Step difference absorbing paste and method for manufacturing laminated electronic component using the same

Abstract

The present application aims to provide a step difference absorbing paste capable of improving the adhesion of a step difference absorbing pattern layer to an inner side wafer and also capable of improving the operability in work. The step difference absorbing paste has a first ceramic powder, ethyl cellulose, and terpene phenol, wherein A1 is 10 to 26 parts by mass, A1 is the total content of the ethyl cellulose and the terpene phenol in the step difference absorbing paste when the content of the first ceramic powder in the step difference absorbing paste is set to 100 parts by mass, the average mass molecular weight of the terpene phenol is 220 to 650, and the content of the terpene phenol is 30 to 67 parts by mass when the total content of the ethyl cellulose and the terpene phenol is set to 100 parts by mass.

Description

Technical Field

[0001] This invention relates to a step difference absorbing paste and a method for manufacturing a laminated electronic component using the step difference absorbing paste. Background Technology

[0002] As an example of a multilayer electronic component, a multilayer ceramic capacitor, as shown in Patent Document 1, can be obtained, for example, by the manufacturing method described below. First, a green laminate is obtained by stacking multiple inner green sheets having internal electrode pattern layers. Next, the green laminate is pressurized and heated using a mold, cut into a chip shape, and then fired to obtain a component body. Then, external electrodes are formed on this component body to obtain a multilayer ceramic capacitor.

[0003] Here, on the inner side of the green sheet, the internal electrode pattern layer is usually not formed on its entire surface, but rather in the gaps between the internal electrode pattern layers.

[0004] However, if lamination is performed with gaps created by the internal electrode pattern layer, the force applied to the inner green sheet by pressing becomes uneven due to the presence of these gaps. Therefore, undesirable deformations such as bending of the inner green sheet at the gap portions and thickness variations in the capacitor forming portion become problems.

[0005] Therefore, step difference absorption paste is sometimes used to form step difference absorption pattern layers by filling the gaps in the internal electrode pattern layers.

[0006] However, as the laminated ceramic capacitor becomes thinner, the strength of the inner green sheet increases, but this tends to reduce the adhesion between the step difference absorption pattern layer and the inner green sheet.

[0007] To mitigate this tendency, methods exist to impart high adhesion to the step difference absorbing pattern layer. However, if high adhesion is applied to the step difference absorbing pattern layer, there is a tendency for unintended adhesion and reduced operability in operations due to this adhesion.

[0008] [Existing technical documents]

[0009] [Patent Literature]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2000-133547 Summary of the Invention

[0011] The technical problem that the invention aims to solve

[0012] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a step difference absorbing paste that can improve the adhesion between the step difference absorbing pattern layer and the inner green sheet, and also improve the operability of the operation, as well as a method for manufacturing a laminated electronic component using the step difference absorbing paste.

[0013] Means for solving technical problems

[0014] The step difference absorption paste involved in this invention, wherein,

[0015] This step difference absorption paste contains a first ceramic powder, ethyl cellulose, and terpene phenols.

[0016] A1 is available in quantities of 10 to 26 parts by weight.

[0017] A1 refers to the total content of ethyl cellulose and terpene phenols in the step difference absorption paste when the content of the first ceramic powder in the paste is set to 100 parts by mass.

[0018] The average molecular weight of the terpene phenols is 220–650.

[0019] When the total content of the ethyl cellulose and the terpene phenol is set to 100 parts by mass, the content of the terpene phenol is 30 to 67 parts by mass.

[0020] The step difference absorbing paste according to the present invention can improve the adhesion between the step difference absorbing pattern layer and the inner green sheet, and can also improve the operability of the operation.

[0021] The present invention relates to a method for manufacturing a stacked electronic component, wherein,

[0022] It has a process of alternatingly overlapping inner green sheets and inner electrode pattern layers to obtain a green sheet laminate.

[0023] A step difference absorption pattern layer is formed in the gaps between the internal electrode pattern layers.

[0024] The inner green sheet is formed using an inner ceramic paste.

[0025] The inner ceramic paste contains a second ceramic powder and butyral resin.

[0026] The step difference absorption pattern layer is formed using a step difference absorption paste.

[0027] The step difference absorption paste contains a first ceramic powder, ethyl cellulose, and terpene phenols.

[0028] A1 is available in quantities of 10 to 26 parts by weight.

[0029] A1 refers to the total content of ethyl cellulose and terpene phenols in the step difference absorption paste when the content of the first ceramic powder in the paste is set to 100 parts by mass.

[0030] The average molecular weight of the terpene phenols is 220–650.

[0031] When the total content of the ethyl cellulose and the terpene phenol is set to 100 parts by mass, the content of the terpene phenol is 30 to 67 parts by mass.

[0032] The laminated electronic component according to the present invention can improve the adhesion between the step difference absorption pattern layer and the inner green sheet, and can also improve the operability in operation.

[0033] Preferably, the first ceramic powder and the second ceramic powder have substantially the same composition.

[0034] Preferably, A2 is 10 parts by weight or more and 20 parts by weight or less.

[0035] A2 refers to the content of butyral resin in the inner ceramic paste when the content of the second ceramic powder in the inner ceramic paste is set to 100 parts by mass.

[0036] A1 is greater than or equal to A2. Attached Figure Description

[0037] Figure 1A This is a cross-sectional view showing a multilayer ceramic capacitor according to one embodiment of the present invention.

[0038] Figure 1B It is along Figure 1A A cross-sectional view of a multilayer ceramic capacitor with an IB-IB line.

[0039] Figure 2A It means Figure 1A as well as Figure 1B A cross-sectional view of a major part of the manufacturing process of a multilayer ceramic capacitor is shown.

[0040] Figure 2B It means Figure 2A The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0041] Figure 2C It means Figure 2B The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0042] Figure 3A It means Figure 2C The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0043] Figure 3B It means Figure 3A The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0044] Figure 4A It means Figure 3B The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0045] Figure 4B It means Figure 3B The diagram shows a cross-sectional view of the main subsequent parts of the manufacturing process.

[0046] Explanation of reference numerals in the attached figures

[0047] 1...Laminated ceramic capacitors

[0048] 10……Component Body

[0049] 10a…Interior area

[0050] 10b...Exterior Area

[0051] 10c...edge area

[0052] 2...Inner dielectric layer (inner ceramic layer)

[0053] 3a, 3b... Internal electrode layers

[0054] 4a, 4b... External electrodes

[0055] 20……carrier slices

[0056] 30……medial sclera

[0057] 40……Internal Electrode Pattern Layer

[0058] 50……Blank pattern area

[0059] 60……Step Difference Absorption Pattern Layer

[0060] 110……Green laminated body

[0061] 110a……Interior area green laminate

[0062] 110b……Outer assembly area green laminate

[0063] 110c……Green laminated body in the edge region Detailed Implementation

[0064] The present invention will now be described based on embodiments shown in the accompanying drawings. In this embodiment, a multilayer ceramic capacitor is described as an example of a multilayer electronic component.

[0065] Multilayer ceramic capacitors

[0066] like Figure 1A as well as Figure 1B As shown, a laminated ceramic capacitor 1 according to one embodiment of the present invention has an element body 10. The element body 10 has an inner region 10a, an outer region 10b, and an edge region 10c.

[0067] The internal region 10a has an inner dielectric layer 2 (inner ceramic layer 2) and internal electrode layers 3a and 3b that are substantially parallel to a plane including the X and Y axes. The inner dielectric layer 2 and the internal electrode layers 3a and 3b are stacked alternately in the Z-axis direction. In addition, the ends of the internal electrode layers 3a and 3b in the X-axis direction are stacked in such a way that the surfaces of two opposite end faces (planes parallel to the ZY plane) in the X-axis direction of the component body 10 are alternately exposed.

[0068] A pair of external electrodes 4a and 4b are formed on both ends of the component body 10 in the X-axis direction, respectively, and are connected to the internal electrode layers 3a and 3b that are alternately arranged inside the component body 10. The external electrodes 4a and 4b are connected to the exposed ends of the alternately arranged internal electrode layers 3 to form a capacitor circuit.

[0069] The outer casing region 10b is located outside the inner casing region 10a in the stacking direction (Z-axis direction). The outer casing region 10b is composed of an outer dielectric layer (outer ceramic layer). The outer casing region 10b can be a single-layer structure composed of only one outer dielectric layer, or it can be a stacked structure with multiple outer dielectric layers.

[0070] The edge region 10c is located to the side of the interior region 10a. Specifically, as shown... Figure 1B As shown, the area from the end of the component body 10 containing the internal electrode layers 3a and 3b along the Y-axis direction, parallel to the ZX plane, to the end face of the component body 10 along the Y-axis direction (parallel to the ZX plane) is defined as the edge region 10c.

[0071] Here, the X-axis, Y-axis, and Z-axis are perpendicular to each other.

[0072] In addition, "inner side" refers to the side closer to the center of the multilayer ceramic capacitor 1, while "outer side" refers to the side farther away from the center of the multilayer ceramic capacitor 1.

[0073] Furthermore, "substantially parallel" means that almost all parts are parallel, but there may also be slightly non-parallel parts. The inner dielectric layer 2 and the inner electrode layers 3a and 3b may also have slight irregularities or inclinations.

[0074] There are no particular restrictions on the shape and size of the component body 10, and it can be set appropriately according to the application. Generally, the shape is set to a roughly cuboid shape, and the size can usually be set to L0 (0.4mm~5.6mm)×W0 (0.2mm~5.0mm)×T0 (0.2mm~1.9mm).

[0075] The inner dielectric layer 2 is described later. Figures 2A to 2C The inner green sheet 30 shown is formed by firing. Furthermore, as described later... Figure 2C The step difference absorption pattern layer 60 shown also forms the inner dielectric layer 2 after firing.

[0076] There are no particular limitations on the main component of the inner dielectric layer 2; for example, a compound represented by the general formula ABO3 can be used.

[0077] Here, the main component of the inner dielectric layer 2 refers to the component that accounts for 80 or more parts by mass when the inner dielectric layer 2 is set to 100 parts by mass, preferably 90 or more parts by mass.

[0078] Furthermore, the main component of the inner dielectric layer 2 refers to the components that constitute the second ceramic powder after firing. The second ceramic powder is contained within the inner green sheet 30.

[0079] As a specific example of a compound represented by the general formula ABO3, one could cite compounds composed of {(Ba 1-x-y Ca x Sr y )O} u (Ti 1-z Zr z ) v Compounds represented by O2. It should be noted that u, v, x, y, and z are all arbitrary ranges, but are preferably within the following ranges.

[0080] In the above formula, x is preferably 0 ≤ x ≤ 0.1, and more preferably 0 ≤ x ≤ 0.05. By setting x to the above range, the relative permittivity can be increased. Furthermore, in this embodiment, Ca may not necessarily be included. That is, x may also be 0.

[0081] In the above formula, y is preferably 0 ≤ y ≤ 0.1, and more preferably 0 ≤ y ≤ 0.05. By setting y to the above range, the relative permittivity can be increased. Furthermore, in this embodiment, Sr may not necessarily be included. That is, y may also be 0.

[0082] In the above formula, z is preferably 0 ≤ z ≤ 0.3, and more preferably 0 ≤ z ≤ 0.15. By setting z to the above range, the relative permittivity can be increased. Furthermore, in this embodiment, Zr may not necessarily be included. That is, z may also be 0.

[0083] In the above formula, u and v are preferably in a relationship that satisfies u / v = 0.9 to 1.2.

[0084] Furthermore, the main component of the inner dielectric layer 2 is preferably barium titanate. That is, it is preferably x=y=z=0.

[0085] In the inner dielectric layer 2, elements such as Ba, Si, Mg, Mn, V, Zr, and rare earth elements may also be present as secondary components.

[0086] The thickness of the inner dielectric layer 2 is preferably reduced to less than 1 μm.

[0087] The internal electrode layers 3a and 3b are described later. Figure 2B and Figure 2C The internal electrode pattern layer 40, as shown in the specified pattern, is formed by firing. The internal electrode pattern layer 40 contains conductive powder.

[0088] The conductive powder is not particularly limited, but is preferably composed of at least one selected from Cu, Ni and their alloys, and more preferably composed of Ni or Ni alloys and mixtures thereof.

[0089] The preferred alloy of Ni or Ni is an alloy of Ni with at least one element selected from Mn, Cr, Co, and Al, and the Ni content in the alloy is preferably 95% by mass or more. Furthermore, trace elements such as P, Fe, and Mg may be present in the Ni or Ni alloy in amounts of 0.1% by mass or less.

[0090] The thickness of the internal electrode layers 3a and 3b is preferably less than 1 μm.

[0091] The materials used for the external electrodes 4a and 4b are typically copper or copper alloys, nickel or nickel alloys, etc., but silver or silver-palladium alloys can also be used. The thickness of the external electrodes 4a and 4b is not particularly limited, but is usually between 10 μm and 50 μm.

[0092] Manufacturing method of multilayer ceramic capacitors

[0093] Next, an example of a method for manufacturing the multilayer ceramic capacitor 1 according to this embodiment will be described.

[0094] In order to create a structure after firing Figure 1A as well as Figure 1B The inner sheet 30 of the inner dielectric layer 2 shown is prepared with inner dielectric paste (inner ceramic paste).

[0095] In this embodiment, the inner dielectric paste is composed of an organic solvent-based paste obtained by mixing a second ceramic powder (dielectric material) and a second organic carrier, wherein the second organic carrier comprises butyral resin.

[0096] As a second ceramic powder, it can be appropriately selected and mixed from various compounds of composite oxides or oxides that constitute the elements of the second ceramic powder, such as carbonates, nitrates, hydroxides, organometallic compounds, etc.

[0097] The second ceramic powder is typically made into a powder with an average particle size of 2.0 μm or less, preferably 0.1 μm to 0.8 μm. Furthermore, in order to form an extremely thin inner green sheet 30, it is desirable to use a powder finer than the thickness of the inner green sheet 30 as the second ceramic powder.

[0098] The second organic carrier contains butyral resin as a binder. Examples of butyral resins include polyvinyl butyral resin.

[0099] When the content of the second ceramic powder in the inner dielectric paste is set to 100 parts by mass and the content of butyral resin in the inner dielectric paste is set to A2, A2 is preferably greater than 10 parts by mass and less than 20 parts by mass, more preferably 11 to 15 parts by mass.

[0100] By keeping the content of butyral resin within the above range, the following effects (1) to (3) can be obtained.

[0101] (1) It can further improve the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30.

[0102] (2) It can minimize the shrinkage of the inner green sheet 30 in the debonding process and further reduce the generation of cracks in the component body 10 caused by the shrinkage of the inner green sheet 30.

[0103] (3) In the debinding process, there is a tendency for butyral resin to be completely removed, which can further suppress cracks in the component body 10.

[0104] In this embodiment, the degree of polymerization of the polyvinyl butyral resin is preferably 1000 to 2400, more preferably 1000 to 2400 (excluding 1000), and even more preferably 1700 to 2400. That is, a polyvinyl butyral resin with a high degree of polymerization can be used.

[0105] By using such a polyvinyl butyral resin, the strength of the inner green sheet 30 is further improved. However, in this case, the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30 is sometimes reduced.

[0106] In contrast, in this embodiment, by forming a step difference absorbing pattern layer 60 on the inner green sheet 30 using the specified step difference absorbing paste described later, the strength of the inner green sheet 30 can be sufficiently maintained, and the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30 can be sufficiently improved.

[0107] Furthermore, in this embodiment, the polyvinyl butyral resin contained in the inner dielectric paste preferably has a butyralization degree of greater than 55 mol% and less than 69 mol%, more preferably 60 mol% to 65 mol%. By having a butyralization degree within the above range, the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30 can be further improved.

[0108] In addition to butyral resin, the second organic carrier may also contain a second organic solvent. There are no particular limitations on the second organic solvent; various alcohols, ketones, aromatic compounds, etc., can be used, and these second organic solvents can also be mixed. The content of the second organic solvent in the inner dielectric paste is not particularly limited; for example, it can be set to 30% to 90% by mass.

[0109] In the inner dielectric paste, in addition to the second ceramic powder, butyral resin, and second organic solvent as the main components, additives selected from various dispersants, plasticizers, by-product compounds, glass frits, and insulators may be included as needed. When these additives are added to the inner dielectric paste, it is preferable that the total content of these additives is 10% by mass or less.

[0110] Examples of plasticizers included in the inner dielectric paste include phthalates such as dioctyl phthalate or benzyl butyl phthalate, adipic acid, phosphate esters, and ethylene glycol derivatives. The content of the plasticizer in the inner dielectric paste is not particularly limited, but is preferably 5 to 100 parts by weight relative to 100 parts by weight of butyral resin, more preferably 5 to 40 parts by weight. By keeping the plasticizer within the above range, the elongation and flexibility of the inner green sheet 30 become good, and the plasticizer is less likely to seep to the surface of the inner green sheet 30, making operation easier.

[0111] In addition, the paste for the inner dielectric is preferably substantially free of terpene phenols, and is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, relative to 100 parts by weight of butyral resin.

[0112] The inner dielectric paste is obtained by first dispersing a second ceramic powder in a second organic solvent using a bead mill, and then mixing it with a second organic carrier.

[0113] Then, using the inner dielectric paste, apply it through a wire bar coater or scraper, such as... Figure 2AAs shown, the inner green sheet 30 is preferably formed on the carrier sheet 20, which serves as a support, with a thickness of less than 1 μm.

[0114] As the carrier sheet 20, for example, a PET film can be used. In order to improve peelability, it is preferable to perform a demolding treatment (coating with silicone or the like) on the surface where the inner green sheet 30 is formed. The thickness of the carrier sheet 20 is not particularly limited, but is preferably 5 μm to 100 μm.

[0115] The inner green sheet 30 is dried after being formed on the carrier sheet 20. The drying temperature of the inner green sheet 30 is preferably 50°C to 100°C, and the drying time is preferably 1 minute to 20 minutes.

[0116] The thickness of the dried inner green sheet 30 shrinks by 5% to 25% compared to its thickness before drying. In this embodiment, the thickness of the dried inner green sheet 30 is preferably 0.4 μm to 1 μm, more preferably 0.4 μm to 0.8 μm. This is to meet the demand for thinner sheets that has been desired in recent years.

[0117] Next, in order to form on the surface of the aforementioned inner green sheet 30 the structure that will be formed after firing... Figure 1A as well as Figure 1B The internal electrode pattern layer 40 shown in the internal electrode layers 3a and 3b is used to prepare the internal electrode paste.

[0118] The internal electrode paste is composed of an organic solvent-based paste obtained by mixing conductive powder and a third organic carrier.

[0119] Such conductive powders can be spherical, flake-shaped, or of any particular shape. Alternatively, they can be a mixture of powders of these shapes. Furthermore, the particle size of the conductive powder is typically 0.5 μm or less in the case of spherical powders, preferably between 0.01 μm and 0.2 μm. This is to more reliably achieve thin-layer formation.

[0120] The conductive powder is preferably contained in the internal electrode paste at a concentration of 30% to 60% by mass, and more preferably at a concentration of 45% to 55% by mass.

[0121] The third organic carrier, as a main component, contains a third organic binder and a third organic solvent. There are no particular limitations on the third organic binder; examples include ethyl cellulose, acrylic resin, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefins, polyurethane, polystyrene, or copolymers thereof, with ethyl cellulose being the preferred main component.

[0122] When ethyl cellulose is used as the main component in the third organic binder, the content of ethyl cellulose in the third organic binder is preferably 95% by mass or more, and more preferably 100% by mass. Acrylic resins and polyvinyl butyral resins are examples of resins that can be used in combination with ethyl cellulose, even in trace amounts.

[0123] The internal electrode paste preferably also contains terpenoids, which are also present in the step difference absorption paste described later, as a tackifier. By including terpenoids in the internal electrode paste, the adhesion between the inner green sheet 30 and the internal electrode pattern layer 40 can be improved, and internal defects such as cracks after firing can be effectively prevented.

[0124] In the internal electrode paste, it is preferable to contain 1 to 10 parts by mass of a third organic binder and terpene phenols per 100 parts by mass of the conductive powder. The content ratio, average molecular weight, etc. of the third organic binder and terpene phenols contained in the internal electrode paste are the same as those of ethyl cellulose and terpene phenols contained in the step difference absorption paste described later.

[0125] There are no particular limitations on the third organic solvent contained in the internal electrode paste; for example, known solvents such as terpineol, butylcarbidol, and kerosene can be used. Similar to the first organic solvent contained in the step difference absorption paste described later, the third organic solvent is preferably a mixed solvent obtained by mixing terpineol acetate with one or more selected from isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. The composition of the third organic solvent when using such a mixed solvent can be the same as that of the first organic solvent described later.

[0126] The content of the third organic solvent in the internal electrode paste is preferably 50 to 150 parts by mass relative to 100 parts by mass of the conductive powder, more preferably 60 to 100 parts by mass.

[0127] The total content of the aforementioned third organic binder, terpene phenol, and third organic solvent in the third organic carrier is preferably 95% by mass or more, more preferably 100% by mass. Substances that can be included in the third organic carrier together with the third organic binder, terpene phenol, and third organic solvent include plasticizers, leveling agents, etc.

[0128] Ceramic powder can also be included as a general-purpose material in the internal electrode paste. This general-purpose material helps to inhibit the sintering of the conductive powder during the firing process. The ceramic powder used as a general-purpose material is preferably present in the internal electrode paste in an amount of 5 to 30 parts by mass relative to 100 parts by mass of the conductive powder. By keeping the amount of general-purpose material within the above range, the sintering inhibition effect of the conductive powder can be achieved, and electrode interruption in the internal electrode layers 3a and 3b after firing can be prevented.

[0129] The paste for internal electrodes is obtained by dispersing conductive powders and general materials using a bead mill or similar method, and then mixing them with a third organic carrier.

[0130] Next, as Figure 2B As shown, an internal electrode pattern layer 40 with a predetermined pattern is formed on the surface of the inner green sheet 30 formed on the carrier sheet 20.

[0131] The method for forming the internal electrode pattern layer 40 is not particularly limited as long as it is a method that can uniformly form the layer. In this embodiment, a screen printing method using the internal electrode paste described above can be used.

[0132] The thickness of the internal electrode pattern layer 40 is preferably 1.5 μm or less, more preferably 0.4 μm to 1.0 μm. The thickness of the internal electrode pattern layer 40 is preferably thinner within a range that does not cause interruption of the internal electrode layers 3a and 3b.

[0133] The internal electrode pattern layer 40 can then be dried as needed. The drying temperature is not particularly limited, but is preferably 50°C to 120°C, and the drying time is preferably 1 minute to 15 minutes.

[0134] Next, a step difference absorption paste is prepared for forming a step difference absorption pattern layer 60 on the inner green sheet 30 that is complementary to the internal electrode pattern layer 40.

[0135] In this embodiment, the step difference absorption paste is composed of an organic solvent-based paste obtained by mixing a first ceramic powder and a first organic carrier, wherein the first organic carrier comprises ethyl cellulose and terpene phenols. Furthermore, the composition of the first ceramic powder contained in the step difference absorption paste may differ from the composition of the second ceramic powder contained in the aforementioned inner dielectric paste, but is preferably substantially the same.

[0136] When the content of the first ceramic powder in the step difference absorption paste is set to 100 parts by mass, and the total content of ethyl cellulose and terpene phenol in the step difference absorption paste is set to A1, A1 is 10 parts by mass to 26 parts by mass, preferably 12 parts by mass to 22 parts by mass, and more preferably 13 parts by mass to 19 parts by mass.

[0137] By using A1 within the above range, the following effects (1) to (3) can be obtained.

[0138] (1) It can improve the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30.

[0139] (2) It can minimize the shrinkage of the step difference absorption pattern layer 60 in the adhesive removal process and reduce the generation of cracks in the component body 10 caused by the shrinkage of the step difference absorption pattern layer 60.

[0140] (3) In the debinding process, there is a tendency for ethyl cellulose and terpene phenols to be completely removed, which can suppress cracks in the component body 10.

[0141] In addition, A1 is preferably A2 or more, and A1 is more preferably 1.1 times or more of A2.

[0142] In addition, when the total content of ethyl cellulose and terpene phenol is set to 100 parts by mass, the content of terpene phenol is 30 to 67 parts by mass, preferably 40 to 60 parts by mass, and more preferably 50 to 60 parts by mass.

[0143] By ensuring that the content of terpene phenols relative to ethyl cellulose and terpene phenols is within the above-mentioned range, screen printing is easily performed, and the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30 can be improved.

[0144] The average molecular weight of ethyl cellulose is preferably greater than 40,000 and less than 250,000, more preferably 50,000 to 150,000. By having an average molecular weight within the above range, screen printing is easier and the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30 can be further improved.

[0145] Furthermore, the ethoxy content of ethyl cellulose is preferably greater than 46.1% by mass and less than 52.0% by mass, more preferably 48.0% to 49.5% by mass. By keeping the ethoxy content within the above range, the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30 can be further improved.

[0146] The average molecular weight of the terpene phenol is 220–650, preferably 220–400, and more preferably 220–300.

[0147] As the first organic solvent, to prevent flake erosion, it is preferably an immiscible organic solvent that does not cause the butyral resin contained in the inner flake 30 to swell or dissolve well. Specifically, examples include α-terpineol acetate, isobornyl acetate, dihydroterpineol acetate, dihydroterpineyl methyl ether, terpineyl methyl ether, and I-dihydrocarvyl acetate.

[0148] The first organic solvent in the step difference absorption paste preferably contains 50 to 150 parts by mass relative to 100 parts by mass of the first ceramic powder, and more preferably 80 to 100 parts by mass.

[0149] The step difference absorption paste may contain plasticizers, but it is preferable that it contains no plasticizers at all. Specifically, when the total content of ethyl cellulose and terpene phenols in the step difference absorption paste is set to 100 parts by weight, the content of plasticizer is preferably 10 parts by weight or less, more preferably 3 parts by weight or less.

[0150] By being substantially free of plasticizers, the adhesive strength of the step difference absorbing paste at 35°C before heating can be suppressed to a low level. This can prevent accidental adhesion or defects such as adhesion to the mold of the laminating machine in processes other than lamination, and can also prevent plasticizer from seeping to the surface over time.

[0151] Furthermore, in this embodiment, plasticizer refers to a low-molecular-weight compound that imparts plasticity. Specific examples include dioctyl phthalate, benzyl butyl phthalate, phthalic acid, phosphate esters, ethylene glycol, etc.

[0152] Dispersants may also be included in step difference absorption pastes.

[0153] The step difference absorption paste can be obtained by dispersing the first ceramic powder in the first organic solvent and mixing it with the first organic carrier using processes such as bead milling.

[0154] In this embodiment, after forming a predetermined patterned internal electrode pattern layer 40 on the surface of the inner green sheet 30 by printing, in Figure 2B The surface gaps (blank pattern portions 50) of the inner green sheet 30 where the internal electrode pattern layer 40 is not formed are shown, as... Figure 2C As shown, a step difference absorption pattern layer 60 with substantially the same thickness as the inner electrode pattern layer 40 is formed. Specifically, the thickness of the step difference absorption pattern layer 60 is preferably 70% to 110% relative to the inner electrode pattern layer 40, and more preferably 90% to 105%. By including the thickness of the step difference absorption pattern layer 60 within the above range, deviations in the thickness of the inner dielectric layer 2 can be suppressed, and bell deformation of the component body 10 described later can be suppressed.

[0155] Alternatively, a step difference absorption pattern layer 60 may be formed on the surface of the inner green sheet 30 before the inner electrode pattern layer 40 with a specified pattern is formed on the surface of the inner green sheet 30 by printing.

[0156] The method for forming the step difference absorption pattern layer 60 is not particularly limited as long as it is a method that can uniformly form the layer. In this embodiment, a screen printing method using the above-mentioned step difference absorption paste can be used.

[0157] The thickness of the step difference absorption pattern layer 60 is set to be substantially the same as that of the internal electrode pattern layer 40 because by setting it to be substantially the same thickness, it is difficult to generate step differences, especially in the case of multilayering, which can reduce the influence of step differences.

[0158] Subsequently, the internal electrode pattern layer 40 and / or the step difference absorption pattern layer 60 are dried as needed. The drying temperature is not particularly limited, but is preferably 50°C to 120°C, and the drying time is preferably 1 minute to 15 minutes.

[0159] Thus, a predetermined number of inner green sheets 30 are stacked to form an inner region green sheet stack 110a. Furthermore, outer region green sheet stacks 110b are formed at both ends of the inner region green sheet stack 110a in the stacking direction. That is, the inner region green sheet stack 110a is sandwiched between the outer region green sheet stacks 110b. The outer region green sheet stack 110b is a structure in which one or more outer green sheets without an internal electrode pattern layer 40 and a step difference absorption pattern layer 60 are stacked.

[0160] The outer green sheet constituting the outer packaging region green laminate 110b is formed on the carrier sheet 20 using an outer dielectric paste, similar to the inner green sheet 30. As the outer dielectric paste, the inner dielectric paste prepared as described above can be used, or a paste with changes in adhesive type, adhesive addition amount, adhesive polymerization degree, etc., can be used.

[0161] Next, the green laminate 110, which includes the inner green laminate 110a and the outer green laminate 110b, is pressurized and heated using a mold. The preferred temperature at this time is 50°C to 100°C, and the preferred pressure is 5 MPa to 25 MPa.

[0162] like Figure 4A As shown, in the ZX section, the step difference absorption pattern layer 60 of the adjacent inner green sheets 30 in the Z-axis direction is formed in a manner that does not overlap in the Z-axis direction.

[0163] In contrast, such as Figure 3B As shown, in the ZY section, the step difference absorption pattern layers 60 of adjacent inner green sheets 30 in the Z-axis direction are formed in an overlapping manner in the Z-axis direction.

[0164] The ZY section step difference absorbing pattern layer 60, and the inner green sheet 30 and / or outer green sheet stack 10b of the range adjacent to the step difference absorbing pattern layer 60 in the Z-axis direction constitute the edge region green sheet stack 110c, which becomes the edge region 10c after firing.

[0165] like Figure 4A as well as Figure 4BAs shown, the obtained green stack 110 is cut to a specified size, for example, along the cutting surface C1 and the cutting surface C2, and then peeled off from the substrate to become a green chip.

[0166] Here, as Figure 4A As shown, in the ZX section, the cutting surface C1 is determined by alternately cutting the inner electrode pattern layer 40 and the step difference absorption pattern layer 60 along the Z-axis direction, sandwiching the inner green sheet 30.

[0167] In addition, such as Figure 4B As shown, in the YZ section, the cutting surface C2 is determined by cutting only the inner green sheet 30, the outer green sheet stack 110b, and the step difference absorption pattern layer 60 along the Z-axis direction.

[0168] By using this cutting method, a green chip is obtained, and the internal electrode pattern layer 40 of the green chip becomes a structure that is exposed on one cutting surface C1 but not on the other cutting surface C1.

[0169] In addition, an edge region green stack 110c can be formed through the cut surface C2 of the green chip.

[0170] also, Figure 4A as well as Figure 4B It is only a rough cross-sectional diagram, and the number of layers, dimensional relationships, etc., are sometimes different from the actual ones.

[0171] The green die is cured by removing the plasticizer through curing and drying. After curing and drying, the green die, along with the dielectric material and polishing slurry, is placed in a drum container and subjected to drum polishing using a horizontal centrifugal drum mill or similar method. The drum-polished green die is then washed with water and dried. The dried green die undergoes a binder removal process, a firing process, and, if necessary, an annealing process to obtain the desired product. Figure 1A and Figure 1B The component body 10 (sintered body) shown.

[0172] Next, external electrode paste is printed or transferred onto the component body 10 and fired to form external electrodes 4a and 4b, thus manufacturing the multilayer ceramic capacitor 1.

[0173] Assuming that no step difference absorption pattern layer is formed, in addition to the deviation in the thickness of the inner dielectric layer, the main body of the component may sometimes deform (bell deformation) into a bell-shaped structure that protrudes outward from the center in the stacking direction.

[0174] In contrast, by forming the step difference absorption pattern layer 60, not only can the thickness deviation of the inner dielectric layer 2 be reduced, but the bell-shaped deformation of the component body 10 can also be suppressed, as well as the deformation of the multilayer ceramic capacitor 1. Moreover, by preventing the deformation of the multilayer ceramic capacitor 1, not only can the desired capacitance be obtained, but insulation failure is also less likely to occur, thus ensuring reliability.

[0175] However, as the laminated ceramic capacitor 1 becomes thinner, the strength of the inner green sheet 30 increases, but this tends to reduce the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30.

[0176] To mitigate this tendency, there are methods to give the step difference absorbing pattern layer 60 high adhesive strength. However, if the step difference absorbing pattern layer 60 is given high adhesive strength, there is a tendency for unintended adhesion and other operational difficulties to occur due to this adhesive strength.

[0177] In contrast, the step difference absorbing paste according to this embodiment contains a first ceramic powder, ethyl cellulose, and a specified terpene phenol in a prescribed composition. According to the step difference absorbing paste according to this embodiment, the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30 can be improved, and the operability in operation can also be improved.

[0178] The reasons are as follows. In this embodiment, the inner green sheet 30 contains butyral resin, and the step difference absorbing pattern layer 60 contains ethyl cellulose. Furthermore, the step difference absorbing pattern layer 60 also contains terpene phenols at a predetermined content. Since terpene phenols are miscible with both butyral resin and ethyl cellulose, when the green laminate 110 is pressed and heated for bonding, the entanglement of the molecular chains of butyral resin and terpene phenols increases through thermal diffusion, and the entanglement of the molecular chains of ethyl cellulose and terpene phenols also increases. That is, at high temperatures during the lamination process, the adhesion between the inner green sheet 30 containing butyral resin and the step difference absorbing pattern layer 60 containing ethyl cellulose is increased via terpene phenols.

[0179] Furthermore, the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30 helps the lamination of the inner green sheet 30, which can effectively suppress cracks in the element body 10 after firing.

[0180] Furthermore, the step difference absorbing pattern layer 60 formed by the step difference absorbing paste according to this embodiment has the characteristic of low adhesion at low temperatures. Therefore, it has good operability in operations other than the lamination process. Specifically, in addition to preventing the inner green sheet 30 and the like from accidentally adhering to certain substances in processes other than the lamination process, it can also prevent a part of the green laminate 110 from accidentally adhering to the mold of the lamination machine when the green laminate 110 is pressed and heated to press it together.

[0181] That is, the step difference absorbing pattern layer 60 formed by the step difference absorbing paste according to this embodiment has high adhesion at high temperatures in the lamination process, thus improving the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30. On the other hand, the adhesion is low at low temperatures outside the lamination process, thus improving operability.

[0182] Furthermore, in the prior art, during the process of winding a carrier sheet 20 having an inner green sheet 30, an inner electrode pattern layer 40, and a step difference absorption pattern layer 60, the step difference absorption pattern layer 60 is sometimes transferred (back transfer) onto the back side of the carrier sheet 20. In contrast, the step difference absorption paste according to this embodiment has low adhesion at low operating temperatures other than those in the lamination process, thus preventing the aforementioned back transfer.

[0183] Furthermore, in this embodiment, since the adhesion between the step difference absorbing pattern layer 60 and the inner green sheet 30 is sufficiently high during the lamination process, the step difference absorbing paste does not actually need to contain plasticizers. Therefore, in this embodiment, the absence of plasticizers in the step difference absorbing paste also contributes to high workability.

[0184] The embodiments of the present invention have been described above, but the present invention is not necessarily limited to the above embodiments, and various changes can be made without departing from the spirit of this disclosure.

[0185] For example, in the above embodiments, a multilayer ceramic capacitor is exemplified as a multilayer electronic component according to the present invention. However, the multilayer electronic component according to the present invention is not limited to multilayer ceramic capacitors, and can also be applied to multilayer ceramic substrates, etc.

[0186] Alternatively, a predetermined number of stacked body units, each having multiple inner green sheets 30, an internal electrode pattern layer 40, and a step difference absorption pattern layer 60 formed by the method involved in this invention, can be formed, and these stacked body units can be further stacked to produce the final green body 110.

[0187] Furthermore, the internal electrode pattern layer 40 and the step difference absorption pattern layer 60 can also be formed by transfer printing.

[0188] (Example)

[0189] The present invention will now be described with reference to more detailed embodiments, but the present invention is not limited to these embodiments.

[0190] Adhesion strength at 35°C and adhesion strength at 75°C

[0191] For the inner green sheet 30 with the step difference absorption pattern layer 60, the adhesive strength at 35°C and the adhesive strength at 75°C were determined by the following method. In Tables 1 to 3, "adhesive strength at 35°C" refers to "adhesive strength at 35°C", and "adhesive strength at 75°C" refers to "adhesive strength at 75°C".

[0192] The inner green sheet 30 (sample) with the step difference absorption pattern layer 60 formed thereon is manufactured by the following method.

[0193] A paste for forming the inner dielectric layer 30 was prepared. BaTiO3-based ceramic powder (second ceramic powder), polyvinyl butyral resin (degree of polymerization: 1700), propanol, xylene, methyl ethyl ketone, 2-butoxyethanol as the second organic solvent, and di-2-ethylhexyl phthalate as the plasticizer were prepared. Then, relative to 100 parts by weight of the second ceramic powder, 150 parts by weight of the polyvinyl butyral resin, the second organic solvent, and the plasticizer were weighed and mixed with zirconia balls with a diameter of 2 mm in a ball mill for 21 hours to form a slurry, thus obtaining the paste for the inner dielectric layer.

[0194] In addition, when the content of the second ceramic powder in the inner dielectric paste is set to 100 parts by mass, the content of polyvinyl butyral resin (A2) in the inner dielectric paste is 12 parts by mass.

[0195] In addition, 10 parts by weight of plasticizer were added relative to 100 parts by weight of polyvinyl butyral resin.

[0196] Furthermore, the inner dielectric paste does not contain terpenoid phenols.

[0197] Next, a step difference absorption paste for forming the step difference absorption pattern layer 60 is prepared. First, a BaTiO3-based ceramic powder (first ceramic powder) with the same composition as the second ceramic powder contained in the inner dielectric paste described above, ethyl cellulose, terpene phenols having the average molecular weights listed in Tables 1 to 3, and α-terpineol acetate as the first organic solvent are prepared. Then, relative to 100 parts by mass of the first ceramic powder, 122 parts by mass of α-terpineol acetate, ethyl cellulose (average molecular weight: 140,000), and terpene phenols are added, and the mixture is kneaded and slurried using a bead mill and a three-roll mill to obtain the step difference absorption paste.

[0198] Furthermore, when the total content of ethyl cellulose and terpene phenols in the step difference absorption paste is set to 100 parts by mass, the content of plasticizer is less than 0.1 parts by mass.

[0199] In addition, the combination of ethyl cellulose and terpene phenols is as shown in Tables 1 to 3 as “A1 [parts by mass]” and “terpene phenol content [parts by mass]”.

[0200] The “A1 [parts by mass]” recorded in Tables 1 to 3 refers to the total content of ethyl cellulose and terpene phenols when the content of the first ceramic powder is set to 100 parts by mass.

[0201] In addition, the “terpene phenol content [parts by mass]” recorded in Tables 1 to 3 refers to “the content of terpene phenol when the total content of ethyl cellulose and terpene phenol is set to 100 parts by mass”.

[0202] Next, an inner dielectric paste is applied to the surface of the PET film serving as the carrier sheet 20 using a wire bar coater to a specified thickness and then dried to produce an inner green sheet 30 with a thickness of 0.6 μm.

[0203] In addition, a step difference absorption paste is coated on the surface of the carrier sheet 20 (PET film) with a specified thickness using a wire bar coater and then dried to obtain a dried film of the step difference absorption paste with a thickness of 1.0 to 1.5 μm.

[0204] Furthermore, neither the PET film with the inner dielectric paste nor the PET film with the step difference absorption paste were subjected to a peeling process. This is because this experiment was merely to confirm the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30, and therefore, it was not expected that the inner green sheet 30 would peel off from the PET film, nor that the step difference absorption pattern layer 60 would peel off from the PET film.

[0205] The dried film of the step difference absorption paste formed on the PET film is cut into appropriate sizes and laminated with the inner green sheet 30 to obtain the sample (the inner green sheet 30 with the step difference absorption pattern layer 60). The lamination is carried out at a pressure of 2 MPa, a temperature of 35°C or 75°C, and a pressure time of 10 minutes.

[0206] Using an Instron 5543 tensile testing machine, the specimen is stretched in a direction perpendicular to its surface (stretching along the stacking direction of the specimen). The peel strength value is then converted to the adhesive strength of a 1 cm square specimen. The adhesive strength at 35°C should be less than 1 N / cm. 2 Furthermore, the adhesion strength at 75℃ is 1 N / cm. 2 The above is set as good. Additionally, the adhesive strength at 75℃ is 5 N / cm. 2 The above setting is better, with an adhesion strength of 40 N / cm at 75℃. 2 The above settings are considered better. The results are shown in Tables 1-3.

[0207] Adhesion strength at 35℃ is less than 1 N / cm 2 This means that before pressurizing and heating the green laminate 110, it is possible to suppress unnecessary adhesion of certain substances such as inner green sheets 30, thus implying good operability in operation.

[0208] Additionally, the adhesion strength at 75℃ is 1 N / cm. 2 This means that during the pressurized and heated lamination process, the step difference absorbing pattern layer 60 and the inner green sheet 30 have good adhesion.

[0209] [Table 1]

[0210]

[0211] [Table 2]

[0212]

[0213] [Table 3]

[0214]

[0215] Tables 1-3 confirm that A1 is 10-26 parts by mass, and the average molecular weight of terpene phenols is 220-650. When the total content of ethyl cellulose and terpene phenols is set to 100 parts by mass, and the content of terpene phenols is 30-67 parts by mass (sample numbers 12-18, 21-25, 27-31, 33-41, 43-47, 49-56, 65-71), the adhesive strength at 35℃ is less than 1 N / cm. 2 Furthermore, the adhesion strength at 75℃ is 1 N / cm. 2 In summary, it can be confirmed that samples 12-18, 21-25, 27-31, 33-41, 43-47, 49-56, and 65-71 are easy to operate before heating, and that the adhesion between the step difference absorption pattern layer 60 and the inner green sheet 30 is good during the lamination process after heating.

[0216] In addition, the multilayer ceramic capacitor 1 is manufactured by the following method.

[0217] The paste for forming the internal electrode pattern layer 40 is prepared by the following method. First, Ni particles with an average particle size of 0.2 μm are prepared as the conductive powder, BaTiO3-based ceramic powder as the general material, ethyl cellulose as the third organic binder, α-terpineol acetate as the third organic solvent, and rosin as the thickener. Then, 122 parts by mass of α-terpineol acetate, 5.58 parts by mass of ethyl cellulose, and 2.22 parts by mass of rosin are added to a total of 130 parts by mass, which is 100 parts by mass of the conductive powder and 30 parts by mass of the general material. The mixture is then kneaded and slurried using a ball mill and a three-roll mill to obtain the paste for the internal electrode.

[0218] Next, using the inner dielectric paste, inner electrode paste, and step difference absorption paste prepared above, a multilayer ceramic chip capacitor 1 was manufactured.

[0219] First, on the surface of the carrier sheet 20 (PET film) that has undergone demolding treatment, an inner dielectric paste is applied to a specified thickness using a wire bar coater and then dried to produce an inner green sheet 30 with a thickness of 0.6 μm.

[0220] Next, on the obtained inner green sheet 30, an inner electrode pattern layer 40 is formed by screen printing an inner electrode paste, with the screen pattern being a strip of 4.0 × 1.2 mm and a thickness of 0.6 μm after drying (see reference). Figure 2B ).

[0221] Subsequently, on the inner green sheet 30, the blank pattern portion 50 where the internal electrode pattern layer 40 has not been formed (refer to...) Figure 2B A step difference absorption pattern layer 60 with substantially the same thickness as the internal electrode pattern layer 40 is formed by screen printing using a step difference absorption paste (see reference). Figure 2C ), to obtain Figure 2C The inner green sheet 30 shown has an internal electrode pattern layer 40 and a step difference absorption pattern layer 60. In this embodiment, multiple inner green sheets 30 having an internal electrode pattern layer 40 and a step difference absorption pattern layer 60 are prepared.

[0222] Next, except that the degree of polymerization of polyvinyl butyral resin was set to 1500, an outer dielectric paste was prepared in the same manner as the inner dielectric paste prepared above. The outer dielectric paste was applied to the demolded surface of the PET film 20 to a specified thickness using a wire bar coater and then dried to produce an outer green sheet with a thickness of 12 μm.

[0223] Prepare 8 outer green sheets, heat press them together to form an outer green sheet laminate 110b with a thickness of 96μm.

[0224] Under conditions of 75°C and 12 MPa, a green sheet 30 having an internal electrode pattern layer 40 and a step difference absorption pattern layer 60 is pressed onto the resulting outer packaging area green laminate 110b, and the PET film 20 is peeled off (see reference). Figure 3A Repeat this process to stack a desired number of inner green sheets 30 having formed an internal electrode pattern layer 40 and a step difference absorption pattern layer 60 (see reference). Figure 3B Then, the above-mentioned outer casing green laminate 110b with a thickness of 96μm is further formed by hot pressing, and the green laminate 110 is obtained.

[0225] Next, the obtained green laminate 110 is cut into specified dimensions and then subjected to debinding, firing and annealing under the following conditions to obtain the component body 10.

[0226] The adhesive removal was carried out under the following conditions: heating rate: 15℃ / hour; holding temperature: 280℃; holding time: 8 hours; treatment atmosphere: air atmosphere.

[0227] Firing was carried out under the following conditions: heating rate: 200℃ / hour; holding temperature: 1200~1380℃; holding time: 2 hours; cooling rate: 300℃ / hour; processing atmosphere: reducing atmosphere (a mixture of N2 and H2 was introduced with water vapor to adjust the oxygen partial pressure to 10). -6 Pa).

[0228] Annealing was performed under the following conditions: holding temperature: 900℃; holding time: 9 hours; cooling rate: 300℃ / hour; processing atmosphere: humidified N2 gas atmosphere. A humidifier was used to humidify the gases during firing and annealing, with the water temperature set to 35℃.

[0229] The dimensions of the obtained component body 10 are: L0: 1.6mm × W0: 0.8mm × H0: 0.8mm. The thickness of the inner dielectric layer 2 sandwiched between a pair of inner electrode layers 3 is about 0.6μm, and the thickness of the inner electrode layer 3 is 0.6μm.

Claims

1. A step difference absorption paste, wherein, It contains: first ceramic powder, ethyl cellulose, and terpene phenols. A1 is available in quantities of 10 to 26 parts by weight. A1 refers to the total content of ethyl cellulose and terpene phenols in the step difference absorption paste when the content of the first ceramic powder in the paste is set to 100 parts by mass. The average molecular weight of the terpene phenols is 220–650. When the total content of the ethyl cellulose and the terpene phenol is set to 100 parts by mass, the content of the terpene phenol is 30 to 67 parts by mass.

2. A method for manufacturing a stacked electronic component, wherein, It has a process of alternatingly overlapping inner ceramic green sheets and internal electrode pattern layers to obtain a green laminate. A step difference absorption pattern layer is formed in the gaps between the internal electrode pattern layers. The inner ceramic green sheet is formed using an inner ceramic paste. The inner ceramic paste contains a second ceramic powder and butyral resin. The step difference absorption pattern layer is formed using a step difference absorption paste. The step difference absorption paste comprises: a first ceramic powder, ethyl cellulose, and terpene phenols. A1 is available in quantities of 10 to 26 parts by weight. A1 refers to the total content of ethyl cellulose and terpene phenols in the step difference absorption paste when the content of the first ceramic powder in the paste is set to 100 parts by mass. The average molecular weight of the terpene phenols is 220–650. When the total content of the ethyl cellulose and the terpene phenol is set to 100 parts by mass, the content of the terpene phenol is 30 to 67 parts by mass.

3. The method for manufacturing a stacked electronic component according to claim 2, wherein, The first ceramic powder and the second ceramic powder have substantially the same composition.

4. The method for manufacturing a stacked electronic component according to claim 2 or 3, wherein, A2 is greater than 10 parts by weight and less than 20 parts by weight. A2 refers to the content of butyral resin in the inner ceramic paste when the content of the second ceramic powder in the inner ceramic paste is set to 100 parts by mass. A1 is greater than or equal to A2.

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