Multilayer capacitor and its manufacturing method

Abstract

To provide a multilayer capacitor which comprises a margin part and has improved quality, and a manufacturing method thereof.SOLUTION: A manufacturing device 10 for a multilayer capacitor forms on a rotary drum a mother element laminate, in which resin thin film layers and metal thin film layers are alternately laminated, by repeatedly implementing at least 100 times successively the steps of: forming the resin thin film layer by curing a monomer layer, which is formed by depositing monomers using a monomer deposition device 18, on a rotary drum 14 inside of a vacuum chamber 12 by irradiating the monomer layer with electron beams from an electron beam irradiation device 19; applying an oil onto the resin thin film layer partially and in a non-contact manner; and forming the metal thin film layer including an electric insulation part by depositing a metal material on the resin thin film layer, to which the oil is applied, using a metal deposition device 26. During the steps, after the lapse of at least 1.0 sec or more from the irradiation with the electron beams and before the lapse of 3.8 sec from the irradiation with the electron beams, the oil is applied in the non-contact manner.SELECTED DRAWING: Figure 4

Description

[Technical Field] 【0001】 The present invention relates to a multilayer capacitor and a method for manufacturing the same. [Background technology] 【0002】 As a type of capacitor, a multilayer capacitor (also called a "thin-film polymer multilayer capacitor") is known, which has a structure in which dielectric layers containing resin and electrode layers containing metal are alternately stacked. 【0003】 Patent Document 1 describes a thin-film polymer laminated film capacitor and a method for manufacturing the same. The manufacturing method described in this document includes the process of alternately repeating the steps of forming a monomer layer by depositing monomers in a vacuum chamber and then curing the monomer layer by irradiating it with an electron beam to form a resin thin film layer, and forming a metal thin film layer by depositing a metal material, on a rotating drum, thereby producing a laminate in which resin thin film layers and metal thin film layers are alternately stacked on a rotating drum. 【0004】 In such multilayer capacitors, a strip-shaped electrical insulating portion may be provided in the metal thin film layer deposited on top of the resin thin film layer. This electrical insulating portion can form a "margin portion" when its positions overlap in the stacking direction. 【0005】 Previously, it had been reported that indentations (recesses) occurred on the surface of multilayer capacitors due to this margin area. More specifically, it was thought that because the margin area does not have a thin metal film layer, its thickness becomes smaller than the surrounding area when viewed as part of the entire multilayer structure, resulting in indentations on the surface of the multilayer capacitor. 【0006】 Patent Document 2, based on this understanding, proposes a method for eliminating indentations on the surface of a multilayer capacitor. This document describes a laminate having a laminated unit comprising a dielectric layer and a first metal thin film layer and a second metal thin film layer laminated on the dielectric layer. The first metal thin film layer and the second metal thin film layer are distinguished by a strip-shaped electrical insulating portion. This document describes an embodiment in which the laminated positions of the electrical insulating portions of adjacent laminated units differ, and the laminated positions of the electrical insulating portions of every other laminated unit are not the same throughout the entire laminate. [Prior art documents] [Patent Documents] 【0007】 [Patent Document 1] International Publication No. 2015 / 118693 [Patent Document 2] Japanese Patent Application Publication No. 11-147279 [Overview of the Initiative] [Problems that the invention aims to solve] 【0008】 The inventors of this case have found that in a multilayer capacitor having a margin, not only can a depression occur on the capacitor surface corresponding to the margin, but a protrusion adjacent to the depression can also be formed. Such irregularities caused by the margin can adversely affect the quality of the multilayer capacitor. Specifically, such irregularities can increase the risk of dielectric breakdown and make the capacitor more prone to cracking during the heat pressing process after removing the mother-element multilayer from the rotating drum. Dielectric breakdown, in particular, can be a problem in multilayer capacitors used for high-voltage (200V or higher) applications. 【0009】 The present invention aims to provide a multilayer capacitor having a margin and improved quality, and a method for manufacturing the same. [Means for solving the problem] 【0010】 The above problems can be solved by the following embodiments of the present invention. <Aspect 1> Inside the vacuum chamber, on a rotating drum, (a) A monomer layer formed by vapor deposition of monomers is cured by electron beam irradiation to form a thin resin film layer. (b) Applying oil partially and non-contact onto the resin thin film layer, (c) Depositing a metal material onto the resin thin film layer to which the oil has been applied to form a metal thin film layer having an electrical insulating portion. A method for manufacturing a multilayer capacitor, comprising repeating the following steps in this order at least 100 times to form a matrix element laminate on the rotating drum in which the resin thin film layer and the metal thin film layer are alternately stacked, In step (a), at least 1.0 second has elapsed since the start of irradiation with the electron beam, and before 3.8 seconds have elapsed since the start of irradiation with the electron beam, the oil is applied non-contact in step (b). Manufacturing method for multilayer capacitors. <Aspect 2> At least a portion of the matrix laminate constitutes an active portion, and in this active portion, with respect to two adjacent metal thin film layers separated by one resin thin film layer, the positions of the electrical insulating portions of each do not overlap with each other in the stacking direction. The manufacturing method described in Embodiment 1. <Aspect 3> With respect to a group of metal thin film layers stacked alternately among the aforementioned metal thin film layers, the positions of the electrical insulating portions of each layer overlap in the stacking direction, forming a margin, and the average displacement of the positions of the electrical insulating portions in this margin is less than 5% of the average width of these electrical insulating portions. The manufacturing method described in embodiment 1 or 2. <Aspect 4> The manufacturing method according to any one of embodiments 1 to 3, wherein the average thickness of the metal thin film layer is 1 nm to 20 nm and / or has a deposition resistance value of 10 to 45 Ω / □. <Aspect 5> When the degree of curing of the monomer when irradiated with an electron beam of 4.5 kV and 100 μA for 5 seconds is defined as x, the control value S is 24.85e -0.041x ≦S≦85.018e -0.026x is satisfied, the control value S is given by the following formula 1: S=(A / C) / D×T (Formula 1) (where A is the current value of the electron beam (unit: mA), C is the rotational speed of the drum (unit: m / min), D is the thickness per layer of the resin thin film layer (unit: μm), and T is the time from electron beam irradiation to oil application (unit: seconds)) calculated according to the manufacturing method according to any one of Aspects 1 to 4. <Aspect 6> The manufacturing method according to any one of Aspects 1 to 5, wherein the degree of curing of the resin thin film layer is 85% or less when the formation of the mother element laminate is completed. <Aspect 7> A multilayer capacitor having a structure in which at least 100 layers of a resin thin film layer and a metal thin film layer are alternately laminated, each of the metal thin film layers has an electrical insulation portion, Regarding two adjacent metal thin film layers through one resin thin film layer, the positions of the respective electrical insulation portions do not overlap each other in the lamination direction, Regarding a group of metal thin film layers laminated alternately among the metal thin film layers, the positions of the respective electrical insulation portions overlap each other in the lamination direction to form a margin portion, and the average of the displacements at the positions of the respective electrical insulation portions in this margin portion is less than 5% with respect to the average width of these electrical insulation portions, and on the surface of the multilayer capacitor, in a portion corresponding to the margin portion in the lamination direction, no recess is formed, or a recess having a size of a certain value or less is formed. Multilayer capacitor. <Aspect 8> The multilayer capacitor according to aspect 7, wherein the height of the recess having a size not greater than a certain value is less than 1 / 25 of the thickness of the multilayer capacitor. <Aspect 9> Regarding the recess having a size not greater than a certain value and the protrusion formed adjacent to the recess, The sum of the height of the recess and the height of the protrusion is less than 1 / 20 of the thickness of the multilayer capacitor, and / or, The height of the protrusion is less than 1 / 75 of the thickness of the multilayer capacitor. The multilayer capacitor according to aspect 7 or 8. <Aspect 10> The multilayer capacitor according to any one of aspects 7 to 9, wherein the average thickness of the metal thin film layer is 1 nm to 20 nm and / or has a deposition resistance value of 10 to 45 Ω / □. <Aspect 11> The multilayer capacitor according to any one of aspects 7 to 10, wherein the average width of the electrical insulating portion is 600 μm or less. <Aspect 12> The multilayer capacitor according to any one of aspects 7 to 11, wherein the thickness of the multilayer capacitor is 3 mm or less. <Aspect 13> The multilayer capacitor according to any one of aspects 7 to 12, wherein the resin thin film layer contains a thermosetting resin and / or a radiation-curable resin. <Aspect 14> The multilayer capacitor according to any one of aspects 7 to 13, wherein the average thickness of the resin thin film layer is 1.5 μm or less. 【Advantages of the Invention】 【0011】 According to the present invention, it is possible to provide a multilayer capacitor having a margin portion and improved quality and a method for manufacturing the same. 【Brief Description of the Drawings】 【0012】 [Figure 1] FIG. 1 is a schematic perspective view of one embodiment of a multilayer capacitor according to the present disclosure. [Figure 2]Figure 2 shows a schematic cross-sectional view of a conventional multilayer capacitor. [Figure 3] Figure 3 shows a schematic cross-sectional view of the multilayer capacitor according to this disclosure. [Figure 4] Figure 4 is a schematic diagram showing one embodiment of a manufacturing apparatus for producing multilayer capacitors. [Figure 5] Figure 5 is a schematic cross-sectional view of a portion of the surface of a multilayer capacitor, illustrating the method for determining the size of the uneven areas. [Figure 6] Figure 6 is a graph showing the relationship between the control value S related to the manufacturing conditions and the degree of monomer curing (%) under constant curing conditions for Examples 1-8 and Comparative Examples 1-8. [Modes for carrying out the invention] 【0013】 The method for manufacturing a multilayer capacitor according to this disclosure is carried out in a vacuum chamber on a rotating drum, The process includes repeating steps (a) to (c) below in this order at least 100 times to form a matrix element laminate on a rotating drum in which resin thin film layers and metal thin film layers are alternately stacked: (a) A monomer layer formed by monomer deposition is cured by electron beam irradiation to form a resin thin film layer. (b) Applying oil partially and non-contact onto a thin resin film layer, (c) Depositing a metal material onto an oil-coated resin thin film layer to form a metal thin film layer having an electrical insulating portion. 【0014】 The method for manufacturing a multilayer capacitor according to this disclosure is further characterized in that, in step (a) above, at least 1.0 second has elapsed since the start of electron beam irradiation, and before 3.8 seconds have elapsed since the start of electron beam irradiation, an oil is applied non-contact in step (b). 【0015】 The present invention will be described below with reference to the drawings. The drawings are not to scale. The drawings are illustrative and do not limit the present invention. 【0016】 Figure 1 is a schematic perspective view of one embodiment of a multilayer capacitor according to the present disclosure. The multilayer capacitor 1 has a structure 2 in which resin thin film layers and metal thin film layers are alternately stacked, and has external electrodes 3 and 4. 【0017】 Figure 2 shows a schematic cross-sectional view of a multilayer capacitor 20 manufactured by a conventional manufacturing method. The multilayer capacitor 20 includes metal thin film layers (211a-211f and 212a-212e) and resin thin film layers (white areas above, below, and between the metal thin film layers) stacked along the stacking direction D. For simplicity, Figure 2 shows approximately 10 metal thin film layers and 10 resin thin film layers, but an actual multilayer capacitor may have 100 or more (e.g., 10,000) metal thin film layers and 10,000 resin thin film layers. External electrodes can be attached to both sides of the multilayer capacitor 20 in Figure 2 (left and right sides of Figure 2) (not shown). 【0018】 Each of the metal thin film layers in Figure 2 has an electrical insulating portion (the portion where the black line is interrupted in the figure). Each electrical insulating portion separates one metal thin film layer into two parts, and these two parts are electrically isolated from each other. Preferably, the electrical insulating portion is in the shape of a strip with a certain width. 【0019】 Figure 2 illustrates only the active portion of a multilayer capacitor. In the active portion of the multilayer capacitor, the stacking positions of the electrical insulation portions differ for adjacent metal thin film layers, for example, metal thin film layers 211a and 212a, so that they do not overlap with each other in the stacking direction. By providing external electrodes on both sides of the laminate, for example, metal thin film layer 212a and metal thin film layer 211a each function as electrodes, and the dielectric layer sandwiched between them functions as a dielectric, thus forming a capacitor. In other words, the active portion is the capacitance generating portion of the capacitor. It is preferable to arrange the electrical insulation portions so that the portion that contributes to capacitance generation (effective portion) is maximized. Note that the multilayer capacitor may have reinforcing portions and / or protective portions above and / or below the active portion in the stacking direction (not shown in Figure 2). 【0020】 In the multilayer capacitor 20 shown in Figure 2, for every other group of metal thin film layers, the electrical insulating portions formed in the metal thin film layers (the areas where the black lines are interrupted in the figure) overlap each other in the stacking direction, thereby forming margin portions M1 and M2 (the regions shown by the dotted lines in the figure). 【0021】 In other words, with respect to every other group of metal thin film layers 211a to 211f, the electrical insulating portions formed in the metal thin film layers (the parts where the black lines are interrupted in the figure) overlap each other in the stacking direction D, thereby forming a margin portion M2. 【0022】 Furthermore, with respect to every other group of metal thin film layers 212a to 212e, the electrical insulating portions formed in the metal thin film layers (the areas where the black lines are interrupted in the figure) overlap each other in the stacking direction, thereby forming a margin portion M1. 【0023】 In multilayer capacitors manufactured using conventional manufacturing methods, recesses (251 and 252 in the figure) sometimes occurred on the upper surface of the capacitor due to these "margin portions" (M1 and M2 in the figure) formed by the overlapping positions of the electrical insulating portions in the stacking direction. Furthermore, the inventors of this invention have found that in addition to such recesses, protrusions (241a, 241b, 242a, and 242b in the figure) may also occur adjacent to them. 【0024】 Such irregularities caused by the margin area can lead to problems such as reduced voltage withstand capability and decreased insulation performance, increasing the risk of dielectric breakdown. Dielectric breakdown, in particular, can be a problem in multilayer capacitors used in high-voltage (200V or higher) applications. 【0025】 Furthermore, the protruding portion can cause problems such as cracks in the laminate due to pressure concentration during the heat pressing process after the matrix laminate is removed from the rotating drum. If the cracks are large, it becomes impossible to manufacture the capacitors, reducing production efficiency. Also, if fine cracks occur, the capacitor performance deteriorates, such as reduced insulation or short circuits. 【0026】 Furthermore, the protruding portion can cause gaps when applying external electrodes (especially metallicon). In this case, the metallicon may seep onto the capacitor surface, potentially causing short circuits or cosmetic defects. 【0027】 Conventionally, a solution has been known to suppress the formation of recesses by shifting the position of the electrical insulating portion in the stacking direction. However, such a solution sometimes fails to effectively eliminate unevenness. Furthermore, such a solution results in a relatively small area (width) that functions as a capacitor, leading to the problem that the size of the capacitor required to produce a capacitor of a certain capacitance becomes larger. 【0028】 In response to this, the inventors of this case found that the manufacturing conditions when forming the electrical insulation part during the capacitor manufacturing process are important in solving the above problem. 【0029】 Specifically, when forming the electrical insulation portion, the monomer layer is cured with an electron beam, and then oil is non-contactively applied to the cured monomer layer (resin thin film layer) in a pattern corresponding to the margin portion. When a metal material is deposited on this resin thin film layer containing oil, the metal thin film layer is not formed in the areas corresponding to the oil, and as a result, a metal thin film layer with an electrical insulation portion is formed. 【0030】 The inventors of this case have found that when applying oil non-contact, if the degree of curing of the monomer layer cured with an electron beam is insufficient (i.e., soft), the resin thin film layer is pushed aside by the pressure of the oil application, causing a depression, and the pushed-aside resin moves to both sides, forming a protrusion. 【0031】 In this case, reducing the oil application pressure can be considered as a method to suppress unevenness. Specifically, this could be done by increasing the distance from the nozzle used for non-contact oil application to the resin thin film layer, or by enlarging the spray hole. However, with such methods, it may not be possible to obtain the desired margin width, and in particular the margin width may become too large, which could result in a decrease in the capacitance output efficiency of the capacitor and a corresponding increase in size. 【0032】 In response to this, the inventors of this case have found that the occurrence of unevenness can be avoided or suppressed by setting the time from the start of electron beam irradiation to the application of oil in the curing process to a certain level or longer (1.0 second or more). Generally, it is thought that the longer the time elapsed after electron beam irradiation, the more the monomer layer hardens. That is, hardening progresses during electron beam irradiation, and hardening also progresses after electron beam irradiation due to heat, etc. Although there is no intention to limit the theory, it is thought that by setting the time from the start of electron beam irradiation to the application of oil in the curing process to a certain level or longer (1.0 second or more), the degree of hardening of the resin thin film layer when the oil is applied becomes relatively high, and as a result, indentations in the resin thin film layer caused by the oil application pressure are suppressed. 【0033】 While it is possible to suppress the occurrence of irregularities by simply increasing the degree of hardening during oil application by increasing the intensity of electron beam irradiation, this would result in excessive hardening of the laminate. This can lead to problems such as cracking during the film formation process or the subsequent pressurized heat treatment process. Furthermore, extending the time between electron beam irradiation and oil application too long is industrially undesirable, as it leads to excessive hardening of the laminate, decreased production efficiency, and the need for larger equipment. 【0034】 In contrast, the method of the present invention avoids this problem by setting the time from electron beam irradiation to oil application in the hardening treatment to a certain level or less (3.8 seconds or less). This prevents or suppresses the occurrence of cracks during or after the pressing process. Furthermore, even if cracks do not occur, the residual stress inside the laminate caused by pressing a laminate with a relatively high degree of hardening can be reduced, thus ensuring long-term mechanical stability even under harsh conditions. 【0035】 According to the manufacturing method described herein, the occurrence of uneven surfaces can be suppressed without excessively increasing the degree of curing of the resin thin film layer during the manufacturing process. This avoids problems caused by excessively high curing of the resin thin film layer while also avoiding problems caused by uneven surfaces, and as a result, it is possible to provide a multilayer capacitor with excellent quality. 【0036】 The present invention also includes multilayer capacitors, one embodiment of which is: A multilayer capacitor having a structure (particularly the active portion) in which resin thin film layers and metal thin film layers are alternately stacked in at least 100 layers each, Each of the thin metal layers has an electrical insulating portion. Regarding two metal thin film layers adjacent to each other via a single resin thin film layer, the positions of their respective electrical insulating portions do not overlap with each other in the stacking direction. Regarding a group of metal thin film layers stacked alternately, the electrical insulating portions of each layer overlap each other in the stacking direction, forming a margin, and the average displacement of these electrical insulating portions is less than 5% of the average width of the electrical insulating portions, and On the surface of the multilayer capacitor, no recesses are formed in the area corresponding to the margin in the stacking direction, or recesses of a certain size or smaller are formed. 【0037】 Figure 3 shows a schematic cross-sectional view of the multilayer capacitor 30 according to this disclosure. The basic configuration of the multilayer capacitor 30 is the same as that of the multilayer capacitor 20 described above. 【0038】 Figure 3, like Figure 2, illustrates only the active portion of the multilayer capacitor. In the active portion, the stacking positions of the electrical insulating portions are different for adjacent metal thin film layers, for example, metal thin film layers 311a and 312a, so that they do not overlap with each other in the stacking direction. The multilayer capacitor may have reinforcing and / or protective portions above and / or below this active portion in the stacking direction (not shown in Figure 3). 【0039】 In the multilayer capacitor 30 shown in Figure 3, for every other group of metal thin film layers, the electrical insulating portions formed in the metal thin film layers (the areas where the black lines are interrupted in the figure) overlap with each other in the stacking direction, thereby forming a margin (the area shown by the dotted line in the figure). 【0040】 In other words, for every other group of metal thin film layers 311a to 311f, the electrical insulating portions formed in the metal thin film layers (the parts where the black lines are interrupted in the figure) overlap each other in the stacking direction D, thereby forming a margin portion M2'. 【0041】 Furthermore, with respect to every other group of metal thin film layers 312a to 312e, the electrical insulating portions formed in the metal thin film layers (the parts where the black lines are interrupted in the figure) overlap each other in the stacking direction, thereby forming a margin portion M1'. 【0042】 On the other hand, in the multilayer capacitor 30 of Figure 3, unlike the multilayer capacitor 20 of Figure 2, no irregularities are formed on the surface portions (351 and 352) corresponding to the margin portions M1' and M2', or the irregularities are suppressed. 【0043】 In one aspect of the present invention, the electrical insulating portions of the multilayer capacitor 30 overlap each other in the stacking direction, thereby maximizing the area that functions as a capacitor (effective area). In this case, a capacitor with a relatively large capacitance can be manufactured in a relatively compact size. 【0044】 On the other hand, in a multilayer capacitor 30 according to one aspect of the present invention, even though the positions of the electrical insulating portions of the metal thin film layers overlap each other in the stacking direction to form a margin, the formation of unevenness in the surface portion of the multilayer capacitor corresponding to this margin is suppressed or avoided. 【0045】 Furthermore, the multilayer capacitor 30 in Figure 3 exhibits good quality because the degree of hardening of the resin thin film layer during its manufacturing process is suppressed, thus reducing the occurrence of cracks and other defects. 【0046】 Such a multilayer capacitor as shown in Figure 3 can be obtained by optimizing the manufacturing conditions when forming the electrical insulation portion according to the manufacturing method of this disclosure. Therefore, this disclosure includes a multilayer capacitor manufactured according to the manufacturing method of the present invention. 【0047】 Furthermore, the positions of the electrical insulating portions in the margin area do not necessarily need to substantially completely overlap each other in the lamination direction. 【0048】 In other words, in one embodiment of the present invention, with respect to every other group of metal thin film layers (particularly in the active portion), the electrical insulating portions formed on the metal thin film layers overlap each other at least partially (particularly partially) in the stacking direction, thereby forming a margin portion. 【0049】 In this case, for example, adjacent electrical insulating parts in the margin area may have a deviation of 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, less than 5%, 4% or less, 3% or less, 2% or less, or 1% or less relative to their average width. 【0050】 If the positions of the electrical insulating portions in the margin area are not completely overlapping but are at least partially offset, then in addition to the effect of optimizing the manufacturing conditions (especially the timing of oil application) when forming the electrical insulating portions according to the present invention, the effect of offsetting the positions of the electrical insulating portions in the margin area is added, and the formation of irregularities on the capacitor surface can be suppressed and avoided even more effectively. 【0051】 The methods related to this disclosure are described in more detail below. 【0052】 <<Manufacturing Method for Multilayer Capacitors>> <Resin thin film layer formation process> The method relating to this disclosure includes a step of curing a monomer layer formed by vapor deposition of monomers by irradiation with an electron beam to form a resin thin film layer (resin thin film layer formation step, step a). 【0053】 In the resin thin film layer formation process, for example, a monomer compound is heated to evaporate and vaporize, and this evaporated and vaporized monomer compound is deposited on a cooled rotating drum (or on a laminate precursor formed on the rotating drum) to form a monomer layer. 【0054】 Then, the monomer layer formed in this manner is cured by electron beam irradiation to form a thin resin film layer. 【0055】 Regarding the electron beam irradiation conditions, the intensity (unit: mA) is preferably 10 to 200 mA, and more preferably 20 to 180 mA. Furthermore, the acceleration voltage per 1 μm of resin thin film layer thickness is preferably 2 kV / μm to 30 kV / μm, and more preferably 3 kV / μm to 20 kV / μm. The distance between the electron source and the monomer layer may be 20 mm to 450 mm, and preferably 50 mm to 200 mm. 【0056】 The electron beam irradiation time is preferably 0.01 to 0.6 seconds, more preferably 0.02 to 0.5 seconds, even more preferably 0.03 to 0.4 seconds, and particularly preferably 0.04 to 0.3 seconds. 【0057】 (resin) The resin thin film layer is a monomer layer cured by electron beam irradiation. The resin thin film layer contains a polymer formed from the monomers in the monomer layer. The resin thin film layer does not need to be completely cured and may contain unpolymerized monomers. 【0058】 The resin thin film layer preferably includes a thermosetting resin and / or a radiation-curable resin. 【0059】 The resin thin film layer preferably comprises an acrylate resin and / or a vinyl resin. 【0060】 (monomer) Examples of monomers include polyfunctional monomers having multiple (particularly two) polymerizable functional groups in one molecule, monofunctional monomers having one polymerizable functional group in one molecule, and mixtures thereof. Polyfunctional monomers and monofunctional monomers can be polymerized via their polymerizable functional groups under conditions such as electron beam irradiation to form polymers. 【0061】 Polymerizable functional groups in the monomer include vinyl groups (particularly acrylate groups and methacrylate groups), acrylonitrile groups, and epoxy groups. Preferably, the polyfunctional monomer and / or monofunctional monomer have at least one of acrylate groups and methacrylate groups. Most preferably, both the polyfunctional monomer and the monofunctional monomer have acrylate groups. 【0062】 (Polyfunctional monomers) Polyfunctional monomers are particularly difunctional monomers. Polyfunctional monomers preferably have an acrylate group or a methacrylate group. Most preferably, polyfunctional monomers have an acrylate group. 【0063】 Particularly preferred polyfunctional monomers include: Tricyclodecane dimethanol diacrylate, Tricyclodecane dimethanol dimethacrylate, Dodecane-1,12-diyl dimethacrylate, Dodecane-1,12-diyl diacrylate, 1,9-nonanediol diacrylate, α,α'-[propane-2,2-diylbis-(4,1-phenylene)]bis[ω-(acryloyloxy)poly(oxyethylene)] These are some examples. 【0064】 (Monofunctional monomer) The monofunctional monomer preferably has an acrylate group or a methacrylate group. Most preferably, the monofunctional monomer has an acrylate group. 【0065】 Particularly preferred monofunctional monomers include: 2-(biphenyl-2-yloxy)-ethyl acrylate, 4-phenylbenzyl acrylate, 2-[(tricyclo[5.2.1.0(2,6)]deca-4-en-9-yl)oxy]ethyl acrylate, 2-[(tricyclo[5.2.1.0(2,6)]deca-4-en-9-yl)oxyethyl methacrylate] These are some examples. 【0066】 The average thickness of the resin thin film layer is preferably 1.5 μm or less. The lower limit of the average thickness of the resin thin film layer is not particularly limited, but may be 50 nm or more, or even 100 nm or more. More preferably, the average thickness of the resin thin film layer is 0.1 to 1.2 μm. 【0067】 <Patterning process> The manufacturing method according to this disclosure includes a step (patterning step, step b) of partially and non-contactly applying oil onto the resin thin film layer formed as described above. 【0068】 "Non-contact oil application," also known as "patterning," can be performed, for example, by spraying evaporated or vaporized oil from a nozzle, which then liquefies on the surface of a thin resin film layer and deposits it in a strip-like pattern. 【0069】 When the raw material for a metal thin film layer is deposited on a resin thin film layer coated with oil in this manner, the metal thin film layer is not formed in the areas of the resin thin film layer coated with oil, and these areas become electrical insulating areas. The application of oil can be carried out according to known methods, depending on the desired shape of the electrical insulating area, and in particular, can be appropriately adjusted according to the desired width of the electrical insulating area. 【0070】 In one embodiment of the present disclosure, a patterning process is performed on at least a portion (particularly the active portion) of the manufactured matrix stack such that the positions of the electrical insulating portions of two adjacent metal thin film layers separated by a single resin thin film layer do not overlap in the stacking direction. 【0071】 An example using Figure 3, which illustrates only the active portion, will be explained for reference. In the laminated condenser 30 of Figure 3, for example, two metal thin film layers 311f and 312e (each represented by a black line in the figure) are adjacent to each other via a resin thin film layer (the white portion in the figure). The metal thin film layers 311f and 312e are each separated into two parts by an electrical insulating portion (the portion where the black line is interrupted in the figure). 【0072】 The electrical insulating portion of the metal thin film layer 311f and the electrical insulating portion of the metal thin film layer 312e do not overlap each other in the stacking direction D, so that when an external electrode is attached to the side of the capacitor, a capacitor is formed between the margin portion M1' and the margin portion M2'. 【0073】 From the viewpoint of maximizing the effective area of ​​the capacitor, it is preferable that the distance between margin portion M1' and margin portion M2' be large. Margin portions M1' and M2' are provided away from the center of the multilayer capacitor and close to the sides. 【0074】 (Optimization of oil application) In the manufacturing method according to the present invention, oil is applied non-contact at least 1.0 second after the start of electron beam irradiation of the monomer layer, and before 3.8 seconds after the start of electron beam irradiation. 【0075】 As described above, this allows the hardened monomer layer to have a degree of hardening sufficient to withstand deformation pressure caused by non-contact oil application, while avoiding problems such as cracking that may occur due to excessive hardening. 【0076】 Non-contact oil application is preferably performed at least 1.1 seconds after the start of electron beam irradiation of the monomer layer, and before 3.7 seconds after the start of electron beam irradiation. 【0077】 Non-contact oil application is more preferably performed at least 1.1 seconds after the start of electron beam irradiation to the monomer layer, and before 3.5 seconds have elapsed since the start of electron beam irradiation. 【0078】 The timing of non-contact oil application is preferably optimized according to the monomer used. For example, if the monomer is tricyclodecanedimethanol dimethacrylate, it is preferable to apply the oil non-contact 1.5 to 3.5 seconds after the start of electron beam irradiation of the monomer layer. If the monomer is tricyclodecanedimethanol diacrylate, it is preferable to apply the oil non-contact 1.0 to 3.0 seconds after the start of electron beam irradiation of the monomer layer. If the monomer is 1,9-nonanediol diacrylate, it is preferable to apply the oil non-contact 1.0 to 2.5 seconds after electron beam irradiation of the monomer layer. 【0079】 (Optimization of control value S) In one preferred embodiment of the present disclosure, the control value (control value S) in the manufacturing method is optimized. Specifically, when the degree of curing of the monomer after irradiating the monomer with an electron beam (4.5kV, 100μA) for 5 seconds is denoted as x, The control value S is, 24.85e -0.041x ≤S ≤ 85.018e -0.026x It satisfies the condition. 【0080】 This control value S is more preferably, 33.98e -0.040x ≤S ≤ 77.21e -0.028x It satisfies the condition. 【0081】 The control value S can be calculated according to the formula "S = (A / C) / D × T", where A is the electron beam current value (in mA), C is the drum rotation speed (in m / min), D is the thickness of each layer of the resin thin film (in μm), and T is the time from the start of electron beam irradiation to oil application (in seconds). 【0082】 The electron beam current is preferably 20 to 180 mA. 【0083】 The rotational speed of the drum may be 10 m / min to 150 m / min, preferably 30 m / min to 100 m / min. 【0084】 The thickness of each resin thin film layer is preferably 1.5 μm or less, and more particularly 0.01 to 1.5 μm or even 0.1 to 1.2 μm. 【0085】 The time from the start of electron beam irradiation to oil application is between 1.0 and 3.8 seconds. 【0086】 <Metal thin film layer formation process> The manufacturing method according to this disclosure includes a step of depositing a metal material onto a resin thin film layer coated with oil as described above to form a metal thin film layer having an electrical insulating portion (metal thin film layer formation step, step c). 【0087】 As described above, when the raw material for a metal thin film layer is deposited on a resin thin film layer coated with oil, the metal thin film layer does not form in the areas of the resin thin film layer coated with oil, and these areas become electrically insulating. In other words, the presence of the coated oil causes the formation of the electrically insulating areas. 【0088】 The metal thin film layer formation process can be carried out by conventionally known methods, for example, the method described in International Publication No. 2015 / 118693 can be used. 【0089】 In the metal thin film layer formation process, for example, a metal material is deposited using an electron beam heating evaporation method to form a metal thin film layer. More specifically, for example, an electron beam is irradiated from an electron gun onto a metal material contained in a crucible (metal evaporation source), and the energy of the electron beam evaporates and vaporizes the metal material in the crucible, thereby performing deposition. In this process, the distance between the evaporation source and the rotating drum may be, for example, in the range of 50 mm to 300 mm. 【0090】 The metallic material constituting the thin metallic layer is not particularly limited, but examples include at least one selected from the group consisting of Al, Cu, Zn, Sn, Au, Ag, and Pt, and combinations thereof. The metallic material is preferably Al. 【0091】 The metal thin film layer preferably has a smaller thickness than the resin thin film layer. 【0092】 The metal thin film layer may have a thickness of 1 nm to 40 nm, preferably 1 to 20 nm. Furthermore, the metal thin film layer preferably has a deposition resistance of 1 to 60 Ω / □, 5 to 50 Ω / □, or 10 to 450 Ω / □. 【0093】 In one embodiment of the present disclosure, the thickness of the metal thin film layer is reduced, so that the metal thin film layer has an average thickness of 1 nm to 20 nm and / or an evaporation resistance of 10 to 45 Ω / □. More preferably, the metal thin film layer has an average thickness of 1 nm to 15 nm and / or an evaporation resistance of 15 to 40 Ω / □. 【0094】 As described above, by setting the time from the start of electron beam irradiation to oil application to 1.0 second or more, the degree of hardening of the resin thin film layer at the time of oil application will be above a certain level, and as a result, the occurrence of irregularities in the surface area corresponding to the margin can be suppressed or avoided. 【0095】 On the other hand, if the degree of hardening during the manufacturing process of multilayer capacitors is too high, problems such as delamination and cracking of the laminate may occur. 【0096】 In contrast, when the thickness of the metal thin film layer is reduced as described above, even if the degree of hardening of the resin thin film layer is relatively high, the overall hardness of the laminate is reduced, and as a result, the occurrence of cracks and other defects can be suppressed more effectively. 【0097】 The thickness of the metal thin film layer is preferably 1 / 8 to 1 / 70, more preferably 1 / 10 to 1 / 60, of the thickness of the resin thin film layer. 【0098】 (Electrical insulation part) The electrical insulation portion preferably has a width of 0.01 mm to 1.5 mm, 0.05 mm to 1.0 mm, 0.1 mm to 0.6 mm, or even 0.1 mm to 0.3 mm. If the width of the electrical insulation portion is too large, it may not be possible to secure the desired effective portion (capacitance generation portion) of the capacitor. Conversely, if the width of the electrical insulation portion is too small, good electrical insulation in the electrical insulation portion may not be ensured, and ease of manufacturing may be impaired. 【0099】 (Margin section) In one embodiment of the present disclosure, with respect to a group of metal thin film layers stacked alternately (particularly in the active portion), the positions of the electrical insulating portions of each layer overlap each other at least partially in the stacking direction, forming a margin portion. 【0100】 Furthermore, in one embodiment of the present disclosure, with respect to a group of electrical insulating portions forming a margin (particularly in the active portion), their positions in the stacking direction substantially overlap each other. More specifically, the average displacement of the positions of each electrical insulating portion in the margin portion is less than 5% of the average width of the electrical insulating portions. 【0101】 The average of this deviation is more preferably 4% or less, 3% or less, 2% or less, or 1% or less with respect to the average width of the electrical insulation portion. 【0102】 To illustrate with an example using Figure 3, the electrical insulating portions of the metal thin film layers 312a to 312e form a group, creating a margin portion M1'. In the case of Figure 3, the positions of each electrical insulating portion in this margin portion M1' are substantially aligned in the stacking direction, and as a result, the average of the positional displacements of each electrical insulating portion is substantially zero with respect to the average width of these electrical insulating portions. 【0103】 In this case, compared to the case where the position of the electrical insulation part in the margin is shifted, the area that functions as a capacitor (effective area) is maximized, so it is possible to manufacture a capacitor with a relatively large capacitance in a relatively compact size. Also, compared to the case where the position of the electrical insulation part is shifted, processes such as oil application can be simplified, thus reducing the control burden in the manufacturing process. 【0104】 The average displacement of the electrical insulation portion in the stacking direction can be obtained by randomly selecting 50 or more electrical insulation portions from a group of electrical insulation portions belonging to a single margin portion, measuring the displacement width (μm) from the adjacent electrical insulation portion below in the stacking direction for each portion, calculating the average value, and then calculating the ratio to the average width of the above randomly selected 50 or more electrical insulation portions. 【0105】 <Lamination process> In the method according to this disclosure, the above steps, namely the "resin thin film layer formation step (step a)", the "patterning step (step b)", and the "metal thin film layer formation step (step c)", are repeated at least 100 times on a rotating drum in a vacuum chamber to form a matrix element laminate in which resin thin film layers and metal thin film layers are alternately stacked on a rotating drum. 【0106】 For the method of alternately stacking resin thin film layers and metal thin film layers on a rotating drum in a vacuum chamber, known methods can be used, for example, the method described in International Publication No. 2015 / 118693 can be used. 【0107】 (Rotating drum) The rotating drum may be cooled to a predetermined temperature within the range of 0°C to 20°C. To cool the rotating drum to a predetermined temperature within the range of 0°C to 20°C, for example, a cooling medium (antifreeze or water) within the range of -5°C to 20°C can be circulated in the space inside the rotating drum. 【0108】 The rotational speed of the rotating drum is typically around 10 m / min to 150 m / min. The outer surface (substrate surface) of the rotating drum is finished smoothly, preferably to a mirror-like finish. 【0109】 The matrix element laminate may have 10 to 10,000 layers, 50 to 5,000 layers, or 100 to 3,000 layers. Of these, the active portion may have 5 to 9,800 layers. 【0110】 <Subsequent steps> From the matrix element laminate formed as described above, a multilayer capacitor can be formed according to a conventional method (for example, the method described in International Publication No. 2015 / 118693). 【0111】 Specifically, for example, the matrix element stack formed on the rotating drum is removed from the rotating drum and taken out of the vacuum chamber. The matrix element stack removed from the vacuum chamber is usually curved in an arc shape with approximately the same curvature as the outer surface of the rotating drum. This matrix element stack can be flattened by pressing it under heating. After cutting the flattened matrix element stack into a stick shape, external electrodes are formed, and these are further cut into chip shapes to obtain a multilayer capacitor. The formation of external electrodes can also be carried out by known methods. 【0112】 In one preferred embodiment of the manufacturing method according to this disclosure, the degree of curing of the resin thin film layer is 85% or less, more preferably 70% or less, when the formation of the mother element laminate is completed. 【0113】 In this case, the occurrence of cracks when the matrix element laminate is flattened by heating and pressing can be suppressed or avoided, making it possible to provide a multilayer capacitor with particularly excellent quality. 【0114】 The degree of curing of a resin thin film layer can be measured using an infrared spectrophotometer. By measuring the absorbance of C=O groups and C=C groups in the resin thin film layer and raw material monomers of the laminate, and using the first ratio of the absorbance of C=O groups to C=C groups in the resin thin film layer and the second ratio of the absorbance of C=O groups to C=C groups in the raw material monomers, the degree of curing (%) can be calculated. 【0115】 More specifically, the degree of hardening (%) can be calculated using the following formula: Degree of curing (%) = 100 × {1 - (absorbance of C=C groups in the resin thin film layer / absorbance of C=O groups in the resin thin film layer) / (absorbance of C=C groups in the raw material monomer / absorbance of C=O groups in the raw material monomer)} 【0116】 According to the manufacturing method of this disclosure, a multilayer capacitor can be obtained in which the surface area corresponding to the margin portion has reduced irregularities. In particular, according to the manufacturing method of this disclosure, a multilayer capacitor can be obtained in which the surface area corresponding to the margin portion has reduced irregularities, and cracks and fractures have also been reduced. For details of the multilayer capacitor obtained by the manufacturing method of this disclosure, please refer to the description of the multilayer capacitor according to this disclosure below. 【0117】 One embodiment of the manufacturing method according to the present invention will be described in detail with reference to the drawings. 【0118】 Figure 4 shows a manufacturing apparatus 10 for carrying out the method according to the present invention for manufacturing multilayer capacitors. The manufacturing apparatus 10 comprises a vacuum chamber 12, a rotating drum 14 that rotates within the vacuum chamber 12, and a monomer deposition apparatus 18, an electron beam irradiation apparatus 19, a first plasma processing apparatus 22, a metal thin film layer patterning apparatus 24, a metal deposition apparatus 26, and a second plasma processing apparatus 28, all arranged around the rotating drum 14 along the rotation direction 14a of the rotating drum 14. A vacuum evacuation apparatus and a purging apparatus (not shown) are connected to the vacuum chamber 12. 【0119】 The rotating drum 14 is driven to rotate in the rotation direction 14a by a rotary drive device (not shown). The rotating drum 14 is cooled by a cooling mechanism 16 to a predetermined temperature, preferably in the range of 0°C to 20°C, more preferably in the range of 5°C to 15°C. 【0120】 The monomer deposition apparatus 18 heats and evaporates / vaporizes monomers for forming a resin thin film layer, deposits / deposits them on the rotating drum 14, thereby forming a monomer layer. 【0121】 The electron beam irradiation device 19 polymerizes or crosslinks the monomer layer, thereby forming a resin thin film layer. 【0122】 The first plasma processing apparatus 22 is, for example, an oxygen plasma apparatus, which activates the surface of the resin thin film layer by oxygen plasma treatment to improve the adhesion between the resin thin film layer and the metal thin film layer. The first plasma processing apparatus 22 is not limited to an oxygen plasma apparatus, but may be a nitrogen plasma apparatus, an argon plasma apparatus, or any other plasma processing apparatus. 【0123】 In plasma processing using the first plasma processing apparatus 22, the resin thin film layer formed in the resin thin film layer formation process may be plasma-treated under conditions within the range of 50W to 1000W. 【0124】 The metal thin film layer patterning apparatus 24 sprays evaporated and vaporized oil, used as a patterning material, from a nozzle, depositing it in a band-like pattern on the surface of the resin thin film layer. 【0125】 The metal deposition apparatus 26 deposits a metal material onto the surface of the rotating drum 14 using an electron beam heating deposition method to form a thin metal film layer. Specifically, an electron beam is irradiated from an electron gun onto the metal material contained in a crucible (metal deposition source), and the energy of the electron beam causes the metal material in the crucible to evaporate and vaporize, depositing onto the rotating drum 14. The metal deposition apparatus 26 is not limited to the electron beam heating deposition method, but may also use other vacuum deposition methods such as resistance heating deposition or sputtering. 【0126】 The second plasma processing apparatus 28 is, for example, an oxygen plasma processing apparatus, which removes the patterning material deposited by the metal thin film layer patterning apparatus 24 and activates the surface of the metal thin film layer by oxygen plasma treatment to improve the adhesion between the metal thin film layer and the resin thin film layer. The second plasma processing apparatus 28 is not limited to an oxygen plasma processing apparatus, but may be a nitrogen plasma processing apparatus, an argon plasma processing apparatus, or any other plasma processing apparatus. 【0127】 In the plasma treatment using the second plasma processing apparatus 28, the metal thin film layer formed in the metal thin film layer formation process may be plasma treated under conditions within the range of 50W to 1000W. 【0128】 The monomer deposition apparatus 18, electron beam irradiation apparatus 19, first plasma processing apparatus 22, metal thin film layer patterning apparatus 24, metal deposition apparatus 26, and second plasma processing apparatus 28, as well as a vacuum evacuation apparatus and a purging apparatus (not shown), can be controlled by a control device. 【0129】 An exemplary embodiment of a multilayer capacitor using this manufacturing apparatus 10 is as follows: First, a monomer layer is formed on the outer circumference of the rotating drum 14 using a monomer deposition apparatus 18, and this monomer layer is cured by an electron beam irradiation apparatus 19 to form a resin thin film layer (resin thin film layer formation step). Next, the surface of the resin thin film layer is activated by oxygen plasma treatment using a first plasma treatment apparatus 22 (first plasma treatment step). Next, a patterning material is deposited in a strip shape on the resin thin film layer using a metal thin film layer patterning apparatus 24. Next, a metal thin film layer is formed on the resin thin film layer using a metal deposition apparatus 26 (metal thin film layer formation step). At this time, the metal thin film layer is not formed in the areas where the patterning material is deposited, and these areas become the electrically insulating parts of the laminate. Next, the surface of the metal thin film layer is activated by oxygen plasma treatment using a second plasma treatment apparatus 28 (second plasma treatment step). This makes it possible to remove the patterning material deposited by the metal thin film layer patterning apparatus 24. Furthermore, when the monomer layer is formed again by the monomer deposition apparatus 18, the metal constituting the metal thin film layer and the carbon contained in the monomer constituting the resin thin film layer chemically bond together, resulting in improved adhesion between the metal thin film layer and the resin thin film layer. 【0130】 <<Multilayer Capacitor>> This disclosure includes the following multilayer capacitors: A multilayer capacitor having a structure (particularly the active portion) in which resin thin film layers and metal thin film layers are alternately stacked in at least 100 layers each, Each of the thin metal layers has an electrical insulating portion. Regarding two metal thin film layers adjacent to each other via a single resin thin film layer, the positions of their respective electrical insulating portions do not overlap with each other in the stacking direction. Regarding a group of metal thin film layers stacked alternately, the electrical insulating portions of each layer overlap each other at least partially in the stacking direction, forming a margin. Preferably, the average displacement of these electrical insulation parts is less than 5% of the average width of the electrical insulation parts, and On the surface of the multilayer capacitor, no recesses are formed in the portion corresponding to the margin portion in the stacking direction, or recesses of a certain size or less are formed. 【0131】 This "structure in which resin thin film layers and metal thin film layers are alternately stacked in at least 100 layers each" is particularly found in the active portion of a multilayer capacitor. 【0132】 The method for manufacturing the multilayer capacitor according to this disclosure is not particularly limited, but preferably it can be manufactured by the manufacturing method according to this disclosure described above. 【0133】 For details regarding the components of the multilayer capacitor related to this disclosure (such as the resin thin film layer, metal thin film layer, electrical insulation portion, and margin portion), please refer to the above description of the manufacturing method related to this disclosure. 【0134】 <Electrical Insulation Section> In the multilayer capacitor according to this disclosure, in at least a portion of the multilayer capacitor (particularly the active portion), the positions of the electrical insulating portions of two metal thin film layers adjacent to each other via a single resin thin film layer do not overlap in the stacking direction. 【0135】 Furthermore, in the multilayer capacitor according to this disclosure, with respect to a group of metal thin film layers stacked alternately in at least a portion of the multilayer capacitor (particularly the active portion), the positions of the electrical insulating portions of each layer overlap at least partially (particularly partially) with respect to each other in the stacking direction, forming a margin portion. 【0136】 Preferably, the average displacement of the position of each electrical insulation part in this margin is less than 5% of the average width of these electrical insulation parts. 【0137】 These characteristics regarding the location of the electrical insulation part are as described above. 【0138】 <Uneven part> As described above, in the multilayer capacitor according to this disclosure, no recesses are formed on the surface of the multilayer capacitor in the area corresponding to the margin in the stacking direction, or recesses of a certain size or less are formed. 【0139】 In one preferred embodiment of the multilayer capacitor according to the present disclosure, a recess of a certain size or less is formed on the surface corresponding to at least one margin portion, the height of which is less than 1 / 25 of the thickness of the multilayer capacitor. More preferably, this height is 1 / 30 or less, and even more preferably 1 / 40 or less. 【0140】 In another preferred embodiment of the multilayer capacitor according to the present disclosure, a recess of a certain size or less and a protrusion adjacent to the recess are formed on a surface corresponding to at least one margin portion, wherein the sum of the height of the recess and the height of the protrusion is less than 1 / 20 of the thickness of the multilayer capacitor, and / or the height of the protrusion is less than 1 / 75 of the thickness of the multilayer capacitor. More preferably, the sum of the height of the recess and the height of the protrusion is less than 1 / 25 of the thickness of the multilayer capacitor, and / or the height of the protrusion is less than 1 / 80 of the thickness of the multilayer capacitor. 【0141】 If the size of the uneven surface meets these conditions, defects caused by the uneven surface can be suppressed or avoided, and a high-quality multilayer capacitor can be obtained. 【0142】 In addition, two protrusions may be formed adjacent to a recess, but preferably both of the two protrusions adjacent to the recess satisfy the above-mentioned requirements regarding their height. Furthermore, if the multilayer capacitor has two or more margin portions (especially two), the surface portion corresponding to at least one of the margin portions, preferably the surface portion corresponding to all of the margin portions (especially two margin portions), satisfies the above-mentioned conditions regarding the uneven surface. 【0143】 The method for measuring the size of the uneven areas will be explained with reference to Figure 5. Figure 5 is a schematic cross-sectional view showing a part of the multilayer capacitor 50, and is an enlarged view of the capacitor surface area corresponding to the margin. Note that in Figure 5, the size of the uneven areas is exaggerated for illustrative purposes. 【0144】 The size of the uneven portion can be measured relative to the surface 510 of the multilayer capacitor 50 (the surface located outside the uneven portion). Specifically, the height Hc of the recess 551 is defined as the depth of the recess 551 relative to the surface 510, and the height Hv of the protrusion 541 is defined as the height of the protrusion 541 relative to the surface 510. The sum of the heights of the recess 551 and the protrusion 541 is HT = Hc + Hv. The height of the protrusion 542 can be determined in the same manner. 【0145】 The heights of the recesses and protrusions are preferably 100 μm or less, more preferably 50 μm or less, even more preferably 25 μm or less, and particularly preferably 10 μm or less. 【0146】 The number of layers in a multilayer capacitor (the number of layers in a multilayer unit consisting of a resin thin film layer and a metal thin film layer) may be 10 to 10,000 layers, 50 to 5,000 layers, or 100 to 3,000 layers. Of these, the number of layers in the active section may be 5 to 9,800 layers, or even 300 to 8,000 layers. 【0147】 The thickness of the multilayer capacitor is preferably 3 mm or less. The lower limit of this thickness is not particularly limited, but may be, for example, 0.5 mm or more, or 1 mm or more. 【0148】 (Reinforcement section) The multilayer capacitor according to this disclosure may further have a reinforcing portion on one or both sides thereof. The thickness of the reinforcing portion is not particularly limited, but may be, for example, 20 to 200 μm. 【0149】 The reinforcing portion may have a structure in which a resin thin film layer and a metal thin film layer having an electrical insulating portion are alternately laminated. Preferably, the electrical insulating portion in the reinforcing portion is located in the central part of the multilayer capacitor, that is, in a portion away from both sides of the multilayer capacitor. The positions of these electrical insulating portions can overlap each other in the lamination direction to form a reinforcing portion margin. 【0150】 The reinforcing portion may serve to protect the laminated structure (also called the active portion) described above, as shown in Figure 3, etc. That is, the reinforcing portion may serve to protect the active portion from thermal load and / or external force damage during the manufacturing process or use of the laminated capacitor. In addition, the metal layer in the reinforcing portion improves the adhesion strength of the external electrodes. 【0151】 (Protection Department) Multilayer capacitors may have a protective layer made solely of resin, particularly on their outermost layer (one or both sides). The thickness of the protective layer is not particularly limited, but may be, for example, 2 μm to 20 μm. The protective layer may serve to protect the active components from thermal load and / or external force damage during the manufacturing process or use of the multilayer capacitor. 【0152】 (Application) The multilayer capacitors described herein can be used in various electronic component applications and are particularly suitable for use in high-voltage applications. [Examples] 【0153】 The present invention will be described in more detail below with reference to examples. The present invention is not limited by the examples. 【0154】 <<Determination of Hardening Degree>> The degree of hardening was investigated for the following monomers 1 to 4 after constant electron beam irradiation: Monomer 1: Tricyclodecanedimethanol dimethacrylate Monomer 2: Mixture of tricyclodecanedimethanol dimethacrylate and tricyclodecanedimethanol diacrylate = 7:3 • Monomer 3: Tricyclodecanedimethanol diacrylate • Monomer 4: 1,9-nonanediol diacrylate 【0155】 The degree of hardening was determined for each monomer from 1 to 4 as follows: (1) Drop the monomer stock solution onto a glass slide and spread it with a 22 μm coater to form a monomer layer on the glass slide. (2) The monomer layer is cured by irradiating it with an electron beam for 5 seconds under the conditions of an output of 4.5kV and a current of 100μA in a vacuum. (3) The surface of the monomer layer after the above curing treatment was measured with an infrared spectrophotometer and compared with the measured value of the monomer layer before curing, and the degree of curing (%) was calculated as described above in the specification. 【0156】 As a result, the degree of hardening (x) of each monomer, as measured by an infrared spectrophotometer, was as shown in Table 1 below. 【0157】 [Table 1] 【0158】 <<Examples 1-2 and Comparative Examples 1-2>> In Examples 1-2 and Comparative Examples 1-2, "Monomer 1," which had a curing degree of 12.5% ​​after 5 seconds of electron beam irradiation, was used to manufacture multilayer capacitors under various manufacturing conditions, and the presence or absence of irregularities was investigated. 【0159】 <Example 1> (Manufacturing of multilayer capacitors) The laminate was manufactured using the following procedure: Inside the vacuum chamber, on a rotating drum, (a) A monomer layer is formed by vapor deposition of monomers, and the monomer layer is cured by irradiation with an electron beam to form a resin thin film layer. (b) Apply oil non-contact on the resin thin film layer in a strip pattern with a width of 200 μm, (c) A metal thin film layer is formed by depositing a metal material onto an oil-coated resin thin film layer, thereby forming a margin (electrically insulating portion) in the area corresponding to the oil-coated area. (d) By repeatedly performing steps (a) to (c) in this order, a matrix element laminate in which resin thin film layers and metal thin film layers are alternately stacked is formed on a rotating drum. 【0160】 Furthermore, the application of oil and the formation of the electrical insulating portion were carried out so that at least a portion of the mother element laminate constituted the active portion. That is, when the above steps (a) to (c) were repeated, the positions of the electrical insulating portions of two metal thin film layers adjacent to each other via a single resin thin film layer were made so as not to overlap in the stacking direction, thereby forming the active portion. 【0161】 After removing the above-mentioned matrix element laminate formed on the rotating drum from the rotating drum, 2 kgf / cm² 2 The material was flattened by pressing it under heating pressure. Then, the flattened matrix laminate was cut into stick shapes, external electrodes were formed, and these were further cut into chip shapes to obtain a thin-film polymer multilayer capacitor. 【0162】 In Example 1, the manufacturing conditions for the matrix laminate were set as shown in Table 2 below. (In Table 2, A: electron beam current value (unit: mA), C: drum rotation speed (unit: m / min), D: thickness of each resin thin film layer (unit: μm), T: time from start of electron beam irradiation to oil application (unit: seconds)). 【0163】 In Example 1, the control value S = (A / C) / D × T was 20.7. The acceleration voltage per 1 μm of resin thin film thickness was 19 kV / μm. The distance between the electron source and the monomer layer was 100 mm. 【0164】 The parameters of the multilayer capacitor in Example 1 were as follows: Thickness of multilayer capacitor: 1700 μm Multilayer capacitor dimensions (length x width): 3.2 x 2.5 mm Average thickness of the resin thin film layer: 0.23 μm Average thickness of the metal thin film layer: 15 nm Average width of electrical insulation layer: 200 μm Average displacement of electrical insulation in the margin area: 3% 【0165】 The electron beam irradiation time in the following examples and comparative examples ranged from 0.06 seconds to 0.24 seconds. The electron beam irradiation time can be calculated from the electron beam irradiation width (length of the irradiation area in the direction of drum rotation) on the monomer layer and the drum rotation speed. For example, in Example 1, the electron beam irradiation time was approximately 0.1 seconds. In Example 2, the drum rotation speed was half that of Example 1, so the electron beam irradiation time was double, approximately 0.2 seconds. The number of layers in the multilayer capacitors in the following examples and comparative examples (number of layers of multilayer units consisting of resin thin film layers and metal thin film layers) was 1000 layers or more. 【0166】 (Evaluation of unevenness) The multilayer capacitors manufactured as described above were evaluated for the presence or absence of surface irregularities. 【0167】 Specifically, the surface irregularities of the multilayer capacitor's surface, particularly those corresponding to the margin area, were observed and quantified using a microscope and evaluated according to the following criteria: Good (〇): The sum of the height of the recess and the height of the protrusion is less than 1 / 20 of the thickness of the multilayer capacitor, the height of the recess is less than 1 / 25 of the thickness of the multilayer capacitor, and the height of the protrusion is less than 1 / 75 of the thickness of the multilayer capacitor. Defective (×): The sum of the height of the recess and the height of the protrusion is 1 / 20 or more of the thickness of the multilayer capacitor, or the height of the recess is 1 / 25 or more of the thickness of the multilayer capacitor, or the height of the protrusion is 1 / 75 or more of the thickness of the multilayer capacitor. 【0168】 The height of the uneven portion was determined as described above, referring to Figure 5. 【0169】 The evaluation results for Example 1 are shown in Table 2 below. 【0170】 (Cracked evaluation) Furthermore, the multilayer capacitors manufactured as described above were evaluated for cracking. Specifically, the cross-section of the multilayer capacitors was observed visually and with a microscope. If no cracks or fissures were observed, the capacitor was rated as good (○), and if cracks or fissures were observed, it was rated as poor (×). The results are shown in Table 2 below. 【0171】 <Example 2> In Example 2, multilayer capacitors were manufactured in the same manner as in Example 1, except that the manufacturing conditions were changed as shown in Table 2 below, and the unevenness and cracks were evaluated. The evaluation results for Example 2 are shown in Table 2 below. 【0172】 <Comparative Example 1> In Comparative Example 1, a multilayer capacitor was manufactured in the same manner as in Example 1, except that the manufacturing conditions were changed as shown in Table 2 below, and the unevenness and cracks were evaluated. The evaluation results for Comparative Example 1 are shown in Table 2 below. 【0173】 <Comparative Example 2> In Comparative Example 2, a multilayer capacitor was manufactured in the same manner as in Example 1, except that the manufacturing conditions were changed as shown in Table 2 below, and the unevenness and cracks were evaluated. The evaluation results for Comparative Example 2 are shown in Table 2 below. 【0174】 [Table 2] 【0175】 As can be seen in Table 2, Examples 1 and 2, in which the time from the start of electron beam irradiation to oil application was in the range of 1.0 to 3.8 seconds, showed better results in terms of surface formation or cracking compared to Comparative Examples 1 and 2, in which the time from the start of electron beam irradiation to oil application was 0.80 seconds and 5.00 seconds, respectively. 【0176】 <<Examples 3-4 and Comparative Examples 3-4>> In Examples 3-4 and Comparative Examples 3-4, the manufacturing and evaluation of multilayer capacitors were carried out in the same manner as in Example 1, except that monomer 2 was used instead of monomer 1, and the multilayer capacitors were manufactured under the manufacturing conditions shown in Table 3 below. The results are shown in Table 3 below. 【0177】 [Table 3] 【0178】 As can be seen in Table 3, even when monomer 2 was used instead of monomer 1, Examples 3 and 4, in which the time from the start of electron beam irradiation to oil application was in the range of 1.0 to 3.8 seconds, showed better results in terms of surface formation or cracking compared to Comparative Examples 3 and 4, in which the time from the start of electron beam irradiation to oil application was 0.8 seconds and 4.2 seconds, respectively. 【0179】 <<Examples 5-6 and Comparative Examples 5-6>> In Examples 5-6 and Comparative Examples 5-6, the manufacturing and evaluation of multilayer capacitors were carried out in the same manner as in Example 1, except that monomer 3 was used instead of monomer 1, and the multilayer capacitors were manufactured under the manufacturing conditions shown in Table 4 below. The results are shown in Table 4 below. 【0180】 [Table 4] 【0181】 As can be seen in Table 4, even when monomer 3 was used instead of monomer 1, Examples 5 and 6, in which the time from the start of electron beam irradiation to oil application was in the range of 1.0 to 3.8 seconds, showed better results in terms of surface formation or cracking compared to Comparative Examples 5 and 6, in which the time from the start of electron beam irradiation to oil application was 0.6 seconds and 5.0 seconds, respectively. 【0182】 <<Examples 7-8 and Comparative Examples 7-8>> In Examples 7 to 8 and Comparative Examples 7 to 8, a multilayer capacitor was manufactured and evaluated in the same manner as in Example 1, except that monomer 4 was used instead of monomer 1, and the manufacturing conditions shown in Table 5 below were used. The results are shown in Table 5 below. 【0183】 【Table 5】 【0184】 As can be seen in Table 5, in Examples 7 and 8 where the time from the start of electron beam irradiation to oil application was within the range of 1.0 to 3.8 seconds even when monomer 4 was used instead of monomer 1, good results were shown regarding the formation of unevenness or cracks as compared with Comparative Examples 7 and 8 where the time from the start of electron beam irradiation to oil application was 0.5 seconds and 4.1 seconds. 【0185】 <Summary of Results> The experimental results of Examples 1 to 8 and Comparative Examples 1 to 8 are summarized in FIG. 6. FIG. 6 is a graph showing the relationship between the control value S regarding the manufacturing conditions and the degree of curing (%) of the monomer under certain curing conditions for Examples 1 to 8 (indicated by "〇" or "●" in the graph) and Comparative Examples 1 to 8 (indicated by "×" in the graph). FIG. 6 shows straight lines obtained by exponential approximation for cases where the control value S was relatively high (Examples 2, 4, 6, and 8) and cases where the control value S was relatively low (Examples 1, 3, 5, and 7) among the results for each monomer (vertical axis y (or S), horizontal axis x). In any of the cases where the value of x, which is an index of the ease of curing of the monomer, is 12.5%, 40.0%, 58.0%, and 82.6%, it was found that the formation of uneven portions was well suppressed when 24.85e -0.041x ≦S≦85.018e -0.026x was satisfied (particularly when 33.98e -0.040x ≦S≦77.21e -0.028x was satisfied). 【Explanation of Signs】 【0186】 1 Multilayer capacitor (thin-film polymer multilayer capacitor) 2. Laminated structure of resin thin film layer and metal thin film layer 3, 4 External electrode 20 Multilayer Capacitors 211a~211f Metal thin film layer 212a~212e Metal thin film layer M1, M2 Margin Section 251, 252 recesses 241a, 241b, 242a, 242b protrusions D Stacking direction 30 Multilayer Capacitors 311a~311f Metal thin film layer 312a~312e Metal thin film layer M1', M2' Margin Section 351, 352 Surface areas corresponding to the margins 10 Manufacturing equipment 12 Vacuum Chamber 14-rpm drum 14a Direction of rotation 16 Cooling device 18. Monomer deposition apparatus 19 Electron beam irradiation device 22. First Plasma Processing Unit 24 Metal Thin Film Patterning Apparatus 26 Metal vapor deposition equipment 28. Second Plasma Processing Unit 50 Multilayer Capacitors 510 Surface of a multilayer capacitor 551 recess 541 Convex part 542 Convex part HT: Sum of the height of the recess and the height of the protrusion Hc recess height Hv Height of the protrusion

Claims

[Claim 1] Inside the vacuum chamber, on a rotating drum, (a) A monomer layer formed by vapor deposition of monomers is cured by electron beam irradiation to form a resin thin film layer. (b) Applying oil partially and non-contact on the resin thin film layer, (c) Depositing a metal material onto the resin thin film layer to which the oil has been applied to form a metal thin film layer having an electrical insulating portion. A method for manufacturing a multilayer capacitor, comprising repeating the following steps in this order at least 100 times to form a matrix element laminate on the rotating drum in which the resin thin film layer and the metal thin film layer are alternately stacked, After at least 1.0 second has elapsed since the start of irradiation with the electron beam in step (a), and before 3.8 seconds have elapsed since the start of irradiation with the electron beam, the oil is applied non-contact in step (b). The acceleration voltage of the electron beam per 1 μm of thickness of the resin thin film layer is 2 kV / μm to 30 kV / μm. The distance between the electron beam source and the monomer layer is 20 mm to 450 mm. The current value of the electron beam is 20 to 180 mA. The average thickness of the aforementioned resin thin film layer is 1.5 μm or less. The average thickness of the metal thin film layer is 1 nm to 40 nm, and / or the metal thin film layer has a deposition resistance of 10 to 45 Ω / □. The aforementioned electrical insulating portion has a width of 0.01 mm to 1.5 mm. The irradiation time of the electron beam is in the range of 0.01 seconds to 0.6 seconds. The rotational speed of the aforementioned rotating drum is 10 m / min to 150 m / min. Manufacturing method for multilayer capacitors. [Claim 2] The acceleration voltage of the electron beam per 1 μm of thickness of the resin thin film layer is 3 kV / μm to 20 kV / μm, The distance between the electron beam source and the monomer layer is 50 mm to 200 mm. The current value of the electron beam is 20 to 180 mA. The average thickness of the aforementioned resin thin film layer is 0.1 to 1.2 μm. The average thickness of the metal thin film layer is 1 nm to 20 nm, and / or the metal thin film layer has a deposition resistance of 10 to 45 Ω / □. The aforementioned electrical insulating portion has a width of 0.05 mm to 0.6 mm. The irradiation time of the electron beam is in the range of 0.06 seconds to 0.24 seconds. The rotational speed of the aforementioned rotating drum is 30 m / min to 100 m / min. The manufacturing method according to claim 1. [Claim 3] At least a portion of the matrix element laminate constitutes an active portion, and in this active portion, with respect to two adjacent metal thin film layers separated by one resin thin film layer, the positions of the electrical insulating portions of each do not overlap with each other in the stacking direction. The manufacturing method according to claim 1 or 2. [Claim 4] With respect to a group of metal thin film layers stacked alternately among the aforementioned metal thin film layers, the positions of the electrical insulating portions of each layer overlap in the stacking direction, forming a margin, and the average displacement of the positions of the electrical insulating portions in this margin is less than 5% of the average width of these electrical insulating portions. The manufacturing method according to claim 1 or 2. [Claim 5] When the monomer is irradiated with an electron beam of 100 μA at 4.5 kV for 5 seconds, the degree of curing of the monomer is denoted as x. The control value S is, 24.85e －０．０４１ｘ ≦S≦85.018e －０．０２６ｘ Satisfying the conditions, The control value S is given by the following equation 1: S=(A / C) / D×T (Formula 1) (In the formula, A is the electron beam current value (in mA), C is the drum rotation speed (in m / min), D is the thickness of each layer of the resin thin film (in μm), and T is the time from electron beam irradiation to oil application (in seconds)) Calculated according to, The manufacturing method according to claim 1 or 2. [Claim 6] The manufacturing method according to claim 1 or 2, wherein the degree of curing of the resin thin film layer is 85% or less at the time when the formation of the matrix element laminate is completed. [Claim 7] A manufacturing method according to claim 1 or 2, The aforementioned multilayer capacitor has a structure in which at least 100 layers of resin thin film layers and metal thin film layers are alternately stacked. Each of the aforementioned metal thin film layers has an electrical insulating portion. With respect to two metal thin film layers adjacent to each other via one resin thin film layer, the positions of the electrical insulating portions of each layer do not overlap with each other in the stacking direction. With respect to a group of metal thin film layers stacked alternately among the aforementioned metal thin film layers, the positions of the electrical insulating portions of each overlap with each other in the stacking direction, forming a margin, and the average displacement of the positions of the electrical insulating portions in this margin is less than 5% of the average width of these electrical insulating portions, and On the surface of the multilayer capacitor, no recess is formed in the portion corresponding to the margin in the stacking direction, or a recess of a certain size or less is formed. method. [Claim 8] The method according to claim 7, wherein the height of the recess of a certain size or less is less than 1 / 25 of the thickness of the multilayer capacitor. [Claim 9] With respect to the recess of a certain size or less, and the protrusion formed adjacent to this recess, The sum of the height of the recess and the height of the protrusion is less than 1 / 20 of the thickness of the multilayer capacitor, and / or The height of the protrusion is less than 1 / 75 of the thickness of the multilayer capacitor. The method according to claim 7. [Claim 10] The method according to claim 7, wherein the average thickness of the metal thin film layer is 1 nm to 20 nm and / or has a deposition resistance of 10 to 45 Ω / □. [Claim 11] The method according to claim 7, wherein the average width of the electrical insulating portion is 600 μm or less. [Claim 12] The method according to claim 7, wherein the thickness of the multilayer capacitor is 3 mm or less. [Claim 13] The method according to claim 7, wherein the resin thin film layer comprises a thermosetting resin and / or a radiation-curable resin. [Claim 14] The method according to claim 7, wherein the average thickness of the resin thin film layer is 1.5 μm or less.

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