plasticizer is preferably contained in the adhesive layer 28 in an amount of 0 to 200 parts by mass, preferably 20 to 200 parts by mass, and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the binder.

  The adhesive layer 28 further contains an antistatic agent, and the antistatic agent contains one of the imidazoline-based surfactants, and the weight-based addition amount of the antistatic agent is the weight of the binder (organic polymer material). It is preferable that it is below the reference addition amount. That is, it is preferable that the antistatic agent is contained in the adhesive layer 28 in an amount of 0 to 200 parts by weight, preferably 20 to 200 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the binder.

  The thickness of the adhesive layer 28 is preferably about 0.02 to 0.3 μm, and is preferably thinner than the average particle size of the dielectric particles contained in the 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 strength is reduced, and if it is too thick, a gap is easily formed inside the element body after sintering depending on the thickness of the adhesive layer, and the electrostatic capacity corresponding to the volume. Tends to decrease significantly.

  The adhesive layer 28 is formed on the surface of the carrier sheet 26 as the third support sheet by a method such as a bar coater method, a die coater method, a reverse coater method, a dip coater method, or a kiss coater method, and is dried as necessary. . The drying temperature is not particularly limited, but is preferably room temperature to 80 ° C., and the drying time is preferably 1 to 5 minutes.

  (4) In order to form an adhesive layer on the surfaces of the electrode layer 12a and the blank pattern layer 24 shown in FIG. 2A, a transfer method is employed in this embodiment. That is, as shown in FIG. 2B, the adhesive layer 28 of the carrier sheet 26 is pressed against the surfaces of the electrode layer 12a and the blank pattern layer 24 as shown in FIG. By peeling off the carrier sheet 26, the adhesive layer 28 is transferred to the surfaces of the electrode layer 12a and the blank pattern layer 24 as shown in FIG. The transfer of the adhesive layer 28 may be performed on the surface of the green sheet 10a shown in FIG.

  The heating temperature during transfer is preferably 40 to 100 ° C., and the applied pressure is preferably 0.2 to 15 MPa. The pressurization may be a pressurization or a calender roll, but is preferably performed by a pair of rolls.

  Thereafter, the electrode layer 12a is bonded to the surface of the green sheet 10a formed on the surface of the carrier sheet 30 shown in FIG. For that purpose, as shown in FIG. 3B, the electrode layer 12a and the blank pattern layer 24 of the carrier sheet 20 are pressed together with the carrier sheet 20 onto the surface of the green sheet 10a via the adhesive layer 28, and heated and pressurized. As shown in FIG. 3C, the electrode layer 12a and the blank pattern layer 24 are transferred to the surface of the green sheet 10a. However, since the carrier sheet 30 on the green sheet side is peeled off, when viewed from the green sheet 10 a side, the green sheet 10 a is transferred to the electrode layer 12 a and the blank pattern layer 24 via the adhesive layer 28.

  The heating and pressurization at the time of transfer may be pressurization / heating with a press or pressurization / heating with a calender roll, but is preferably performed with a pair of rolls. The heating temperature and pressure are the same as when the adhesive layer 28 is transferred.

  2A to 3C, a single layer of electrode layer 12a having a predetermined pattern is formed on a single green sheet 10a. In order to laminate the green sheet 10a on which the electrode layer 12a is formed, for example, the steps shown in FIGS. 4A to 6C may be repeated. 4 (A) to 6 (C), members that are the same as those shown in FIGS. 3 (A) to 4 (C) are denoted by the same reference numerals, and description thereof is partially omitted. .

  First, as shown in FIGS. 4A to 4C, the adhesive layer 28 is transferred to the counter electrode layer side surface (back surface) of the green sheet 10a. Thereafter, as shown in FIGS. 5A to 5C, the electrode layer 12 a and the blank pattern layer 24 are transferred to the back surface of the green sheet 10 a through the adhesive layer 28.

  Next, as shown in FIGS. 6A to 6C, the green sheet 10 a is transferred to the surfaces of the electrode layer 12 a and the blank pattern layer 24 via the adhesive layer 28. Thereafter, by repeating these transfers, as shown in FIG. 7, a preliminary laminated body Un in which the electrode layers 12a and the green sheets 10a are alternately laminated is obtained.

  Note that without adopting the steps shown in FIGS. 5C to 6C, the lower carrier sheet 20 is not peeled off from the step shown in FIG. 5B, but the upper carrier sheet is peeled off. On top of that, a laminate unit U1 shown in FIG. 4C may be laminated. Thereafter, the upper carrier sheet 20 is peeled off again, and the laminate unit U1 shown in FIG. 4C is laminated thereon, and the operation of peeling the upper carrier sheet 20 again is repeated. As shown in FIG. 4, a pre-laminated body Un in which the electrode layers 12a and the green sheets 10a are alternately laminated is obtained. The method of stacking (stacking) the stacked unit U1 shown in FIG. 4C to obtain the preliminary stacked body Un is superior in stacking work efficiency.

  In the present embodiment, the number of green sheets 10a stacked in the preliminary stacked body Un shown in FIG. 7 is not particularly limited, but is preferably 10 to 100.

  In the present embodiment, next, either the upper carrier sheet 20 or the lower carrier sheet 30 in the preliminary laminate Un shown in FIG. 7 is peeled off, and the preliminary laminate Un is dried in that state. The drying temperature during the drying treatment is preferably 80 to 120 ° C. The drying time is, for example, 15 minutes to 3 hours.

  At the time of drying, the reduction rate of the weight of the preliminary laminate Un after drying with respect to the weight of the preliminary laminate Un before drying is 0.2 to 1.0%, more preferably 0.2 to 0.6%. The drying process is performed as follows.

  As shown in FIG. 8 (A) and FIG. 8 (B), the dried pre-laminated body Un is transported onto the lower mold of the temporary press device by the transport plate 50 together with the carrier sheet 20 or 30. Therefore, the pressing mechanism 52 presses the preliminary laminated body Un that has been temporarily placed. The pressure at the time of temporary placement of the preliminary laminated body Un by the transport plate 50 is a pressure of 0.1 MPa or more, preferably 0.5 MPa or more.

  At the time of temporary placement of the preliminary laminate Un by the transport plate 50, the transport plate 50 is heated and the preliminary stack Un is heated to a predetermined temperature. The heating temperature is preferably 50 to 85 ° C. Although the pressurization time at the time of temporary placement is not particularly limited, it is usually 1 to 60 seconds, preferably about 1 to 30 seconds.

  The pre-laminated body Un to be stacked is always dried before being temporarily placed. Although the total number of stacks of the preliminary laminate Un is not particularly limited, it is preferably about 10 to 100. As the total number of the stacked stacks of the preliminary stacked bodies Un increases, the total number of stacked final stacked bodies Uf increases.

  When the preliminary laminated body Un is laminated until the final laminated body Uf is reached, the transport plate shown in FIG. 8B moves in the horizontal direction from above the final laminated body Uf, and is not shown in the figure. The upper die is pulled down toward the lower die 40, and a temporary press is performed.

  The pressure at the time of temporary pressing is a pressure of 5 MPa or more, preferably 5 to 10 MPa. If the pressure of the temporary press is too low, it tends to be difficult to maintain the shape as a laminate in subsequent steps (for example, a cutting step). Moreover, when the pressure of a temporary press is too large, there exists a tendency for the deformation | transformation of a laminated body to become large, and it is not preferable.

  Further, it is preferable that the lower mold 40 and the upper mold are heated to a predetermined temperature during the temporary pressing. Although the heating temperature at the time of temporary press is not specifically limited, Preferably it is 50-90 degreeC. The pressurization time during temporary pressing is preferably 1 to 60 seconds.

  In addition, when the press pressure capability of the conveyance board 50 is high, you may temporarily press the final laminated body Uf using the conveyance board 50, without using a temporary press apparatus.

  (5) Thereafter, the laminate is cut into a predetermined size to form a green chip. The green chip is subjected to solidification / drying processing, binder removal processing, and baking processing, and heat treatment is performed to reoxidize the dielectric layer.

Solidification and drying treatment
In the case where a base metal such as Ni or Ni alloy is used for the conductor material of the internal electrode layer, the following conditions are particularly preferable.

Temperature increase rate: 10-50 ° C./hour,
Holding temperature: 150-200 ° C.
Retention time: 2-6 hours,
Atmosphere: Air.

  The binder removal treatment may be performed under normal conditions, but when a base metal such as Ni or Ni alloy is used as the conductor material of the internal electrode layer, it is particularly preferable to perform under the following conditions.

Temperature increase rate: 5 to 300 ° C./hour,
Holding temperature: 200-600 ° C.
Retention time: 0.5-20 hours,
Atmosphere: A mixed gas of humidified N ₂ and H ₂ .

  The firing conditions are preferably the following conditions.

Temperature increase rate: 50 to 500 ° C./hour,
Holding temperature: 1100-1300 ° C.
Retention time: 0.5-8 hours,
Cooling rate: 50 to 500 ° C./hour,
Atmospheric gas: A mixed gas of humidified N ₂ and H ₂ or the like.

However, the oxygen partial pressure in the air atmosphere during firing is preferably 10 ⁻² Pa or less, particularly 10 ⁻² to 10 ⁻⁸ Pa. If the above range is exceeded, the internal electrode layer tends to oxidize, and if the oxygen partial pressure is too low, the electrode material of the internal electrode layer tends to abnormally sinter and tend to break.

The heat treatment after such firing is preferably carried out at a holding temperature or maximum temperature of preferably 1000 ° C. or higher, more preferably 1000 to 1100 ° C. If the holding temperature or maximum temperature during heat treatment is less than the above range, the dielectric material is insufficiently oxidized and the insulation resistance life tends to be shortened. In addition to a decrease, it tends to react with the dielectric substrate and shorten its lifetime. The oxygen partial pressure during the heat treatment is higher than the reducing atmosphere during firing, and is preferably 10 ⁻³ Pa to 1 Pa, more preferably 10 ⁻² Pa to 1 Pa. Below the range, it is difficult to re-oxidize the dielectric layer 10, and when the range is exceeded, the internal electrode layer 12 tends to oxidize.

The sintered body (element body 4) thus obtained is subjected to end surface polishing by, for example, barrel polishing, sand plast, etc., and terminal electrode paste 6 is baked to form terminal electrodes 6 and 8. The firing conditions for the terminal electrode paste are preferably, for example, about 10 minutes to 1 hour at 600 to 800 ° C. in a humidified mixed gas of N ₂ and H ₂ . Then, if necessary, a pad layer is formed on the terminal electrodes 6 and 8 by plating or the like. In addition, what is necessary is just to prepare the paste for terminal electrodes like the above-mentioned electrode paste.

  The multilayer ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board by soldering or the like and used for various electronic devices.

  In the method for manufacturing a multilayer ceramic capacitor according to the present embodiment, a predetermined number of green sheets 10a are stacked to form a preliminary stacked body Un, and then the preliminary stacked body Un is dried, and the dried preliminary stacked body Un is stacked. Thus, the final laminate Uf is obtained. By doing so, residual solvents or plasticizers are less likely to volatilize at a time in the solidification / drying step and the binder removal step of the final laminate Un, and delamination can be suppressed.

  Moreover, in this embodiment, since the decreasing rate of the weight of the pre-lamination body Un after drying with respect to the weight of the pre-lamination body Un before drying is made into the predetermined range, it does not dry too much and stack property is good. It is sufficient, and when the final laminated body is obtained by pressing, lamination deviation between the preliminary laminated bodies can be suppressed.

  The present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention.

  For example, the method of the present invention is not limited to a method for manufacturing a multilayer ceramic capacitor, but can also be applied as a method for manufacturing other multilayer electronic components.

  Hereinafter, the present invention will be described based on further detailed examples, but the present invention is not limited to these examples.

Example 1
Preparation of Green Sheet Paste BaTiO ₃ powder (BT-02 / Sakai Chemical Industry Co., Ltd.) was used as a starting material for ceramic powder. (Ba _0.6 Ca _0.4 ) SiO ₃ : 1.48 parts by mass, Y ₂ O ₃ : 1.01 parts by mass, MgCO ₃ : 0.72% by mass with respect to 100 parts by mass of this BaTiO ₃ powder. , Cr ₂ O ₃ : 0.13 mass%, and V ₂ O ₅ : 0.045 mass% were prepared ceramic powder subcomponent additives.

First, only the minor component additive was mixed with a ball mill to form a slurry. That is, auxiliary components (total amount 8.8 g) and ethanol / n-propanol 1: 1 solvent (16 g) were preliminarily pulverized with a ball mill for 20 hours. Next, with respect to BaTiO ₃ : 191.2 g, a preliminary pulverized slurry of additive additives, ethanol: 38 g, n-propanol: 38 g, xylene: 28 g, mineral spirit: 14 g, and a plasticizer component DOP (dioctyl phthalate): 6 g and polyethylene glycol-based nonionic dispersant (HLB = 5-6): 1.4 g as a dispersant were added and mixed by a ball mill for 4 hours. In addition, as the polyethylene glycol-based nonionic dispersant (HLB = 5 to 6) as a dispersant, a block polymer of polyethylene glycol and a fatty acid ester was used.

  Next, 15% lacquer of BH6 (polyvinyl butyral resin / PVB) manufactured by Sekisui Chemical Co., Ltd. (BH6 manufactured by Sekisui Chemical Co., dissolved in ethanol / n-propanol = 1: 1) is solidified as a binder resin in the dispersion paste. 6% by mass was added as a minute (80 g as lacquer addition amount). Thereafter, the resultant was ball milled for 16 hours to obtain a ceramic paste (green sheet paste).

  The degree of polymerization of the polyvinyl butyral resin as the binder resin was 1400, the degree of butyralization was 69% ± 3%, and the amount of residual acetyl groups was 3 ± 2%. This binder resin was contained in the ceramic paste at 6 parts by mass with respect to 100 parts by mass of ceramic powder (including ceramic powder subcomponent additives). Further, when the total volume of the ceramic powder, the binder resin, and the plasticizer in the ceramic paste was 100% by volume, the volume ratio occupied by the ceramic powder was 67.31% by volume. Moreover, the mass ratio of the ceramic powder in the whole paste was 49 mass%.

  Moreover, DOP as a plasticizer was contained in the ceramic paste at 50 parts by mass with respect to 100 parts by mass of the binder resin. The water was contained in an amount of 2 parts by mass with respect to 100 parts by mass of the ceramic powder. The polyethylene glycol-based nonionic dispersant as the dispersant was contained in an amount of 0.7 parts by mass with respect to 100 parts by mass of the ceramic powder.

  Further, in the paste, 5 parts by mass of mineral spirit which is at least one of hydrocarbon solvents, industrial gasoline, kerosene, and solvent naphtha is added to 100 parts by mass of the ceramic powder. It was. Further, the paste contains an alcohol solvent and an aromatic solvent as a solvent, the total mass of the alcohol solvent and the aromatic solvent is 100 parts by mass, and toluene as an aromatic solvent is 15 masses. Department was included.

Production of Green Sheet The paste obtained as described above was applied to a PET film as a support film shown in FIG. 3 (A) with a wire bar coater at a thickness of 1.2 μm and dried to give a green sheet 10a. Was made. The coating speed was 50 m / min, and the drying conditions were a temperature in the drying furnace of 60 ° C. to 70 ° C. and a drying time of 2 minutes.

Release layer paste A paste was prepared in the same manner as the green sheet paste except that BaTiO ₃ in the green sheet paste was changed to BT-01, and the paste was ethanol: propanol: xylene (42.5: 42). .5: 15) diluted 5 times with a mixed solvent was used as a peeling paste.

Adhesive layer paste An organic vehicle was used as the adhesive layer paste. Specifically, a mixed solution of 50 parts by mass of bis (2-hexylhexyl) phthalate DOP as a plasticizer and 900 parts by mass of MEK as a plasticizer is further diluted 10 times with MEK with respect to 100 parts by mass of polyvinyl butyral resin. Thus, an adhesive layer paste was obtained.

Internal electrode paste (transferred electrode layer paste)
For 100 parts by mass of Ni particles having an average particle size of 0.2 μm,
BaTiO ₃ powder (BT-01 / Sakai Chemical Industry Co., Ltd.): 20 parts by weight,
Organic vehicle: 58 parts by mass (8 parts by mass of polyvinyl butyral resin dissolved in 92 parts by mass of terpineol),
Bis (2-hexylhexyl) phthalate DOP as a plasticizer: 50 parts by mass
Terpineol: 5 parts by mass,
Dispersant: 1 part by weight,
Acetone: 45 parts by weight
Was added and kneaded with three rolls to form a slurry for internal electrodes.

Preparation of Electrode Step Absorption Printing Paste The same ceramic powder and subcomponent additives used for the green sheet paste were prepared so as to have the same blending ratio.

  To the ceramic powder and auxiliary component additive (150 g), an ester polymer dispersant (1.5 g), terpineol (5 g), acetone (60 g), and dioctyl phthalate (5 g) as a plasticizer are added. And mixed for 4 hours. Next, 8% lacquer of 8% lacquer (polyvinyl butyral resin having a polymerization degree of 1450 and a butyralization degree of 69 mol% ± 3%) manufactured by Sekisui Chemical Co., Ltd. was added to this mixed solution. Mass% and terpineol 92 mass%) was added in an amount of 120 g and mixed for 16 hours. Then, the excess solvent acetone was removed, and paste was produced by adding 40-100g of terpineol as viscosity adjustment.

Formation of Green Sheet, Transfer of Adhesive Layer and Electrode Layer First, using the above dielectric green sheet paste, a 1.2 μm thick green using a wire bar coater on a PET film (second support sheet) A sheet was formed. Next, in order to form a release layer on another PET film (first support sheet), the above release layer paste is applied and dried with a wire bar coater to form a 0.2 μm release layer. did.

  Electrode layer 12a and blank pattern layer 24 were formed on the surface of the release layer. The electrode layer 12a was formed with a thickness of 1 μm by a printing method using the internal electrode paste. The blank pattern layer 24 was formed with a thickness of 1 μm by a printing method using the above electrode level difference absorbing printing paste. In printing using the electrode level difference absorbing printing paste, no inconvenience such as the paste flowing out of the mesh of the printing plate making was observed.

  Further, an adhesive layer 28 was formed on another PET film (third support sheet). The adhesive layer 28 was formed with a thickness of 0.1 μm by the wire bar coater using the above adhesive layer paste.

  First, the adhesive layer 28 was transferred to the surfaces of the electrode layer 12a and the blank pattern layer 24 by the method shown in FIG. At the time of transfer, a pair of rolls were used, the pressure was 1 MPa, the temperature was 80 ° C., and it was confirmed that transfer could be performed satisfactorily.

  Next, the internal electrode layer 12a and the blank pattern layer 24 were adhered (transferred) to the surface of the green sheet 10a through the adhesive layer 28 by the method shown in FIG. At the time of transfer, a pair of rolls were used, the pressure was 1 MPa, the temperature was 80 ° C., and it was confirmed that transfer could be performed satisfactorily.

  Next, the internal electrode layer 12a and the green sheet 10a were successively laminated by the method shown in FIGS. 4 to 7 to form a plurality of preliminary laminated bodies Un. The number of laminated green sheets 10a in each preliminary laminated body Un was 30 layers. Next, each preliminary laminate was dried.

  Drying treatment conditions were 100 ° C. and 120 minutes. The weight of the pre-lamination body before drying and the weight of the pre-lamination body after drying were measured, respectively, and the reduction rate of the weight of the pre-lamination body after drying with respect to the weight of the pre-lamination body before drying was determined. The reduction rate was 0.3%.

  The preformed body Un after drying was temporarily placed on the lower mold 40 using the conveying plate 50 shown in FIG. The pressure at the time of temporary placement was 0.15 MPa, the heating temperature was 60 ° C., and the pressurization time was 30 seconds. This preliminary laminated body Un was laminated in the number of 30, and was temporarily pressed to obtain a final laminated body Uf. The applied pressure at the time of temporary pressing was 5.9 MPa, the heating temperature was 50 ° C., and the pressing time was 30 seconds.

  The final stack Uf after the temporary pressing was evaluated for stacking misalignment and stackability. The results are shown in Table 1.

As shown in FIG. 9, the stacking deviation ΔD was obtained by measuring the maximum horizontal deviation in the electrode layer between the stacked preliminary stacks Un in the final stack Uf. Further, regarding stackability, two preforms were temporarily pressed under the above conditions, and the adhesion strength between layers of the obtained laminate was measured by a tensile tester.

  Next, the final laminated body Uf was cut into a predetermined size and subjected to solidification / drying treatment, binder removal treatment, firing and annealing (heat treatment) to produce a chip-shaped sintered body. In addition, the size after baking of each chip | tip was 3.2 mm x 1.6 mm x 0.6 mm.

Solidification and drying treatment
Temperature rising rate: 50 ° C / hour,
Holding temperature: 160 ° C.
Retention time: 4 hours,
Atmospheric gas: Air,
I went there.

Binder removal
Temperature rising rate: 15 ° C / hour,
Holding temperature: 600 ° C.
Retention time: 2 hours
Atmosphere gas: humidified mixed gas of N ₂ and H ₂ ,
I went there.

Firing
Temperature increase rate: 200 ° C./hour,
Holding temperature: 1200 ° C,
Retention time: 2 hours
Cooling rate: 200 ° C./hour,
Atmosphere gas: humidified mixed gas of N ₂ and H ₂ ,
Oxygen partial pressure: 10 ⁻⁷ Pa,
I went there.

Annealing (reoxidation)
Temperature increase rate: 200 ° C./hour,
Holding temperature: 1050 ° C.
Retention time: 2 hours
Cooling rate: 200 ° C./hour,
Atmospheric gas: humidified N ₂ gas,
Oxygen partial pressure: 10 ⁻¹ Pa,
I went there. The atmosphere gas was humidified using a wetter at a water temperature of 0 to 75 ° C.

Next, 50 chip-shaped sintered body samples obtained by firing the green chip obtained by cutting the final laminated body were embedded in a synthetic resin, the end surfaces were polished, and a 50 × microscope was used to remove the sample. Lamination was detected. No delamination was observed for all 50 samples, and the delamination generation ratio was 0% as shown in Table 1. The overall evaluation when the stacking misalignment is 10 μm or less, the stacking property is 30 N / cm ² or more, and the delamination is 0% is ◎, the stacking misalignment is 20 μm or less, and the stacking property is 30 N / cm ² or more. In the case where the delamination is 0%, the overall evaluation is ○, and the stacking deviation is 50 μm or less, the stacking property is 25 N / cm ² or more, and the delamination is 0%, the overall evaluation is Δ. When the overall evaluation when the deviation was 80 μm or more or the delamination was 30% or more was evaluated as x, the overall evaluation of Example 1 was “で”.

Comparative Example 1
Example except that the reduction rate of the weight of the pre-laminated body after drying with respect to the weight of the pre-laminated body before drying was 0%, that is, the pre-laminated body Un was laminated without drying to form the final laminated body. In the same manner as in Example 1, a final laminated body Uf was formed, and lamination deviation, stackability, delamination, and comprehensive evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 2 and 3 and Comparative Examples 2 and 3
Example 1 except that the reduction ratio of the weight of the pre-laminated body after drying to the weight of the pre-laminated body before drying was 0.6%, 0.9%, 1.2%, and 1.5%, respectively. In the same manner as above, the final laminate Uf was formed, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
The pressure at the time of temporary pressing of the pre-laminated body Un is set to 0.05 MPa, the heating temperature by the conveying plate 50 is set to 40 ° C., the pressing time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
The pressure at the time of temporary placement of the pre-laminated body Un is set to 0.05 MPa, the heating temperature by the conveying plate 50 is set to 60 ° C., the pressurization time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
The pressure at the time of temporary pressing of the pre-laminated body Un is set to 0.05 MPa, the heating temperature by the conveying plate 50 is set to 40 ° C., the pressing time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 7
The pressure at the time of temporary pressing of the preliminary laminated body Un is set to 0.15 MPa, the heating temperature by the conveying plate 50 is set to 40 ° C., and the pressing time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 8
The pressure at the time of temporary pressing of the preliminary laminated body Un is set to 0.15 MPa, the heating temperature by the conveying plate 50 is set to 60 ° C., the pressing time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 9
The pressure at the time of temporary placement of the pre-laminated body Un is set to 0.15 MPa, the heating temperature by the conveying plate 50 is set to 80 ° C., the pressurization time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 10
The pressure at the time of temporary placement of the pre-lamination body Un is 0.5 MPa, the heating temperature by the conveying plate 50 is 40 ° C., the pressurization time is changed to 1 second, 5 seconds, and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 11
The pressure at the time of temporary placement of the pre-laminated body Un is 0.5 MPa, the heating temperature by the conveying plate 50 is 60 ° C., the pressurization time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 12
The pressure at the time of temporary placement of the pre-laminated body Un is 0.5 MPa, the heating temperature by the conveying plate 50 is 80 ° C., the pressurization time is changed to 1 second, 5 seconds and 30 seconds. A final laminate Uf was formed in the same manner as in Example 1 except that the time was 30 seconds, and the stacking deviation, stackability, delamination, and overall evaluation were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As shown in Evaluation Table 1, when the decreasing rate of the weight of the pre-laminated body after drying is 0.2 to 1.0%, more preferably 0.2 to 0.6%, the stacking deviation is reduced. It was confirmed that the stacking property was improved and the delamination was reduced.

  Further, as shown in Table 1, when the pre-laminated body after drying is stacked (at the time of temporary placement), the pre-laminated body already stacked is preferably at a pressure of 0.1 MPa or more, more preferably 0. It was confirmed that the laminating deviation is preferably reduced when pressing at .15 MP, particularly preferably 0.5 MPa or more.

  Furthermore, when stacking the pre-laminated body after drying, it is preferably pressed against the pre-stacked pre-laminated body under a temperature condition of preferably 50 to 85 ° C., more preferably 60 to 80 ° C. It was confirmed that the deviation was reduced.

FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor manufactured by a method for manufacturing a multilayer ceramic electronic component according to an embodiment of the present invention. FIG. 2A to FIG. 2C are cross-sectional views of a main part showing an example of a lamination process of a green sheet and an electrode layer. FIG. 3A to FIG. 3C are cross-sectional views of relevant parts showing a step subsequent to FIG. FIGS. 4A to 4C are cross-sectional views of relevant parts showing steps subsequent to FIG. FIG. 5A to FIG. 5C are cross-sectional views of relevant parts showing a step subsequent to FIG. 6 (A) to 6 (C) are cross-sectional views of relevant parts showing a step subsequent to FIG. 5 (C). FIG. 7 is a fragmentary cross-sectional view showing a step continued from FIG. FIG. 8A, FIG. 8A, and FIG. 8B are schematic views showing the steps subsequent to FIG. FIG. 9 is a schematic view showing stacking deviation.

Explanation of symbols

2 ... Multilayer ceramic capacitor 4 ... Capacitor body 6, 8 ... Terminal electrode 10 ... Dielectric layer 10a ... Green sheet 12 ... Internal electrode layer 12a ... Electrode layer 20 ... Carrier sheet (first support sheet)
22 ... Release layer 24 ... Blank pattern layer 26 ... Carrier sheet (third support sheet)
28 ... Adhesive layer 30 ... Carrier sheet (second support sheet)
40 ... Lower mold 50 ... Conveying plate Un ... Preliminary laminate Uf ... Final laminate

Claims (4)

A step of stacking a predetermined number of green sheets to obtain a preliminary laminate,
Drying the preliminary laminate,
Stacking the dried pre-laminated body to obtain a final laminated body;
Cutting the final laminate to form a green chip;
Firing the green chip,
A method for producing a multilayer ceramic electronic component, wherein a reduction rate of the weight of the pre-laminated body after drying relative to the weight of the pre-laminated body before drying is 0.3 to 0.9 %. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the preliminary laminated body is formed by stacking 10 to 100 green sheets. Method of manufacturing a multilayer ceramic electronic component according to claim 1 or 2 to form a 10 to 100 by stacking pre-laminate final laminate. Method of manufacturing a multilayer ceramic electronic component according to any of the green claims on the surface is formed an electrode layer of a predetermined pattern of the seat 1-3.

Images