JP4640028B2 - Release layer paste and method for manufacturing multilayer electronic component - Google Patents

Description

  The present invention relates to a release layer paste used for manufacturing a multilayer electronic component such as a multilayer ceramic capacitor, and a method of manufacturing a multilayer electronic component using the release layer paste.

  In recent years, miniaturization of electronic devices has led to the progress of miniaturization and high performance of multilayer electronic components such as multilayer ceramic capacitors. Interlayer dielectric layers of multilayer electronic components (dielectrics sandwiched between a pair of internal electrodes) Layer) Thickness is 1 μm or less, and the number of laminated layers is over 800 layers. In the manufacturing process of such an electronic component, the thickness of the green sheet on which the dielectric layer can be formed after firing becomes extremely thin (usually 1.5 μm or less). A so-called sheet attack phenomenon, in which a gree sheet is dissolved by a solvent, becomes a problem. This sheet attack phenomenon is a problem that must be solved in order to promote thinning because it directly leads to a defect or short circuit of the green sheet.

  In order to eliminate such a sheet attack, Patent Documents 1 to 3 separately prepare a dry type electrode layer obtained by drying the electrode layer paste after forming the electrode layer paste in a predetermined pattern on the support film. There has been proposed a method for transferring an electrode layer having a predetermined pattern in which a type of electrode layer is transferred to the surface of each green sheet or the surface of a laminate of green sheets.

  However, the techniques of Patent Documents 1 to 3 have a problem that it is difficult to peel the electrode layer having a predetermined pattern from the support film.

  Therefore, the present inventors have proposed a technique for forming a release layer for improving the peelability of the electrode layer between the support film and the electrode layer having a predetermined pattern (see Patent Document 4).

  In this Patent Document 4, as a release layer paste used for forming a release layer, an organic vehicle in which a binder is dissolved in a solvent and at least a ceramic powder and a plasticizer are used. As the binder, the same binder as that contained in the green sheet, that is, a butyral resin was used. Further, terpineol or dihydroterpineol has been used as the solvent in the organic vehicle contained in the electrode layer paste used to form the electrode layer having a predetermined pattern.

  However, when the electrode layer paste using terpineol or dihydroterpineol as a solvent is used in combination with a release layer using butyral resin as a binder, the release layer is sheet attacked by the solvent of the electrode layer paste, or for the electrode layer. When the paste is printed, the peeling layer may be scraped off to cause residue.

  Sheet attack of the release layer can cause bleeding, repellency, and pinholes on the electrode layer and blank pattern layer formed on the surface of the release layer, and scraping of the release layer can cause stacking defects (structural defects). As a result, the short-circuit defects of the final laminated electronic component may be increased.

Therefore, it has been strongly desired to prevent sheet attack and scraping of the release layer.
JP-A-63-51616 Japanese Patent Laid-Open No. 3-250612 Japanese Patent Laid-Open No. 7-31326 JP 2003-197457 A

  It is an object of the present invention to prevent sheet attack with respect to an electrode layer paste for forming an electrode layer (a blank pattern layer paste for further forming a blank pattern layer as required), and to print the paste. By providing a release layer paste that can be used to manufacture a multilayer electronic component that can form a release layer that does not sometimes scrape, and a method of manufacturing a multilayer electronic component using the release layer paste. is there.

In order to achieve the above object, according to the present invention,
A release layer paste used for manufacturing a multilayer electronic component,
Used in combination with paste for electrode layers containing terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate,
Including ceramic powder, organic vehicle, plasticizer, and dispersant;
The binder in the organic vehicle is mainly composed of acrylic resin,
The acrylic resin is composed of a copolymer having an acrylic acid ester monomer unit and a methacrylic acid ester monomer unit as main components and an acid value of 1 to 10 mgKOH / g,
A ratio (P / B) of the ceramic powder to the binder and the plasticizer is controlled to 0.67 to 5.56 (excluding 0.67 and 5.56). A release layer paste is provided.

According to the present invention,
A release layer paste used for manufacturing a multilayer electronic component,
Used in combination with paste for electrode layers containing terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate,
Including ceramic powder, organic vehicle, plasticizer, and dispersant;
The binder in the organic vehicle is mainly composed of acrylic resin,
The acrylic resin is composed of a copolymer having an acrylic acid ester monomer unit and a methacrylic acid ester monomer unit as main components and an acid value of 1 to 10 mgKOH / g,
A release layer paste is provided, wherein the binder content is 12 to 100 parts by weight (excluding 12 parts by weight and 100 parts by weight) with respect to 100 parts by weight of the ceramic powder.

  Preferably, the electrode layer paste used in combination is terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, isobornyl acetate, d-dihydrocarbeveol, It further includes one or more selected from menthyl acetate, citronole, perillyl alcohol, and acetoxy-methoxyethoxy-cyclohexanol acetate.

  Preferably, the acrylic resin has a weight average molecular weight of 230,000 to 700,000.

  Preferably, the plasticizer is at least one selected from dibutyl phthalate (DBP), dioctyl phthalate (DOP), and butyl benzyl phthalate (BBP), and is 5 to 100 based on 100 parts by weight of the ceramic powder. Parts by weight (excluding 5 parts by weight and 100 parts by weight).

  Preferably, the ceramic powder has an average particle size of 0.2 μm or less. More preferably, it is 0.1 μm or less.

  Preferably, the dispersant is a polycarboxylate-based dispersant and is contained in an amount of 0.5 to 3 parts by weight with respect to 100 parts by weight of the ceramic powder.

  Preferably, the solvent in the organic vehicle is one or more of acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, butyl acetate, and toluene, and the nonvolatile content concentration is 5 to 20% by weight. Is contained.

According to the present invention,
Forming a release layer on the release treatment side of the first support sheet subjected to the release treatment;
Forming an electrode layer in a predetermined pattern on the surface of the release layer;
Forming a green sheet on the surface of the electrode layer to obtain a green sheet having an electrode layer;
Laminating a green sheet having the electrode layer to form a green chip;
A step of firing the green chip, comprising the steps of:
Any one of the above release layer pastes is used as the release layer paste for forming the release layer.

  Preferably, the mold release treatment applied to the first support sheet is formed by a coating method using a release agent mainly composed of silicone, and the release force of the first support sheet is 7.3 to 20.3 mN / cm (however, excluding 7.3 mN / cm and 20.3 mN / cm).

  Preferably, the ceramic powder contained in the release layer paste is the same as the ceramic powder contained in the paste for forming the green sheet.

  Preferably, the release layer has a thickness of 0.05 to 0.2 μm. More preferably, it is 0.05-0.1 micrometer.

  In the method for manufacturing a multilayer electronic component of the present invention, before the green sheet is formed, the surface of the release layer where the electrode layer is not formed has the same thickness as the electrode layer and the same material as the green sheet. You may form the blank pattern layer comprised by these.

  In the method for manufacturing a multilayer electronic component of the present invention, before laminating the green sheet having the electrode layer, an adhesive layer is formed on the surface opposite to the electrode layer of the green sheet having the electrode layer, and the adhesive layer is formed. A green sheet having the electrode layer may be laminated.

  The release layer paste of the present invention includes, for example, a step of forming a release layer on the release treatment side of the first support sheet that has been subjected to a release treatment, and an electrode layer is formed in a predetermined pattern on the surface of the release layer A step of forming a green sheet on the surface of the electrode layer to obtain a green sheet having an electrode layer, a step of stacking the green sheets having the electrode layer to form a green chip, and the green chip. In the manufacturing method of the multilayer electronic component having the step of firing, it can be used for forming the release layer.

  The release layer paste of the present invention contains a specific acrylic resin as a main component in a binder constituting the paste. The specific acrylic resin contained in the paste in the present invention is terpineol, dihydroterpineol, terpineol acetate contained as a solvent in the electrode layer paste or blank pattern layer paste for forming the electrode layer or blank pattern layer. Or, it is hardly dissolved or swollen in dihydroterpineol acetate (slightly soluble). For this reason, the peeling layer formed using the peeling layer paste of the present invention has an effect that the sheet layer is not attacked with respect to the electrode layer paste and the blank pattern layer paste. As a result, the printability of the electrode layer paste and blank pattern layer paste for forming the electrode layer and blank pattern layer on the release layer formed using the release layer paste of the present invention is stabilized. Specifically, it is possible to suppress bleeding, repelling, and pinholes in the electrode layer and blank pattern layer formed on the surface of the release layer. Bleeding, repellency, and pinholes in the electrode layer and blank pattern layer are likely to occur when the support sheet appears due to dissolution of the release layer, but the release layer formed using the release layer paste of the present invention Since the sheet paste and the blank pattern layer paste are not subjected to sheet attack, the dissolved electrode layer or blank pattern layer itself does not crack, and even when printing is performed, the residue or the like does not fall off. The electrode layer and blank pattern layer formed on the surface of the release layer do not cause bleeding, repelling, or pinholes.

  In addition, in addition to the above-mentioned terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate as a solvent in the electrode layer paste and blank pattern layer paste for forming the electrode layer and blank pattern layer, Terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, isobornyl acetate, d-dihydrocarbeveol, menthyl acetate, citronol, perillyl alcohol, and acetoxy-methoxyethoxy The same applies when one or more selected from cyclohexanol acetate are used in combination.

  In addition, the release layer formed using the release layer paste of the present invention is not scraped when the electrode layer paste or the blank pattern layer paste is printed, and no debris is generated. For this reason, generation | occurrence | production of the defect (structural defect) at the time of lamination | stacking is suppressed, and the short circuit defect of multilayer electronic components, such as a multilayer ceramic capacitor finally obtained, can be reduced.

  In the present invention, preferably, the peel force of the first support sheet is controlled to 7.3 to 20.3 mN / cm (excluding 7.3 mN / cm and 20.3 mN / cm), so that terpineol and dihydroterpineol The release layer formed using the release layer paste of the present invention does not fall off from the first support sheet even when used in combination with the electrode layer paste using terpineol acetate or dihydroterpineol acetate as a solvent. .

  The multilayer electronic component is not particularly limited, and examples thereof include multilayer ceramic capacitors, multilayer piezoelectric elements, multilayer chip inductors, multilayer chip varistors, multilayer chip thermistors, multilayer chip resistors, and other surface mount (SMD) chip type electronic components. The

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 according to an embodiment of the present invention, and FIGS. 2A to 2C are diagrams illustrating a method for forming an electrode layer and a green sheet according to an embodiment of the present invention. 3 (A) to 3 (C) are principal part sectional views showing a method for forming an adhesive layer according to an embodiment of the present invention, and FIG. 4 (A), FIG. 4 (B) and FIG. FIGS. 5A and 5B are cross-sectional views showing a main part of a method for laminating a green sheet having an electrode layer according to an embodiment of the present invention. FIGS. 6A and 6B are other views of the present invention. FIGS. 7A to 7C and FIGS. 8A to 8C are other cross-sectional views showing a method for laminating a green sheet having an electrode layer according to the embodiment. FIG. 9A is a cross-sectional view of a main part showing a method for laminating a green sheet having an electrode layer according to the embodiment, and FIG. A photograph showing the state of the release layer after printing the paste once, FIG. 9B is a photograph showing the state of the release layer after printing the electrode layer paste 3000 times on the surface of the release layer of Example 1, 10A is a photograph showing the state of the release layer after the electrode layer paste is printed once on the surface of the release layer of Comparative Example 1, and FIG. 10B is an electrode on the surface of the release layer of Comparative Example 1. It is a photograph which shows the state of the peeling layer after printing the layer paste 3000 times.

  In the present embodiment, a multilayer ceramic capacitor will be described as an example of a multilayer ceramic electronic component.

Multilayer Ceramic Capacitor As shown in FIG. 1, a multilayer ceramic capacitor 2 according to an embodiment of the present invention includes a capacitor body 4 having a configuration in which dielectric layers 10 and internal electrode layers 12 are alternately stacked.

  A pair of external electrodes 6 and 8 are formed at both ends of the capacitor element body 4 so as to be electrically connected to the internal electrode layers 12 arranged alternately in the element element body 4. The internal electrode layers 12 are laminated such that the side end faces are alternately exposed on the surfaces of the two opposite ends of the capacitor body 4. The pair of external electrodes 6 and 8 are formed at both ends of the capacitor body 4 and are connected to the exposed end surfaces of the alternately arranged internal electrode layers 12 to constitute a capacitor circuit.

  The outer shape and dimensions of the capacitor body 4 are not particularly limited and can be appropriately set according to the application. Usually, the outer shape is substantially a rectangular parallelepiped shape, and the dimensions are usually vertical (0.4 to 5.6 mm) × It can be about horizontal (0.2-5.0 mm) × height (0.2-1.9 mm).

  The dielectric layer 10 is formed by firing the green sheet 10a shown in FIG. 2C and the like, and the material thereof is not particularly limited, and examples thereof include calcium titanate, strontium titanate and / or barium titanate. Consists of dielectric material. In the present embodiment, the thickness of the dielectric layer 10 is preferably 5 μm or less, more preferably 3 μm or less.

  The internal electrode layer 12 is formed by firing an electrode layer 12a having a predetermined pattern made of the electrode layer paste shown in FIGS. 2B and 2C. The thickness of the internal electrode layer 12 is preferably 1.5 μm or less, more preferably 1.0 μm or less.

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

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.

Formation of Release Layer (1) In this embodiment, first, the release layer 22 is formed on the carrier sheet 20 as shown in FIG.

  As the carrier sheet 20, for example, a PET film or the like is used, and a release agent mainly composed of silicone or the like is coated to improve the peelability, and the peel force of the carrier sheet 20 from the release layer 22 described later. However, it is preferably controlled within a range of 7.3 to 20.3 mN / cm (excluding 7.3 mN / cm and 20.3 mN / cm), more preferably 10 to 18 mN / cm. By controlling the peeling force within this range, as described later, even if it is used in combination with paste for electrode layers using terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate as a solvent, the peeling layer described later 22 does not fall off the carrier sheet 20. Although the thickness of the carrier sheet 20 is not specifically limited, Preferably it is 5-100 micrometers.

  The thickness of the release layer 22 is preferably 0.05 to 0.2 μm, more preferably about 0.05 to 0.1 μm. If the release layer 22 is too thin, the effect of forming it cannot be obtained. On the other hand, if the release layer 22 is too thick, an electrode layer 12a (see FIG. 2B), which will be described later, is difficult to peel off from the carrier sheet 20. Therefore, the electrode layer 12a may be damaged during peeling.

  The method for forming the release layer 22 is not particularly limited as long as it can form a very thin layer uniformly. In this embodiment, a coating method using a release layer paste (for example, by a wire bar coater or a die coater) is used. Used.

  The release layer paste used in the present embodiment contains ceramic powder, an organic vehicle, and a plasticizer. Further, it usually contains a release agent.

  As the ceramic powder, one having the same composition as the ceramic powder contained in the green sheet 10a described later is used. By doing so, the composition does not change even if the component of the release layer 22 reacts with the green sheet 10a during firing.

  The particle size of the ceramic powder is preferably smaller than the thickness of the release layer 22 after the paste is formed and dried. Specifically, it is preferably 0.2 μm or less, more preferably 0.1 μm or less.

  If the average particle size of the ceramic powder is too large, it is difficult to make the release layer 22 thin. On the other hand, if the particle size of the ceramic powder is too small, dispersion is very difficult, so the lower limit is preferably 0.01 μm. It is.

  The ceramic powder is contained in a range where the nonvolatile content concentration in the release layer paste is 5 to 20 wt%, more preferably 10 to 15 wt%. If the content of the ceramic powder is too small, the paste viscosity becomes small and it becomes difficult to form a layer by coating. On the other hand, if the content of the ceramic powder is too large, it is difficult to reduce the coating thickness.

The organic vehicle contains a binder and a solvent. As the binder, a specific acrylic resin is a main component in the present invention. The content of the acrylic resin in the binder is preferably 95% by weight or more, and more preferably 100% by weight. As a resin that can be used in combination with an acrylic resin although there is a very small amount, there are ethyl cellulose, polyvinyl acetal resin, and the like. Examples of the polyvinyl acetal resin include polyvinyl acetal (acetal group R = CH ₃ ), polyvinyl acetoacetal, polyvinyl butyral (acetal group R = C ₃ H ₇ ), polyvinyl formal (acetal group R = H), polyvinyl benzal, polyvinyl Examples include phenyl acetal, polyvinyl propional, polyvinyl hexanal, and polyvinyl benzal.

  The acrylic resin used in this embodiment is a co-polymer containing an acrylic acid ester monomer unit and a methacrylic acid ester monomer unit (hereinafter sometimes abbreviated as (meth) acrylic acid ester monomer unit) as main components. Composed of coalescence.

  The copolymerization ratio of acrylate monomer units and methacrylate ester monomer units is, for example, based on weight% when the former uses butyl acrylate monomer units and the latter uses methyl methacrylate monomer units. For example, it can be set to about 10-30: 90-70.

  Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples thereof include t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate. In this embodiment, the glass transition temperature (Tg) is higher than room temperature in the final resin state. It is preferable to use a combination of these monomers.

  The total content of (meth) acrylic acid ester monomer units in the acrylic resin is preferably 95% by weight or more, and more preferably 100% by weight. A very small amount of the third monomer unit that can be used in combination with the (meth) acrylate monomer unit can be copolymerized with the (meth) acrylate monomer unit. Although not particularly limited, for example, there are (meth) acrylic acid monomer units, aromatic vinyl monomer units, vinyl ester monomer units, vinyl ether monomer units, and the like. Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene and the like. Examples of the vinyl ester monomer include vinyl acetate and vinyl propionate. Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and hydroxybutyl vinyl ether.

The acrylic resin used in the present embodiment has an acid value (mg of KOH required to neutralize free acid in 1 g of acrylic resin) of 1 to 10 mgKOH / g, preferably 2 to 7 mgKOH / g. The acid value of the acrylic resin is related to the dispersion with the ceramic powder, but if the acid value of the acrylic resin is outside the above range, the dispersibility of the ceramic powder becomes extremely poor. Actually, the ceramic powder does not disperse below 1 mg KOH / g. On the other hand, if it exceeds 10 mgKOH / g, an agglomeration effect is generated, dispersibility is deteriorated, and the peeling force tends to increase, which is not preferable.
The acid value of the acrylic resin can be adjusted by the amount of the (meth) acrylic acid monomer unit. For example, when the blending amount of acrylic acid monomer units or methacrylic acid monomer units is increased, the acid value tends to increase, and conversely when it is decreased, the acid value tends to decrease. The acid value of the acrylic resin can be measured by a method based on JIS-K0070.

  The weight average molecular weight (Mw) of the acrylic resin used in the present embodiment is not particularly limited, but is preferably 230,000 to 700,000, more preferably 40 in terms of polystyrene using gel permeation chromatography (GPC). 10,000 to 700,000. If the weight average molecular weight is too small, sheet attack is likely to occur, and conversely if too high, dispersion becomes difficult.

  The acrylic resin used in this embodiment preferably has a higher glass transition temperature Tg, and more preferably an acrylic resin having a Tg of room temperature or higher. By using an acrylic resin having a Tg of room temperature or higher, the peel strength of the release layer 22 can be further reduced.

  The binder is contained in the release layer paste in an amount of 12 to 100 parts by weight (excluding 12 parts by weight and 100 parts by weight), preferably 24 to 50 parts by weight, based on 100 parts by weight of the ceramic powder. If the amount of the binder is too small, the strength of the release layer 22 becomes weak, and if it is too large, the electrode layer 12a and the blank pattern layer 24 tend to be peeled off.

  Alternatively, the ratio (P / B) of the ceramic powder to the binder and the plasticizer described later is 0.67 to 5.56 (excluding 0.67 and 5.56), preferably 1.0. The binder amount is adjusted so as to be controlled to ˜2.78. If (P / B) is too small, the strength of the release layer 22 will be weak, and if it is too large, the electrode layer 12a and the blank pattern layer 24 will tend to become heavy.

  Examples of the solvent include, but are not limited to, alcohol, butyl carbitol, acetone, methyl ethyl ketone (MEK), mineral spirit, methyl isobutyl ketone (MIBK), toluene, xylene, ethyl acetate, butyl acetate, and butyl stearate. Are preferably one or more of acetone, MEK, MIBK, ethyl acetate, butyl acetate and toluene.

  The solvent is contained in a range where the nonvolatile content in the release layer paste is 5 to 20% by weight, more preferably 10 to 15% by weight. When the amount of the solvent is too small, it is difficult to apply thinly, and when it is too large, the viscosity becomes too low and the powder tends to settle and easily separate.

  Although it does not specifically limit as a plasticizer, A phthalic acid ester, adipic acid, phosphoric acid ester, glycols, etc. are illustrated. In the present embodiment, preferably, dioctyl adipate (DOA), butyl butylene glycol phthalate (BPBG), didodecyl phthalate (DDP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), butyl benzyl phthalate ( BBP), dibutyl sebacate and the like are used. Among these, it is particularly preferable to use one or more selected from DBP, DOP, and BBP. By using one or more selected from DBP, DOP and BBP, there is an advantage that the peel strength is lowered.

  The plasticizer is contained in an amount of preferably 5 to 100 parts by weight (excluding 5 parts by weight and 100 parts by weight), more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the ceramic powder. The plasticizer controls the Tg of the binder in the organic vehicle and, when added, increases the peel strength of the release layer, but improves the stackability (adhesion during lamination). Basically, there is no problem even if the addition of the plasticizer is zero, but when it is added to improve stacking properties, transfer, etc., the upper limit is preferably 100 parts by weight with respect to 100 parts by weight of the ceramic powder. This is because the addition of the plasticizer increases the adhesiveness of the release layer and adheres to the screen or adheres to the running system, making continuous printing difficult.

  Although it does not specifically limit as a dispersing agent, A polycarboxylate type dispersing agent, a nonionic dispersing agent, etc. are illustrated. In addition, there are block polymer type dispersants and graft polymer type dispersants. In the present embodiment, a polycarboxylate-based dispersant is preferably used.

  The dispersant is contained in an amount of preferably 0.5 to 3 parts by weight, more preferably 1 to 1.5 parts by weight with respect to 100 parts by weight of the ceramic powder. The dispersant has an effect of improving the dispersibility of the pigment (ceramic powder) and improving the stability (change with time) of the paint.

  If the content of the dispersant is too small, the effect of adding this becomes insufficient, and if it is too large, there may be a disadvantage that the dispersibility is lowered due to micelle formation or reaggregation.

  Although it does not specifically limit as a mold release agent, Paraffin, wax, fatty acid ester, silicone oil, etc. are illustrated. The release agent used here may be the same as or different from the release agent contained in the green sheet 10a.

  The release agent is preferably contained in an amount of 5 to 20 parts by weight, more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the binder in the organic vehicle.

  The release layer paste may further contain an additive such as a charging aid.

  The release layer paste can be formed by mixing each of the above components with a ball mill or the like to form a slurry.

  The release layer paste is applied onto the carrier sheet 20 and then dried to form the release layer 22. The drying temperature is not particularly limited, but is preferably 50 to 100 ° C., and the drying time is preferably 1 to 10 minutes.

Formation of Electrode Layer (2) Next, as shown in FIG. 2B, the surface of the release layer 22 formed on the carrier sheet 20 has a predetermined pattern that becomes the internal electrode layer 12 shown in FIG. An electrode layer (internal electrode pattern) 12a is formed.

  The thickness of the electrode layer 12a is preferably about 0.1 to 2.0 μm, more preferably about 0.1 to 1.0 μm. The thickness of the electrode layer 12a is in the above range in the current technology, but it is more preferable that the electrode layer 12a is thin in a range where the electrode is not interrupted. 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. In the present embodiment, since the electrode layer 12a is formed on the release layer 22, electrode repelling can be effectively prevented, and the electrode layer 12a can be formed satisfactorily and with high accuracy.

  The method for forming the electrode layer 12a is not particularly limited as long as the layer can be formed uniformly. For example, a thick film forming method such as a screen printing method or a gravure printing method using electrode layer paste, vapor deposition, sputtering, or the like. In this embodiment, a case where a paste for an electrode layer is used and a screen printing method or a gravure printing method which is one type of a thick film method is used is illustrated.

  The electrode layer paste used in the present embodiment contains a conductive powder and an organic vehicle.

  Although it does not specifically limit as electroconductive powder, It is preferable to comprise by at least 1 sort (s) chosen from Cu, Ni, and these alloys, More preferably, it comprises Ni or Ni alloy, and also these mixtures. .

  Ni or an Ni alloy is preferably an alloy of Ni and at least one element selected from Mn, Cr, Co, and Al, and the Ni content in the alloy is preferably 95% by weight or more. In addition, in Ni or Ni alloy, various trace components, such as P, Fe, and Mg, may be contained about 0.1 wt% or less.

  Such a conductive powder is not particularly limited in shape, such as spherical or flake shaped, and may be a mixture of these shapes. Moreover, the particle diameter of electroconductive powder is 0.1-2 micrometers normally in the case of spherical shape, Preferably about 0.2-1 micrometer is used.

  The conductive powder is preferably contained in the electrode layer paste at 30 to 70% by weight, more preferably 40 to 50% by weight.

  The organic vehicle contains a binder and a solvent. The binder is not particularly limited, and examples thereof include ethyl cellulose, acrylic resins, butyral resins such as polyvinyl butyral, acetal resins such as polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, and copolymers thereof. In this embodiment, a butyral resin such as polyvinyl butyral is used. The binder is preferably contained in the electrode layer paste in an amount of 8 to 20 parts by weight with respect to 100 parts by weight of the conductive powder.

  Examples of the solvent include, but are not limited to, terpineol, butyl carbitol, kerosene, acetone, isobornyl acetate, and the like. In this embodiment, terpineol, dihydroterpineol, terpineol acetate, or dihydroterpineol acetate (hereinafter referred to as these compounds). As the solvent, a terpineol derivative is used as appropriate. These solvents may be used alone or in combination of two or more. The solvent is preferably contained in the electrode layer paste at 20 to 65% by weight, more preferably 30 to 50% by weight.

  In this embodiment, in addition to the above-mentioned terpineol derivative, as a solvent, further, terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, isobornyl acetate, d -Contains one or more selected from dihydrocarbeveol, menthyl acetate, citronol, perillyl alcohol, and acetoxy-methoxyethoxy-cyclohexanol acetate (hereinafter these solvents are referred to as other solvents as appropriate) You may do it.

  In the electrode layer paste used in the present embodiment, the above-mentioned terpineol derivative is included as an essential component, and if necessary, the other solvent described above may be added, but when the terpineol derivative and another solvent are used in combination. The ratio of the terpineol derivative and other solvent is preferably terpineol derivative: other solvent = 100: 0 to 50:50 (weight ratio). When the content of the terpineol derivative is less than 50% by weight, it tends to be difficult to make a coating material when preparing the electrode layer paste. Note that the total content of the terpineol derivative and the other solvent in the case of using another solvent is in the above range.

  In the electrode layer paste, ceramic powder having the same composition as that of the ceramic powder contained in the green sheet 10a described later may be included as a co-material as in the case of the release layer paste. The common material has an effect of suppressing the sintering of the conductive powder in the firing process. The ceramic powder used as the co-material is preferably contained in the electrode layer paste in an amount of 5 to 25 parts by weight with respect to 100 parts by weight of the conductive powder.

  The electrode layer paste preferably contains a plasticizer or a pressure-sensitive adhesive for the purpose of improving the adhesion to the green sheet. Examples of the plasticizer include phthalic acid ester, adipic acid, phosphoric acid ester, glycols and the like. The plasticizer is preferably contained in an amount of 10 to 300 parts by weight with respect to 100 parts by weight of the binder in the organic vehicle. If the plasticizer content is too small, there will be no effect of addition, and if it is too much, the strength of the electrode layer 12a formed will be significantly reduced, and excessive plasticizer will tend to exude from the electrode layer 12a.

  The electrode layer paste can be formed by mixing each of the above components with a ball mill or the like to form a slurry.

Formation of Blank Pattern Layer (3) In this embodiment, the electrode layer 12a shown in FIG. 2B is formed after or before the electrode layer 12a having a predetermined pattern is formed on the surface of the release layer 22 by the printing method. A blank pattern layer 24 having the same thickness as the electrode layer 12a is formed in the surface gap (blank pattern portion 50) of the release layer 22 that is not formed. The reason why the thickness of the blank pattern layer 24 is set to the same thickness as that of the electrode layer 12a is that a step is formed unless it is substantially the same.

  The blank pattern layer 24 is made of the same material as a green sheet 10a described later. Further, the blank pattern layer 24 can be formed by the same method (using blank pattern layer paste) as the electrode layer 12a or the green sheet 10a described later.

  This blank pattern layer paste is applied to the blank pattern portion 50 between the electrode layers 12a. Thereafter, the electrode layer 12a and the blank pattern layer 24 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.

Formation of Green Sheet (4) Next, as shown in FIG. 2C, a green sheet 10a that becomes the dielectric layer 10 shown in FIG. 1 after firing is formed on the surfaces of the electrode layer 12a and the blank pattern layer 24. .

  The thickness of the green sheet 10a is preferably about 0.5 to 30 μm, more preferably about 0.5 to 10 μm.

  The method for forming the green sheet 10a is not particularly limited as long as the layer can be formed uniformly. In this embodiment, a case where a dielectric paste is used and a doctor blade method is used is illustrated.

  The dielectric paste used in the present embodiment is usually composed of an organic solvent-based paste obtained by kneading ceramic powder and an organic vehicle.

  The ceramic powder can be appropriately selected from various compounds to be complex oxides and oxides, such as carbonates, nitrates, hydroxides, organometallic compounds, and the like, and can be used as a mixture. The ceramic powder 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 ceramic green sheet, it is desirable to use a powder finer than the thickness of the ceramic green sheet.

  The organic vehicle contains a binder and a solvent. The binder is not particularly limited, and examples thereof include various usual binders such as ethyl cellulose, polyvinyl butyral, and acrylic resin. The solvent is not particularly limited, and examples thereof include ordinary organic solvents such as terpineol, alcohol, butyl carbitol, acetone, methyl ethyl ketone (MEK), toluene, xylene, ethyl acetate, butyl stearate, and isobornyl acetate.

  The content of each component in the dielectric paste is not particularly limited. For example, the normal content, for example, the binder is about 1 to 5% by mass, and the solvent (or water) is about 10 to 50% by mass. Good.

  The dielectric paste may contain additives selected from various dispersants, plasticizers, dielectrics, subcomponent compounds, glass frit, insulators, and the like, if necessary. When these additives are added to the dielectric paste, the total content is desirably about 10% by weight or less.

Examples of the plasticizer include phthalate esters such as dioctyl phthalate and benzylbutyl phthalate, adipic acid, phosphate esters, glycols, and the like.
When using a butyral resin as the binder, the plasticizer preferably has a content of 25 to 100 parts by weight with respect to 100 parts by weight of the binder resin. If the amount of the plasticizer is too small, the green sheet tends to become brittle. If the amount is too large, the plasticizer oozes out and is difficult to handle.

  Using the dielectric paste as described above, the green sheet 10a is formed on the surface of the electrode layer 12a and the blank pattern layer 24 by a doctor blade method or the like.

Formation of Adhesive Layer (5) In this embodiment, next to the carrier sheet 20, as shown in FIG. 3A, the adhesive layer 28 is formed on the surface of the carrier sheet 26 as the second support sheet. A formed adhesive layer transfer sheet may be prepared.

  The carrier sheet 26 can be composed of a sheet made of the same material as the carrier sheet 20. The thickness of the adhesive layer 28 is preferably 0.3 μm or less, and is preferably thinner than the average particle size of the ceramic powder contained in the green sheet 10a.

  The method for forming the adhesive layer 28 on the surface of the carrier sheet 26 is not particularly limited as long as the layer can be formed uniformly, but in this embodiment, an adhesive layer paste is used, for example, bar coater method, die coater method, reverse coater. A method such as a dip coater method or a kiss coater method is used.

  The adhesive layer paste used in the present embodiment contains an organic vehicle and a plasticizer.

  The organic vehicle contains a binder and a solvent. The binder may be the same as or different from the binder included in the green sheet 10a. A solvent is not specifically limited, The normal organic solvent as mentioned above can be used.

  Although it does not specifically limit as a plasticizer, A phthalic acid ester, adipic acid, phosphoric acid ester, glycols, etc. are illustrated.

  The adhesive layer paste may contain a ceramic powder having the same composition as the ceramic powder contained in the green sheet 10a, and may further contain a charge remover such as an imidazoline-based charge remover.

  The adhesive layer paste can be formed by mixing the above-mentioned components with a ball mill or the like to form a slurry.

  This adhesive layer paste is applied and formed on the surface of the carrier sheet 26 as the second support sheet by the above various application methods, and then the adhesive layer 28 is dried as necessary.

Formation of Laminate Unit (6) Next, an adhesive layer 28 is formed on the surface of the green sheet 10a formed on the electrode layer 12a and the blank pattern layer 24 shown in FIG. 2C, and FIG. The laminate unit U1a shown in FIG.

  In the present embodiment, a transfer method is adopted as a method for forming the adhesive layer 28. That is, as shown in FIGS. 3A and 3B, the adhesive layer 28 of the adhesive layer transfer sheet prepared as described above is pressed against the surface of the green sheet 10a, heated and pressurized, Thereafter, the carrier sheet 26 is peeled off, whereby the adhesive layer 28 is transferred to the surface of the green sheet 10a as shown in FIG. 3C to obtain a laminate unit U1a.

  By forming the adhesive layer 28 by a transfer method, it is possible to effectively prevent the components of the adhesive layer from penetrating into the green sheet 10a, the electrode layer 12a, or the blank pattern layer 24. Therefore, there is no possibility of adversely affecting the composition of the green sheet 10a, the electrode layer 12a, or the blank pattern layer 24. Furthermore, even when the adhesive layer 28 is formed thin, the adhesive layer components do not soak into the green sheet 10a, the electrode layer 12a, or the blank pattern layer 24, so that the adhesiveness can be kept high.

  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.

Formation of Green Chip (7) Next, a plurality of the obtained laminate units U1a are stacked to form a green chip.

  In the present embodiment, the laminate unit U1a is laminated through the adhesive layer 28 as shown in FIGS. 4 (A), 4 (B), 5 (A), and 5 (B). This is done by bonding body units together. Hereinafter, the lamination method will be described.

  First, as shown to FIG. 4 (A), the laminated body unit U1a produced above and another laminated body unit U1b produced by the method similar to the laminated body unit U1a are prepared.

  Next, the carrier sheet 20 is peeled off from the laminate unit U1b, and the laminate unit U1b is brought into a state where the carrier sheet 20 is peeled off. In this embodiment, since the laminate unit U1b is formed on the carrier sheet 20 via the release layer 22, the carrier sheet 20 can be easily and satisfactorily peeled from the laminate unit U1b. Further, the electrode layer 12a and the blank pattern layer 24 are not damaged at the time of peeling. In addition, although it is preferable that the peeling layer 22 is peeled from the laminated body unit U1b with the carrier sheet 20, as long as it is about a small amount, it may remain on the laminated body unit U1b side. Even in this case, the remaining release layer 22 is sufficiently thin compared to the green sheet 10a and the electrode layer 12a, and the dielectric contained in the release layer 22 is the same as the green sheet 10a after firing. Since this constitutes a part of the dielectric layer 10, there is no problem.

  Next, as shown in FIG. 4B, the laminate unit U1b from which the carrier sheet 20 has been peeled off and the laminate unit U1a are bonded and laminated via the adhesive layer 28 of the laminate unit U1a. .

  Next, as shown in FIG. 5A and FIG. 5B, in the same manner, another laminate unit U1c is placed on the laminate unit U1b via the adhesive layer 28 of the laminate unit U1b. Glue and laminate. And the process shown to this FIG. 5 (A) and FIG. 5 (B) is repeated, and a some laminated body unit is laminated | stacked.

  Finally, a green sheet for an outer layer is laminated on the upper surface and / or lower surface of the laminated body, final pressing is performed, and then the laminated body is cut into a predetermined size to form a green chip. The pressure at the final pressurization is preferably 10 to 200 MPa, and the heating temperature is preferably 40 to 100 ° C.

Baking of green chip etc. (8) The obtained green chip is subjected to binder removal processing and baking processing, and further subjected to heat treatment for reoxidizing the dielectric layer as necessary. Then, the external electrode paste is printed or transferred to the capacitor body 4 composed of the formed sintered body and fired to form the external electrodes 6 and 8, whereby the multilayer ceramic capacitor 2 is manufactured. The manufactured multilayer ceramic capacitor 2 is mounted on a printed circuit board or the like by soldering or the like, and used for various electronic devices.

  The release layer paste of the present embodiment contains a specific acrylic resin as a main component in a binder constituting the paste. The specific acrylic resin contained in the paste in this embodiment is terpineol or dihydroterpineol contained as a solvent in the electrode layer paste or blank pattern layer paste for forming the electrode layer 12a or the blank pattern layer 24. It is difficult to dissolve or swell in terpineol acetate or dihydroterpineol acetate (terpineol derivative) (slightly soluble). For this reason, the peeling layer 22 formed using the peeling layer paste of the present embodiment has an effect that the sheet layer is not attacked with respect to the electrode layer paste and the blank pattern layer paste. As a result, the printability of the electrode layer paste and the blank pattern layer paste for forming the electrode layer 12a and the blank pattern layer 24 on the release layer 22 formed using the release layer paste of the present embodiment is stable. To do. Specifically, it is possible to suppress the occurrence of bleeding, repelling, and pinholes in the electrode layer 12a and the blank pattern layer 24 formed on the surface of the release layer 22. Further, the electrode layer 12a and the blank pattern layer 24 themselves are not cracked by dissolution, and even when printing is performed, the residue or the like does not fall off. This is because, in addition to the terpineol derivative, as a solvent in the electrode layer paste and blank pattern layer paste for forming the electrode layer 12a and the blank pattern layer 24, further, terpinyloxyethanol, dihydro Selected from terpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, isobornyl acetate, d-dihydrocarbeveol, menthyl acetate, citronol, perillyl alcohol, and acetoxy-methoxyethoxy-cyclohexanol acetate The same applies when one or more of these are used in combination.

  In addition, the release layer 22 formed using the release layer paste of the present embodiment is not scraped when the electrode layer paste or the blank pattern layer paste is printed, and no debris is generated. For this reason, generation | occurrence | production of the defect (structural defect) at the time of lamination | stacking is suppressed, and the short circuit defect of the finally obtained multilayer ceramic capacitor 2 can be reduced.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

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

  The method for forming the adhesive layer 28 is not limited to the transfer method, and the adhesive layer paste is applied directly on the green sheet 10a and dried without applying the adhesive layer paste to the surface of the carrier sheet 26 as the second support sheet. The adhesive layer 28 may be formed.

  As shown in FIG. 6, the laminate unit is laminated by peeling the carrier sheet 20 from the laminate unit U1a in advance, and then laminating the green sheet 30 for the outer layer (green sheets with no electrode layers formed thereon) The laminated unit U1a may be formed on the thick laminated body) and laminated.

  Moreover, the lamination | stacking method of a laminated body unit can also employ | adopt the process of peeling the carrier sheet 20, after laminating | stacking a laminated body unit, as shown, for example in FIG. 7, FIG. That is, as shown in FIGS. 7A and 7B, first, the laminate unit U1a from which the carrier sheet 20 is not peeled is placed on the green sheet 30 for the outer layer via the adhesive layer 28. Glue and laminate. Next, as shown in FIG. 7C, the carrier sheet 20 is peeled from the multilayer unit U1a. Next, as shown in FIG. 8 (A) to FIG. 8 (C), in the same manner, another laminate unit U1b is placed on the laminate unit U1a via the adhesive layer 28 of the laminate unit U1b. Glue and laminate. Then, by repeating the steps shown in FIGS. 8A to 8C, a plurality of laminate units are laminated. Next, a green sheet for an outer layer is laminated on the upper surface of the laminated body, final pressing is performed, and then the laminated body is cut into a predetermined size to form a green chip. In the case where the steps shown in FIGS. 7 and 8 are employed, the carrier sheet 20 can be selectively and easily peeled off by making the adhesive strength of the adhesive layer 28 stronger than the adhesive strength of the release layer 22. Is particularly effective.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.

Example 1
Preparation of release layer paste
Preparation of additive slurry First, as additive (subcomponent) raw materials, (Ba, Ca) SiO ₃ : 1.48 parts by weight, Y ₂ O ₃ : 1.01 parts by weight, MgCO ₃ : 0.72 parts by weight, MnO: 0.13 parts by weight of _V 2 _O 5: were prepared 0.045 parts by weight. Next, the prepared additive (subcomponent) raw material was mixed to obtain an additive (subcomponent) raw material mixture.

Next, the obtained additive raw material mixture: 4.38 parts by weight and ethyl acetate: 13.9 parts by weight were mixed and ground using a ball mill to obtain an additive slurry. The mixing and pulverization were performed using a 250 cc polyethylene resin container, charged with 450 g of ₂ mmφ ZrO ₂ media, and at a peripheral speed of 45 m / min and 20 hours. The particle diameter of the additive raw material after pulverization was 0.1 μm in median diameter.

Production of Primary Slurry Next, the obtained additive slurry: total amount, BaTiO ₃ powder (BT-01 / Sakai Chemical Industry Co., Ltd.) having an average particle size of 0.1 μm: 100 parts by weight, ethyl acetate: 107.9 Part by weight, 21.4 parts by weight of toluene, and 1.5 parts by weight of a polycarboxylate dispersant were mixed and ground using a ball mill. The mixing and pulverization were performed using a 1 liter polyethylene resin container, charged with 18 g of ₂ mmφ ZrO ₂ media, and at a peripheral speed of 45 m / min for 4 hours.

  Thereafter (after mixing for 4 hours), 7.0 parts by weight of mineral spirit and 6.5 parts by weight of acrylic resin (powder) were further added and further mixed for 16 hours by a ball mill to obtain a primary slurry. As the acrylic resin, a copolymer composed of a butyl acrylate monomer unit and a methyl methacrylate monomer unit having a Tg of 70 ° C., a molecular weight of 450,000, and an acid value of 5 mgKOH / g (copolymerization ratio based on weight% = 18: 82) was used. The non-volatile content concentration of the obtained primary slurry was 32.6%.

In this example, the above (BaTiO ₃ powder + additive material mixture) = ceramic powder (average particle size 0.1 μm).

Dilution of Primary Slurry In this example, since it is difficult to produce a highly dispersed and low concentration slurry in one step, first, a primary slurry having a relatively high concentration is prepared, and then this primary slurry. Is used to produce a release layer paste.

  Specifically, the obtained primary slurry is mixed using a ball mill with the binder lacquer prepared below and the entire primary slurry so that the total amount of acrylic resin is 50 parts by weight and the non-volatile content is 15%. did. The mixing was performed using a 3 liter polyethylene resin container under conditions of a peripheral speed of 45 m / min and 4 hours. In addition, binder lacquer prepared ethyl acetate: 727.5 weight part, toluene: 80.8 weight part, plasticizer (BBP): 26.08 weight part, and acrylic resin: 45.40 weight part, these were mixed. And heated and dissolved at 50 ° C.

  The slurry after mixing has a non-volatile content of 15%, an acrylic resin amount of 50 parts by weight with respect to 100 parts by weight of the ceramic powder, and a plasticizer content of 50 parts by weight with respect to 100 parts by weight of the acrylic resin (100 parts by weight of the ceramic powder). 25 parts by weight), and the ratio (P / B) of the ceramic powder to the acrylic resin and the plasticizer was 1.33 (Sample 3 in Table 1).

The slurry after the high dispersion treatment was mixed using a wet jet mill (HJP-25005, manufactured by Sugino Machine Co., Ltd.) to prepare a release layer paste. The treatment conditions were a pressure of 100 MPa and the number of treatments was one.

Formation of Release Layer A release film paste having a release layer (peeling force: 10.5 mN / cm) having a release layer mainly composed of silicone on the surface of the prepared release layer paste is a 38 μm thick PET film (first By using a bar coater (standard # 2) on the surface of the support sheet) and applying at a coating speed of 4 / min, and drying in a drying furnace at a furnace temperature of 60 ° C. for 1 minute, A release layer having a dry film thickness of 0.1 μm was formed.

Evaluation of release layer
Evaluation of the sheet attack of the sheet attack release layer is performed after the electrode layer paste and blank pattern layer paste used for the following printability evaluation are printed on the surface of the release layer to form the electrode layer and the blank pattern layer. The surface of the release layer opposite to the electrode layer and the blank pattern layer (the surface in contact with the PET film) was observed with a microscope, and the degree of dissolution of the release layer was confirmed by the degree of deformation and hue. The case where dissolution of the release layer could not be confirmed was judged as ◯, and the case where it was confirmed as x.

  As a result, dissolution of the release layer could not be observed, and the result was good.

The evaluation of printability is to print the electrode layer paste and blank pattern layer paste on the surface of the release layer, and to prevent bleeding, repelling, pinholes of the electrode layer and blank pattern layer formed on the surface of the release layer. The occurrence was observed by visual observation.

Specifically, first, Ni electrode paste (electrode layer paste) made of polyvinyl butyral (PVB) as a binder and terpineol as a solvent is applied to the surface of the release layer so that the Ni metal adhesion amount is 0.55 mg / cm ^2. Was printed with a screen printer and dried under the conditions of 90 ° C. and 2 minutes to form a predetermined pattern of electrode layer 12a having a dry film thickness of 1 μm. Next, BaTiO ₃ paste (blank pattern layer paste) made of polyvinyl butyral (PVB) as a binder and terpineol as a solvent is applied to a portion of the release layer where the electrode layer 12a is not formed, with a BaTiO ₃ adhesion amount of 0. It was printed by a screen printer so as to be .43 mg / cm ² and dried at 90 ° C. for 2 minutes to form a blank pattern. For the printing of the blank pattern, a screen plate making having a pattern complementary to the pattern used when printing the electrode layer paste was used. The blank pattern was formed so that the dry film thickness was the same as that of the electrode layer. Thereafter, the occurrence of bleeding, repelling, and pinholes in the electrode layer and blank pattern layer formed on the surface of the release layer was visually observed. A case where no bleeding, repelling, or pinhole generation in the electrode layer or blank pattern layer could be confirmed was judged as ◯, and a case where any one or more was confirmed as x.

  As a result, the occurrence of bleeding, repellency, and pinholes in the electrode layer and blank pattern layer could not be confirmed.

Shitokasu Shitokasu evaluation of the electrode layer paste and blank pattern layer paste used for evaluation of the printability, when printed on the surface of the release layer, the release layer is scraped, whether debris is generated This was done by visual observation. The case where no debris of the release layer could be confirmed was judged as ◯, and the case where it was confirmed as x.

  As a result, the residue of the release layer could not be confirmed, and it was good.

Fluctuation of electrode layer paste adhesion (electrode printing condition)
The evaluation of the fluctuation of the electrode layer paste adhesion amount is performed by printing the electrode layer paste used in the evaluation of the printability 3000 times on the surface of the release layer, and the electrode layer paste adhesion amount after starting and ending printing. Was measured, and the fluctuation amount of the adhesion amount was calculated. The amount of change varies depending on the repellency of the electrode layer and the sheet attack of the release layer. In this example, the case where the variation was less than 10% was judged as ◯, and the case where it was 10% or more was judged as x.

  As a result, the fluctuation amount of the adhesion amount of the electrode layer paste was 2.7%, which was ◯. 9A and 9A are photographs showing a release layer state after printing the electrode layer paste once on the surface of the release layer and a release layer state after printing the electrode layer paste 3000 times on the surface of the release layer. As shown in FIG. As shown in FIGS. 9A and 9B, according to the release layer of Example 1, it can be confirmed that the state of the release layer is still good even when the electrode layer paste is printed 3000 times. .

The peelability of the electrode layer and the blank pattern layer The evaluation of the peelability of the electrode layer and the blank pattern layer is carried out by using the electrode layer paste and blank pattern layer paste used for the evaluation of the printability as described above. After forming the electrode layer and the blank pattern layer, the peeling strength when peeling the electrode layer and the blank pattern layer from the peeling layer was measured.

  Specifically, for example, the sheet in the state shown in FIG. 2B is used with a double-sided tape (Scotch ST-416) so that the PET film (corresponding to the carrier sheet 20 in FIG. 2B) is on top. Affixed to the sample stage, then one end of the PET film was 8 mm / min. The force (mN / cm) acting on the PET film carrier sheet 20 at that time was measured as the peel strength between the electrode layer and the blank pattern layer (90 ° peel test method).

  By reducing the peel strength, the PET film can be favorably peeled from the electrode layer and the blank pattern layer. Moreover, since the damage of the electrode layer and the blank pattern layer at the time of peeling can be effectively prevented, the peel strength is preferably low. On the other hand, if the peel strength is lower than the peel strength at the time of transfer of an adhesive layer or green sheet described later, transfer of the adhesive layer or green sheet becomes difficult. Therefore, in this example, 10 mN / cm or more was considered good. On the other hand, if the peel strength is too high, it becomes difficult to peel the PET film from the electrode layer and the blank pattern layer during lamination. Therefore, in this example, 20 mN / cm or less was considered good.

  As a result, an appropriate value of 15.9 mN / cm was shown. Thereby, while the peeling layer of a present Example can maintain required holding power with respect to PET film, the efficiency of peeling work can be anticipated.

Surface roughness The surface roughness was evaluated by printing the electrode layer paste and blank pattern layer paste used for the above printability evaluation on the surface of the release layer to form the electrode layer and blank pattern layer, The surface roughness (Ra: surface roughness effective value) of the layer and the blank pattern surface was measured using “Surf Coder (SE-30D)” (trade name) manufactured by Kosaka Laboratory Ltd. If the surface roughness is large, short circuit failure occurs. Therefore, in this example, it was judged that the case where Ra was 0.1 μm or less was good.

  As a result, Ra was an appropriate value of 0.077 μm. Thereby, the merit of short circuit defect reduction can be expected.

  The above results are shown in Table 1 described later.

Example 2
Except that the acid value of the acrylic resin was changed as shown in Table 1, a release layer paste was prepared in the same manner as in Example 1, and the same evaluation was performed (Samples 1, 2, 4, and 5). The results are shown in Table 1.

  As shown in Table 1, the surface roughness increased when the acid value was 0 mgKOH / g. Further, when the acid value was 15 mgKOH / g, the peel strength and surface roughness of the electrode layer increased. On the other hand, when the acrylic resin which has an acid value in an appropriate range (1-10 mgKOH / g) was used, it has confirmed that all the characteristics could be satisfied.

Example 3
By changing the content (parts by weight) of the acrylic resin and the plasticizer with respect to 100 parts by weight of the ceramic powder, the content (parts by weight) of the acrylic resin with respect to 100 parts by weight of the ceramic powder, the ceramic powder, the acrylic resin, and the plasticizer Except that the ratio (P / B) was varied as shown in Table 2, a release layer paste was prepared in the same manner as in Example 1, and the same evaluation was performed (Samples 6 to 10). The results are shown in Table 2.

  As shown in Table 2, when the P / B value is decreased, the printability is deteriorated, and when the P / B value is increased, there is a tendency that sheet attack and sheet residue are generated along with the printability. From Table 2, when the P / B value is 0.67 to 5.56 (excluding 0.67 and 5.56), the acrylic resin content is 12 to 100 weights with respect to 100 parts by weight of the ceramic powder. It was confirmed that all the characteristics could be satisfied when the content was 1 part (excluding 12 parts by weight and 100 parts by weight).

Example 4
Except that the content (parts by weight) of the plasticizer relative to 100 parts by weight of the ceramic powder was changed as shown in Table 3, a release layer paste was prepared in the same manner as in Example 1, and the same evaluation was performed (Sample 12). ~ 16). The results are shown in Table 3.

  As shown in Table 3, when the amount of the plasticizer decreases, the peel strength of the electrode layer and the blank pattern layer tends to increase, and the peel becomes heavy. When the amount of the plasticizer increases, the printability and the electrode printing state tend to deteriorate. From Table 3, it was confirmed that all characteristics can be satisfied especially when the plasticizer content is 5 to 100 parts by weight (excluding 5 parts by weight and 100 parts by weight) with respect to 100 parts by weight of the ceramic powder. .

Example 5
A release layer paste was prepared in the same manner as in Example 1 except that the release force on the mold release side of the PET film (first support sheet) was changed as shown in Table 4, and the same evaluation was performed ( Samples 17-23). The results are shown in Table 4.

  As shown in Table 4, when the release force on the mold release side of the PET film decreases, the release layer tends to fall off the PET film together with the electrode layer and blank pattern layer formed thereon, and the release force increases. The peeling of the electrode layer and the blank pattern layer is too heavy, and the lamination efficiency tends to decrease. From Table 4, it was confirmed that all the characteristics could be satisfied especially when the peel force was 7.3 to 20.3 mN / cm (however, excluding 7.3 mN / cm and 20.3 mN / cm).

Example 6
First, a release layer was formed in the same manner as Sample 3 in Example 1. Then, the solvent of the electrode layer paste and the blank pattern layer paste is changed to each solvent shown in Tables 5 and 6 to change the sheet attack, printability, sheet residue, and electrode layer paste adhesion amount of the release layer (electrode The printed state), the peelability of the electrode layer and the blank pattern layer, and the surface roughness were evaluated (samples 24 to 40 and 41 to 43). The results are shown in Tables 5 and 6.

  In Samples 24 to 40 and 41 to 43 in Tables 5 and 6, each solvent was used in a weight ratio of 50:50. That is, for example, in Sample 24, the solvent for the electrode layer paste and the blank pattern layer paste was terpineol: dihydroterpineol acetate = 50: 50 (weight ratio).

  Moreover, the sample shown in Table 5 is a sample with terpineol: each solvent = 50: 50 (weight ratio), and the sample shown in Table 6 is each solvent: terpinyl methyl ether = 50: 50 (weight). Ratio).

  According to Tables 5 and 6, even when the solvent for the electrode layer paste and the blank pattern layer paste is changed as shown in Samples 24 to 36 in Table 5 and Samples 41 to 43 in Table 6, all characteristics can be satisfied. Was confirmed. On the other hand, samples 37 to 40 in Table 5 containing d-dihydrocarbon, menthone, perillyl acetate and butyl carbitol as solvents for the electrode layer paste and blank pattern layer paste generate sheet attack and sheet residue. This resulted in inferior printability and electrode printing state. Incidentally, in these samples 37 to 40, the reason why such a result was obtained was that d-dihydrocarbon, menthone, perillyl acetate and butyl carbitol dissolved the acrylic resin contained in the release layer. Conceivable.

Comparative Example 1
A release layer paste was prepared by changing the acrylic resin of Example 1 to a polyvinyl butyral resin. Specifically, it is as follows.

Preparation of release layer paste
Preparation of additive slurry First, an additive (subcomponent) raw material mixture having the same composition as in Example 1 was prepared.

Next, the obtained additive raw material mixture: 4.3 parts by weight, ethyl alcohol: 3.1 parts by weight, n-propanol: 3.1 parts by weight, xylene: 1.1 parts by weight, and polyethylene glycol-based dispersant: 0.04 part by weight was mixed and ground using a ball mill to obtain an additive slurry. The mixing and pulverization were performed using a 250 cc polyethylene resin container, charged with 450 g of ₂ mmφ ZrO ₂ media, and at a peripheral speed of 45 m / min and 20 hours. The particle diameter of the additive raw material after pulverization was 0.1 μm in median diameter.

Production of Primary Slurry Next, the obtained additive slurry: total amount, BaTiO ₃ powder having an average particle size of 0.1 μm (BT-01 / Sakai Chemical Industry Co., Ltd.): 100 parts by weight, ethyl alcohol: 45.88 Parts by weight, n-propanol: 45.88 parts by weight, xylene: 22.4 parts by weight, dioctyl phthalate (DOP) plasticizer: 3.03 parts by weight, mineral spirit: 7.31 parts by weight, and polyethylene glycol-based dispersant : 1.0 part by weight was mixed and ground using a ball mill. The mixing and pulverization were performed using a 1 liter polyethylene resin container, charged with 18 g of ₂ mmφ ZrO ₂ media, and at a peripheral speed of 45 m / min for 4 hours.

  Thereafter (after mixing for 4 hours), polyvinyl butyral (PVB) resin (polymerization degree 1450, butyralization degree 69%, residual acetyl group amount 12%) was dissolved in ethyl alcohol: n-propanol = 1: 1, resin solids Add 41.6 parts by weight of 15% lacquer (additional amount of polyvinyl butyral resin is 6% by weight with respect to the powder (barium titanate + additive)). Mixing was performed to obtain a primary slurry. The non-volatile content concentration of the obtained primary slurry was 41.3%.

In this comparative example, the above (BaTiO ₃ powder + additive raw material mixture) = ceramic powder (average particle size 0.1 μm).

Dilution of Primary Slurry In this example, since it is difficult to produce a highly dispersed and low concentration slurry in one step, first, a primary slurry having a relatively high concentration is prepared, and then this primary slurry. Is used to produce a release layer paste.

  Specifically, using a ball mill, the obtained primary slurry was mixed with the binder lacquer and the primary slurry as described below so that the total amount of added polyvinyl butyral resin was 9 parts by weight and the non-volatile content was 15%. And mixed. The mixing was performed using a 3 liter polyethylene resin container under conditions of a peripheral speed of 45 m / min and 4 hours. The binder lacquer was composed of 244.81 parts by weight of ethyl alcohol, 244.81 parts by weight of n-propanol, 131.83 parts by weight of xylene, 22.98 parts by weight of dioctyl phthalate (DOP) plasticizer and PVB- 15% lacquer: 303.34 parts by weight were prepared, mixed, and heated and dissolved at 50 ° C.

  The slurry after mixing has a nonvolatile content of 15%, the PVB resin amount is 50 parts by weight with respect to 100 parts by weight of the ceramic powder, and the plasticizer content is 50 parts by weight with respect to 100 parts by weight of the PVB resin. (Sample 11 in Table 2).

The slurry after mixing obtained by high dispersion treatment was treated in the same manner as in Example 1 to prepare a release layer paste.

Formation of Release Layer The release layer paste thus prepared was applied to the surface of the PET film (first support sheet) used in Example 1 and dried under the same conditions, whereby the dry film thickness was 0.2 μm. A release layer was formed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  As shown in Table 2, it was confirmed that sheet attack and sheet residue were generated, and printability deteriorated.

Moreover, the fluctuation amount (electrode printing state) of the electrode layer paste adhesion amount was 28%, which was x. A photograph of the state of the release layer after printing the electrode layer paste once on the surface of the release layer and the state of the release layer after printing the electrode layer paste 3000 times on the surface of the release layer are shown in FIG. ) And FIG. 10B. As shown in FIGS. 10 (A) and 10 (B), according to the release layer of Comparative Example 1, when the electrode layer paste is printed 3000 times, the sheet residue of the release layer is scattered and the state is deteriorated. I can confirm that.
From the above, the significance of Examples 1 to 6 could be confirmed.

Example 7
Green Sheet Paste First, an additive (subcomponent) raw material mixture having the same composition as Example 1 (Sample 3 in Table 1) was prepared.

Next, the obtained additive raw material mixture: 4.3 parts by weight, ethanol: 3.11 parts by weight, propanol: 3.11 parts by weight, xylene: 1.11 parts by weight and dispersant: 0.04 parts by weight The mixture was pulverized using a ball mill to obtain an additive slurry. The mixing and pulverization were carried out using a 250 cc polyethylene resin container, charged with 450 g of ₂ mmφ ZrO ₂ media under conditions of a peripheral speed of 45 m / min and 16 hours. The particle diameter of the additive raw material after pulverization was 0.1 μm in median diameter.

Next, the obtained additive slurry: 11.65 parts by weight, BaTiO ₃ powder (BT-02 / Sakai Chemical Industry Co., Ltd.): 100 parts by weight, ethanol: 35.32 parts by weight, propanol: 35.32 parts by weight Parts, xylene: 16.32 parts by weight, dioctyl phthalate (plasticizer): 2.61 parts by weight, mineral spirit: 7.3 parts by weight, dispersant: 2.36 parts by weight, charging aid: 0.42 parts by weight Parts, organic vehicle: 33.74 parts by weight, MEK: 43.81 parts by weight and 2-butoxyethanol: 43.81 parts by weight were mixed using a ball mill to obtain a paste for green sheets.
The mixing by the ball mill was carried out using a 500 cc polyethylene resin container, charging 900 g of ₂ mmφ ZrO ₂ media, and at a peripheral speed of 45 m / min and 20 hours. In addition, the above organic vehicle has 15 parts by weight of polyvinyl butyral resin having a polymerization degree of 1450 and a butyralization degree of 69% (manufactured by Sekisui Chemical Co., Ltd.): 42.5 parts by weight of ethanol and 42.5 parts by weight of propanol. This was prepared by stirring and dissolving in a part at a temperature of 50 ° C. That is, the resin content (amount of polyvinyl butyral resin) in the organic vehicle was 15% by weight.

Adhesive layer paste Butyral resin (polymerization degree 800, butyralization degree 77%): 2 parts by weight, MEK: 98 parts by weight and DOP (dioctyl phthalate): 1 part by weight Produced.

Preparation of Multilayer Ceramic Capacitor Sample Using the release layer paste, electrode layer paste and blank pattern layer paste prepared in Example 1, the green sheet paste and adhesive layer paste prepared in this example, the following Thus, the multilayer ceramic capacitor 2 shown in FIG. 1 was manufactured.

Formation of Green Sheet First, as in Example 1, a release layer (dry film thickness 0.1 μm) was formed on a PET film, and an electrode layer and a blank pattern layer (both dry film thickness 1 μm) were formed on the surface of the release layer. Formed.

  Next, the green sheet 10a having the electrode layer 12a and the blank pattern 24 is formed by applying the green sheet paste on the electrode layer and the blank pattern with a die coater and then drying the paste. Got. The coating speed is 50 m / min. And drying was performed using the drying furnace which made the furnace temperature 80 degreeC. The green sheet was formed so that the film thickness when dried was 1 μm.

Formation of adhesive layer, transfer of adhesive layer First, prepare another PET film (second support sheet), apply the above adhesive layer paste on the PET film with a die coater, and then dry it. Thus, an adhesive layer was formed. The coating speed is 70 m / min. And drying was performed using the drying furnace which made the furnace temperature 80 degreeC. The adhesive layer was formed so that the film thickness upon drying was 0.1 μm. In addition, unlike the 1st support sheet, said 2nd support sheet used the PET film which gave the surface the peeling process with silicone resin.

  Next, the adhesive layer 28 was transferred onto the produced green sheet 10a having the electrode layer 12a and the blank pattern 24 by the method shown in FIG. 3 to form a multilayer unit U1a. At the time of transfer, a pair of rolls were used, the pressure was 0.1 MPa, the transfer temperature was 80 ° C., the transfer speed was 2 m / min, and it was confirmed that the transfer could be performed satisfactorily.

Production of Green Chip First, a plurality of outer layer green sheets molded to a thickness of 10 μm are laminated so that the thickness at the time of lamination is about 50 μm, and the outer layer that becomes the lid portion (cover layer) of the multilayer capacitor after firing is formed. Formed. The green sheet for the outer layer is a green sheet formed using the green sheet paint produced above so that the thickness after drying is 10 μm.

  Next, 100 laminate units produced as described above were laminated thereon by the method shown in FIGS. Further, a plurality of outer layer green sheets molded to a thickness of 10 μm are laminated thereon so that the thickness at the time of lamination is about 50 μm, and the outer layer that becomes the lid portion (cover layer) of the multilayer capacitor after firing. Formed. And the obtained laminated body was press-molded on conditions of 100 MPa and 70 ° C., and then cut with a dicing machine to obtain a green chip before firing.

Production of sintered body Next, the final laminate was cut into a predetermined size and subjected to binder removal processing, firing and annealing (heat treatment) to produce a chip-shaped sintered body.

The binder removal was performed at a temperature rising rate: 50 ° C./hour, a holding temperature: 240 ° C., a holding time: 8 hours, and an atmospheric gas: in the air. Firing is carried out by heating at a heating rate of 300 ° C./hour, a holding temperature of 1200 ° C., a holding time of 2 hours, a cooling rate of 300 ° C./hour, and an atmosphere gas of N ₂ gas and H ₂ (5 %) And mixed gas. Annealing (reoxidation) was performed with a holding time: 3 hours, a cooling rate: 300 ° C./hour, and an atmosphere gas: N ₂ gas controlled to a dew point of 20 ° C. The atmosphere gas was humidified using a wetter at a water temperature of 0 to 75 ° C.

  Next, after polishing the end surface of the chip-shaped sintered body with sand blasting, an In-Ga alloy paste is applied to the end portion, and then firing is performed to form an external electrode. A sample of a multilayer ceramic capacitor was obtained.

Measurement of short circuit defect ratio The short circuit defect ratio was measured by preparing 50 capacitor samples and examining the number of short circuit defects. Specifically, the resistance value was measured using an insulation resistance meter (E2377A multimeter manufactured by HEWLETT PACKARD), and the sample having a resistance value of 100 kΩ or less was defined as a short defect sample. The ratio of samples was defined as the short defect rate. In this example, the case where the short-circuit defect rate was 10% or less was considered good. As a result, the short-circuit defect rate was 6%, and a very good result was obtained.

FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention. FIG. 2A to FIG. 2C are cross-sectional views showing the main parts of the electrode layer and green sheet forming method according to one embodiment of the present invention. FIG. 3A to FIG. 3C are cross-sectional views of relevant parts showing a method for forming an adhesive layer according to an embodiment of the present invention. 4 (A) and 4 (B) are cross-sectional views showing a main part of a method for laminating green sheets having electrode layers according to an embodiment of the present invention. 5 (A) and 5 (B) are cross-sectional views showing the main part of the process following FIG. 6 (A) and 6 (B) are cross-sectional views showing a main part of a method for laminating green sheets having electrode layers according to another embodiment of the present invention. FIG. 7A to FIG. 7C are cross-sectional views showing the main part of a method for laminating green sheets having electrode layers according to other embodiments of the present invention. FIG. 8A to FIG. 8C are cross-sectional views of relevant parts showing steps subsequent to FIG. 9A is a photograph showing the state of the release layer after the electrode layer paste is printed once on the surface of the release layer of Example 1, and FIG. 9B is an electrode on the surface of the release layer of Example 1. It is a photograph which shows the state of the peeling layer after printing the layer paste 3000 times. 10A is a photograph showing the state of the release layer after the electrode layer paste is printed once on the surface of the release layer of Comparative Example 1, and FIG. 10B is an electrode on the surface of the release layer of Comparative Example 1. It is a photograph which shows the state of the peeling layer after printing the layer paste 3000 times.

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 50 ... Blank pattern portion 26 ... Carrier sheet (second support sheet)
28 ... Adhesive layer 30 ... Green sheet for outer layer U1a to U1c ... Laminate unit

Claims (14)

A release layer paste used for manufacturing a multilayer electronic component,
Used in combination with paste for electrode layers containing terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate,
Including ceramic powder, organic vehicle, plasticizer, and dispersant;
The binder in the organic vehicle is mainly composed of acrylic resin,
The acrylic resin is composed of a copolymer having an acrylic acid ester monomer unit and a methacrylic acid ester monomer unit as main components and an acid value of 1 to 10 mgKOH / g,
A ratio (P / B) of the ceramic powder to the binder and the plasticizer is controlled to 0.67 to 5.56 (excluding 0.67 and 5.56). Release layer paste. A release layer paste used for manufacturing a multilayer electronic component,
Used in combination with paste for electrode layers containing terpineol, dihydroterpineol, terpineol acetate or dihydroterpineol acetate,
Including ceramic powder, organic vehicle, plasticizer, and dispersant;
The binder in the organic vehicle is mainly composed of acrylic resin,
The acrylic resin is composed of a copolymer having an acrylic acid ester monomer unit and a methacrylic acid ester monomer unit as main components and an acid value of 1 to 10 mgKOH / g,
The release layer paste, wherein the content of the binder is 12 to 100 parts by weight (excluding 12 parts by weight and 100 parts by weight) with respect to 100 parts by weight of the ceramic powder.   The electrode layer paste used in combination is terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, isobornyl acetate, d-dihydrocarbeveol, menthyl acetate, The release layer paste according to claim 1 or 2, further comprising one or more selected from citronol, perillyl alcohol, and acetoxy-methoxyethoxy-cyclohexanol acetate.   The release layer paste according to any one of claims 1 to 3, wherein the acrylic resin has a weight average molecular weight of 230,000 to 700,000.   The plasticizer is at least one selected from dibutyl phthalate (DBP), dioctyl phthalate (DOP), and butyl benzyl phthalate (BBP), and 5 to 100 parts by weight (100 parts by weight with respect to 100 parts by weight of the ceramic powder) However, excluding 5 parts by weight and 100 parts by weight), the release layer paste according to any one of claims 1 to 4.   The release layer paste according to claim 1, wherein the ceramic powder has an average particle size of 0.2 μm or less.   The release layer paste according to any one of claims 1 to 6, wherein the dispersant is a polycarboxylate-based dispersant and is contained in an amount of 0.5 to 3 parts by weight with respect to 100 parts by weight of the ceramic powder. .   The solvent in the organic vehicle is one or more of acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and toluene, and is contained so that the nonvolatile content concentration is 5 to 20% by weight. The release layer paste according to any one of? Forming a release layer on the release treatment side of the first support sheet subjected to the release treatment;
Forming an electrode layer in a predetermined pattern on the surface of the release layer;
Forming a green sheet on the surface of the electrode layer to obtain a green sheet having an electrode layer;
Laminating a green sheet having the electrode layer to form a green chip;
A step of firing the green chip, comprising the steps of:
A method for manufacturing a multilayer electronic component, wherein the release layer paste according to claim 1 is used as a release layer paste for forming the release layer.   The mold release treatment applied to the first support sheet is formed by a coating method using a release agent mainly composed of silicone, and the release force of the first support sheet is 7.3 to 20.3 mN / cm (however, The method of manufacturing a multilayer electronic component according to claim 9, which is controlled to be 7.3 mN / cm and 20.3 mN / cm.   The method for producing a multilayer electronic component according to claim 9 or 10, wherein the ceramic powder contained in the release layer paste is the same as the ceramic powder contained in the paste for forming the green sheet.   The method for producing a multilayer electronic component according to claim 9, wherein the release layer has a thickness of 0.05 to 0.2 μm.   Before forming the green sheet, a blank pattern layer having the same thickness as the electrode layer and made of the same material as the green sheet is formed on the surface of the release layer where the electrode layer is not formed. Item 13. A method for manufacturing a multilayer electronic component according to any one of Items 9 to 12. Before laminating the green sheet having the electrode layer, an adhesive layer is formed on the surface opposite to the electrode layer of the green sheet having the electrode layer, and the green sheet having the electrode layer is laminated via the adhesive layer. The manufacturing method of the multilayer electronic component according to any one of claims 9 to 13.

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