JP2014096498A - Method for manufacturing multilayer capacitor, multilayer capacitor, circuit board, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a multilayer capacitor, high in productivity and capable of suppressing a resin used for sealing treatment of a metallikon layer from attaching and remaining to the surface of a multilayer capacitor without using masking treatment, even when a multilayer capacitor having a structure, where a metallikon layer containing a cured resin is provided on an end face of a laminate, is manufactured.SOLUTION: A metallikon layer 100L having voids P is formed on an end face 12L of a laminate, then an uncured resin composition 110UC is impregnated in the voids P in the metallikon layer 100L to prepare an object 120 to be washed, and thereafter the object 120 to be washed is washed with a cleaning liquid. Thus, an object 122 to be subjected to curing treatment, from which the uncured resin composition 110UC present in the vicinity of the metallikon layer 100L is removed, is obtained. Then, a multilayer capacitor is obtained at least through a step where the uncured resin composition 110UC remaining in the metallikon layer 100L of the object 122 to be subjected to curing treatment is cured.

Description

  The present invention relates to a method for manufacturing a multilayer capacitor, a multilayer capacitor, a circuit board, and an electronic device.

  As one type of capacitor, a multilayer capacitor including a multilayer body in which metal layers and resin layers are alternately stacked and a pair of external electrodes provided on an end surface of the multilayer body is known. The multilayer body constituting this multilayer capacitor is a resin film in which a metal thin film is formed in advance by vapor phase film formation methods such as alternately forming metal layers and resin layers using vapor deposition methods, or by vapor deposition. It is produced by a method of superposing films such as superposing etc. In addition, the external electrode electrically connected to the metal layer constituting the laminate is generally formed through at least a step of directly forming a metallicon layer on the end face of the laminate (see Patent Documents 1 to 4). ).

Here, regarding the formation of the external electrode, there are various methods for forming the external electrode after the metallicon layer is formed. For example, the following methods (1) to (4) are exemplified.
(1) After impregnating a metallicon layer with a low-viscosity liquid thermosetting resin, a step of curing the resin, a step of polishing and exposing the surface of the metallicon layer, and a step of plating treatment are sequentially performed in this order. Method to perform (patent document 1).
(2) The step of impregnating the metallicon layer with an epoxy resin under vacuum and pressure, the step of polishing the surface of the metallicon layer, removing the excess epoxy resin and then heat-curing the epoxy resin, and the surface of the metallicon layer being conductive A method in which a step of applying a paste to form a conductive paste layer and a step of forming a plating layer on the surface of the conductive paste layer by dipping are sequentially performed in this order (Patent Document 2).

(3) A step of impregnating a two-layered metallicon layer with an epoxy resin having a viscosity of 250 cps or less and a surface tension of 30 dyne / cm ² or less, and after removing the excess epoxy resin, the epoxy resin is heat-cured. A method in which a step, a step of cutting and polishing the surface of the metallicon layer, and a step of bonding a plate-like terminal to the surface of the first external electrode are sequentially performed in this order (Patent Document 3).
(4) A method of forming a conductive paste layer and a plating layer in this order on the metallicon layer after forming the metallicon layer (Patent Document 4).

Regarding the polishing process of the metallicon layer, Patent Document 1 discloses that it is carried out to smooth the surface of the metallicon layer and remove the resin adhering to the surface. Further, it is disclosed that the surface of the metallicon layer is smoothed by the polishing treatment. In addition, regarding the impregnation treatment of the resin into the metallicon layer, in Patent Document 3, in addition to preventing moisture absorption for improving the corrosion resistance of the metallicon material, in order to ensure impregnation and suppress moisture absorption, It is disclosed that when a resin having a high viscosity or a higher surface tension (a resin having a viscosity exceeding 250 cps or a surface tension exceeding 30 dyne / cm ² ) is used, the impregnation property is lowered and moisture absorption cannot be suppressed.

  As explained above, the polishing treatment of the surface of the metallicon layer after impregnating and curing the resin is performed for the purpose of smoothing the surface, etc. There are effects such as preventing.

JP-A-6-151240 (Claim 1, paragraph number 0023, etc.) JP 11-150038 A (Claim 1, paragraph numbers 0032, 0033, etc.) JP 2004-260029 A (Claims 1, 3, paragraph numbers 0005, 0018, etc.) JP 2011-86802 A (paragraph number 0066)

  The metallicon layer is formed by spraying metal particles in a molten state or a state close thereto on the end face of the laminate. For this reason, the metallicon layer has a porous structure having many voids, and the surface thereof has irregularities caused by metal particles sprayed during thermal spraying. Therefore, as in the techniques described in Patent Documents 1 to 3, when the external electrode is formed, if the resin is impregnated / cured into the metallicon layer, the voids are filled with the resin (sealed). And the surface which has an unevenness | corrugation is smoothed by grind | polishing the surface of the metallicon layer filled with resin with which the space | gap hardened | cured.

  On the other hand, the surface of the metallicon layer after the resin impregnation / curing treatment is covered with an insulating resin. Therefore, in order for the metallicon layer to function as an external electrode, it is necessary to remove the resin covering the surface. In Patent Documents 1 to 3, a polishing process is adopted as the means. Therefore, the metal material constituting the metallicon layer can be reliably exposed by smoothly polishing the surface of the metallicon layer having irregularities and removing the resin. For this reason, the metallicon layer and other conductive members provided on the metallicon layer (for example, other conductive electrodes such as conductive paste layers, plating layers, and plate-like terminals exemplified in Patent Documents 1 to 3) In addition, it is possible to reliably ensure electrical connection to the layers and members of the layer and the connection terminals for connecting the multilayer capacitor to an external circuit, power source, or the like.

  However, the polishing treatment is generally performed in the state of a chip obtained by cutting a laminated body in which a metallicon layer containing a cured resin is formed into the size of the final product, or an intermediate product (a mother product before cutting into the size of the final product). It is necessary to carry out in the state of the element. That is, it is necessary to perform the polishing process for each individual chip or for each individual mother element. In addition to this, the polishing dust generated during polishing may cause a defective insulation of the multilayer capacitor, so that it is necessary to further clean the chip or the mother element after the polishing process. Therefore, the polishing treatment of the surface of the metallicon layer containing the cured resin reduces the productivity of the multilayer capacitor.

  Further, even if an attempt is made to directly form a plating film on the surface of the metallicon layer exposed by the polishing treatment, the exposed surface is in a state where the impregnating resin which is an insulator is scattered on the metal material constituting the metallicon layer. For this reason, the formation of the plating film becomes non-uniform, and a problem that a plating film is not formed tends to occur.

  Further, when the metallicon layer is impregnated with a resin for sealing treatment, the resin also adheres to the upper and lower surfaces of the laminate and the upper and lower surfaces of the metallicon layer. For this reason, the resin adhered and hardened on the lower surface of the laminate and the lower end surface of the external terminal forms a concavo-convex portion or hinders electrical connection on the lower end surface side of the external terminal. Therefore, when the multilayer capacitor is surface-mounted on the printed board with the lower surface side of the multilayer body as the mounting surface, mounting defects are likely to occur.

  On the other hand, as a method for avoiding such a problem, it is effective to perform a masking process before impregnating the metallicon layer with the resin, or to perform an impregnation process using a low-viscosity resin. . However, when the masking process is employed, the number of manufacturing steps is further increased, and the masking process needs to be performed for each individual chip or each individual mother element, so that the productivity of the multilayer capacitor is reduced. In addition, when an impregnation treatment using a low-viscosity resin is employed, it is possible to suppress the occurrence of uneven portions due to the resin adhered and cured on the lower surface of the laminate used as the mounting surface and the lower end surface of the external terminal to some extent. It becomes possible. However, since the adhered resin remains thin on the surface, connection between the lower end surface side of the external terminal and the mounting substrate is hindered, and mounting defects are likely to occur. In addition, since the resin that can be used for the impregnation treatment is limited to the low-viscosity resin, there is less room for material selection. That is, the degree of freedom in product design is reduced in order to improve various characteristics and quality of the multilayer capacitor. In addition to this, it is unavoidable that electrical connection on the lower end surface side of the external terminal is obstructed.

  On the other hand, the technique described in Patent Document 4 does not impregnate the metallicon layer with resin. For this reason, generation | occurrence | production of the various problems accompanying the resin impregnation process as mentioned above can be avoided. However, moisture in the atmosphere tends to enter the voids of the metallicon layer. Therefore, the moisture resistance of the multilayer capacitor may be easily deteriorated. Also, when manufacturing a multilayer capacitor, when washing with an alkaline cleaning liquid in the post-process after the formation of the metallicon layer, the connection between the metallicon layer and the metal layer is corroded by the cleaning liquid through the gap of the metallicon layer, resulting in poor connection. There is also a risk of incurring. Therefore, in order to prevent such a problem more reliably, after all, it is preferable to impregnate the metallicon layer with a resin as in the techniques described in Patent Documents 1 to 3.

  The present invention has been made in view of the above circumstances, and even when producing a multilayer capacitor having a structure in which a metallicon layer containing a cured resin is provided on an end face of the laminate, the productivity is high, and A method of manufacturing a multilayer capacitor that can prevent the resin used for sealing the metallicon layer from adhering to or remaining on the surface of the multilayer capacitor without using a masking process, and a multilayer capacitor and a circuit manufactured using the same It is an object to provide a substrate and an electronic device.

The above-mentioned subject is achieved by the following present invention. That is,
The method for manufacturing a multilayer capacitor according to the present invention includes the step of spraying metal on a region of an end face that is substantially parallel to the thickness direction of the metal layer in the surface of the multilayer body in which metal layers and resin layers are alternately laminated. And forming a second metallicon layer having voids by spraying metal on the other region of the end face, and a resin component in an uncured state. A permeation step for infiltrating the voids of one metallicon layer and the second metallicon layer, and a laminate having a first metallicon layer containing an uncured resin component and a second metallicon layer containing an uncured resin component, By contacting with the cleaning liquid, the uncured resin component present near the surface of the first metallicon layer and the uncured resin component present near the surface of the second metallicon layer are removed. Resin component cured through at least a resin component removing step and a curing step of curing the uncured resin component remaining in the first metallicon layer and the uncured resin component remaining in the second metallicon layer A multilayer capacitor comprising at least a first metallicon layer containing, a second metallicon layer containing a cured resin component, and a laminate is manufactured.

  One embodiment of the method for producing a multilayer capacitor of the present invention is conductive so as to cover at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. It is preferable to further include a conductive paste layer forming step of forming a conductive paste layer.

  Another embodiment of the method for producing a multilayer capacitor of the present invention covers at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. It is preferable to further include a plating layer forming step for forming a plating layer.

  In another embodiment of the method for producing a multilayer capacitor of the present invention, a first metallicon layer containing a cured resin component and a second metallicon layer containing a cured resin component and a laminate produced by undergoing a curing step It is preferable to further include an alkali cleaning step of cleaning at least one member selected from a core member including the above and an intermediate product obtained by post-processing the core member by contacting with an alkaline aqueous solution.

  In another embodiment of the method for manufacturing a multilayer capacitor of the present invention, a multilayer body is a resin layer forming step in which a resin layer is formed by a vapor deposition method, and a metal layer formation in which a metal layer is formed by a vapor deposition method. It is preferable to be manufactured through at least a process of alternately repeating the steps.

  The multilayer capacitor of the present invention is provided in a region of an end surface that is formed by alternately laminating metal layers and resin layers, and on an end surface of the surface of the laminate that is substantially parallel to the thickness direction of the metal layer. The first metallicon layer and the second metallicon layer provided in the other region of the end face and having voids, and the first metallicon layer and the second metallicon layer among the voids of the first and second metallicon layers And a cured resin filled so as to seal voids other than the voids existing in the vicinity of the surface.

  In one embodiment of the multilayer capacitor of the present invention, it is preferable that the surfaces of the first metallicon layer and the second metallicon layer have irregularities resulting from the metal spraying process.

  In another embodiment of the multilayer capacitor of the present invention, the multilayer body includes a resin layer forming step in which a resin layer is formed by a vapor deposition method and a metal layer forming step in which a metal layer is formed by a vapor deposition method. It is preferable to be produced through at least an alternately repeating process.

  Another embodiment of the multilayer capacitor of the present invention is a conductive paste so as to cover at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. It is preferred that a layer is provided.

  Another embodiment of the multilayer capacitor of the present invention is in direct contact with the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. A plating layer is provided so as to cover at least.

  The circuit board of the present invention includes at least a multilayer capacitor, and the multilayer capacitor has a laminate in which metal layers and resin layers are alternately laminated, and an end face that is substantially parallel to the thickness direction of the metal layer of the surface of the laminate. Of the first metallicon layer provided in one region and having voids, the second metallicon layer provided in the other region of the end surface and having voids, and the voids of the first metallicon layer and the second metallicon layer And a cured resin filled so as to seal voids other than the voids present in the vicinity of the surfaces of the first metallicon layer and the second metallicon layer.

  An electronic device according to the present invention includes at least a multilayer capacitor, and the multilayer capacitor includes a laminate in which metal layers and resin layers are alternately laminated, and an end face that is substantially parallel to the thickness direction of the metal layer of the surface of the laminate. Of the first metallicon layer provided in one region and having voids, the second metallicon layer provided in the other region of the end surface and having voids, and the voids of the first metallicon layer and the second metallicon layer And a cured resin filled so as to seal voids other than the voids present in the vicinity of the surfaces of the first metallicon layer and the second metallicon layer.

  As described above, according to the present invention, even when manufacturing a multilayer capacitor having a structure in which a metallicon layer containing a cured resin is provided on the end face of the multilayer body, the productivity is high and the masking is performed. A method of manufacturing a multilayer capacitor capable of suppressing the resin used for sealing the metallicon layer from adhering to or remaining on the surface of the multilayer capacitor without using a treatment, and a multilayer capacitor and a circuit board manufactured using the same And an electronic device can be provided.

It is a schematic cross section which shows an example of the laminated body used for the manufacturing method of the multilayer capacitor of this embodiment. It is a schematic cross section which shows an example of the laminated body in which the metallicon layer was formed in both end surfaces. It is a schematic cross section which shows an example of an osmosis | permeation process and a resin component removal process. Here, FIG. 3A is an enlarged cross-sectional view showing a state immediately after the completion of the permeation process, and FIG. 3B is an enlarged view showing a state immediately after the resin component removal process is finished. It is sectional drawing. It is a schematic cross section which shows an example of the state immediately after finishing implementing a hardening process, ie, an example of a core member. It is a schematic cross section showing an example of the multilayer capacitor produced by the multilayer capacitor manufacturing method of the present embodiment. It is a schematic cross section which shows the other example of the multilayer capacitor produced by the manufacturing method of the multilayer capacitor of this embodiment. It is a schematic cross section which shows the other example of the multilayer capacitor produced by the manufacturing method of the multilayer capacitor of this embodiment. It is a schematic cross section which shows the other example of the multilayer capacitor produced by the manufacturing method of the multilayer capacitor of this embodiment. It is a schematic cross section which shows an example of the principle manufacturing method of a laminated body of a film lamination type. It is a schematic cross section which shows the other example of the laminated body used for the manufacturing method of the multilayer capacitor of this embodiment.

  In the multilayer capacitor manufacturing method of this embodiment, the multilayer capacitor is manufactured through at least a metallicon layer forming step, an infiltration step, a resin component removal step, and a curing step. Details of each process and the multilayer capacitor to be manufactured will be described below.

  First, in the metallicon layer forming step, metal is sprayed on one region of the end face (all end faces) that is substantially parallel to the thickness direction of the metal layer in the surface of the laminate in which the metal layers and the resin layers are alternately laminated. By doing so, a first metallicon layer having voids is formed, and a second metallicon layer having voids is formed by spraying metal on other regions of the end face (all end faces).

  FIG. 1 is a schematic cross-sectional view showing an example of a laminate used in the metallicon layer forming step. A laminated body 10A (10) shown in FIG. 1 has a horizontally long cross section, and has a layer structure in which metal layers 20 and resin layers 30 are alternately laminated. In the drawing, for convenience of explanation, a layer structure in which several metal layers 20 and resin layers 30 are alternately laminated is shown. However, the number of stacked layers of the stacked body 10 is generally about several to several thousand layers.

  Here, the metal layer 20 has a metal layer 20L substantially functioning as an internal electrode having either positive or negative polarity, and a metal layer 20R substantially functioning as an internal electrode having a polarity opposite to that of the metal layer 20L. Including at least two types. The two kinds of metal layers 20L and 20R are provided on both sides of the resin layer 30 so as to sandwich the single resin layer 30, thereby exhibiting a function as a capacitor. As long as the metal layers 20L and 20R have these functions, the arrangement mode in the stacked body 10 is not particularly limited. Note that the metal layer 20L (or the metal layer 20R) substantially functions as one (or the other) polar internal electrode. (1) The entire metal layer 20L (or the metal layer 20R) is one (or the other). And (2) most of the metal layer 20L (or metal layer 20R) functions as one (or the other) polar internal electrode, and the metal layer 20L (or metal When a part of the layer 20R) functions as an internal electrode of the other (or one) polarity, it means either one.

  In the laminated body 10A illustrated in FIG. 1, the metal layer 20 has one end portion (left end portion in the figure) on one end face (left end face in the figure, one region of all end faces) 12L side of the laminated body 10A. Only the exposed metal layer 20L, and the other end portion (the right end portion in the figure) are exposed only on the other end face (the other end region in the figure, the right end face, other region of the end face) 12R side of the laminate 10A. Includes two types of 20R. And the metal layer 20L and the metal layer 20R are alternately arrange | positioned with respect to the thickness direction of 10 A of laminated bodies. Therefore, when external electrodes are provided on the end faces 12L and 12R, the metal layer 20L functions as an electrode of one electrode, and the metal layer 20R functions as an electrode of the other electrode. For this reason, the laminated body 10A functions as a capacitor. The laminated body 10 is not limited to the example shown in FIG. 1 as long as it has a layered structure in which the metal layers 20 and the resin layers 30 are alternately laminated and can function as a capacitor. . The multilayer body 10 can be broadly classified into two types: a thin film lamination type formed by a vapor deposition method and a film lamination type formed by a method of superposing films. Any type of manufacturing method may be used.

  Other embodiments and other details of the laminate 10 will be described later. Further, the laminate 10A used in the metallicon layer forming step, the permeation step, the resin component removal step, and the curing step is usually used as a rod-shaped member that extends from the front side of the paper in FIG. It may be a chip-like member cut to substantially the same size as the multilayer capacitor. However, normally, from the viewpoint of ensuring productivity, it is preferable to use the rod-shaped laminate 10A until at least the above four steps are completed. Therefore, in the following description, it demonstrates on the assumption that the shape of 10 A of laminated bodies is rod shape in all the said 4 processes.

  In the metallicon layer forming step, as shown in FIG. 2, a pair of end faces (that is, end face 12 </ b> L and end face 12 </ b> R in FIG. 1) that are substantially parallel to the thickness direction of the metal layer 20 in the surface of the stacked body 10 </ b> A, First metallized layer 100L (100) having voids and second metallized layer 100R (100) having voids are formed by spraying metal. In FIG. 2, the details of the layer structure of the stacked body 10 </ b> A and the voids in the metallicon layer 100 are omitted.

  In addition, as a material which comprises the metallicon layer 100, if it is a metal material which can function as an electrode, it will not specifically limit, For example, metal materials, such as aluminum, copper, nickel, zinc, alloy materials, such as brass, etc. Can be used as appropriate. The metallicon layer 100 has a structure having a porous void. And the porosity of the metallicon layer 100 is not specifically limited. The porosity can be controlled to an arbitrary value by appropriately selecting the metal spraying conditions. Further, the thickness of the metallicon layer 100 is not particularly limited, but it is generally preferable that the thickness is in the range of about 50 μm to 1000 μm.

  After the metallicon layer forming step, the infiltration step is performed. In the infiltration step, an uncured resin component (uncured resin component) is infiltrated into the voids of the first metallicon layer 100L and the voids of the second metallicon layer 100R. The method for allowing the uncured resin component to penetrate into the gap of the metallicon layer 100 is not particularly limited, and a known method can be used. As such a method, for example, a method of immersing the laminate 10 provided with the metallicon layer 100 in an uncured resin component, or a method of performing such an immersion treatment in a reduced pressure environment (so-called vacuum impregnation treatment). ) And the like. Further, in order to more efficiently infiltrate the uncured resin component into the voids of the metallicon layer 100, pressure treatment is performed, the uncured resin component is heated to reduce the viscosity, or the low viscosity type It is also preferable to use an uncured resin component. Then, after completing the infiltration process, the uncured resin component is substantially infiltrated and filled into the entire gap of the metallicon layer 100. In the multilayer capacitor manufacturing method of the present embodiment, since the resin component removal step is performed after the infiltration step, the top surface 102S of the metallicon layer 100 (the end surfaces 12R and 12L of the metallicon layer 100 and the A masking process for covering a portion other than the surface on the side opposite to the contact surface) with a mask material is unnecessary.

  The uncured resin component is not particularly limited, and for example, a resin component containing a reactive group such as an epoxy group or a reactive double bond as exemplified by an epoxy resin, an acrylic resin, and / or the like, and / or A polymerizable monomer can be used. The uncured resin component may be substantially the same as the resin constituting the resin layer 30 in terms of composition. The curing mechanism of the uncured resin component is not particularly limited. For example, it is cured by applying a physical stimulus such as heat, light, or electron beam, or cured by a chemical action such as a polymerization initiator or a polymerization accelerator. Any curing mechanism such as type may be used. However, from the viewpoint of handleability and convenience in the curing step, which is a subsequent step, it is preferable to use a thermosetting resin component as the uncured resin component. Further, the viscosity of the uncured resin component is not particularly limited as long as the uncured resin component can penetrate into the voids of the metallicon layer 100. The viscosity may be, for example, a low viscosity region of 250 cps or less as disclosed in Patent Document 3 or a high viscosity region significantly exceeding 250 cps. It is preferable that it is in the range of about 10 cps to 1000 cps under the temperature environment. Further, the resin obtained by curing the uncured resin component is usually an insulating resin.

  After completing the infiltration step, the resin component removal step is performed. In the resin component removal step, the laminate 10 having the first metallicon layer 100L containing an uncured resin component and the second metallicon layer 100R containing an uncured resin component is brought into contact with the cleaning liquid. As a result, the uncured resin component present in the vicinity of the surface (top surface 102S, upper end surface 102T, lower end surface 102B) of the first metallicon layer 100L and the surface (top surface 102S, upper end surface 102T, The uncured resin component existing in the vicinity of the lower end surface 102B) is removed. Of course, in the resin component removal step, the uncured resin component covering the surface of the metallicon layer 100 and the upper surface 12T and the lower surface 12B of the laminate 10A is naturally removed.

  FIG. 3 is a schematic cross-sectional view showing an example of the permeation process and the resin component removal process. Specifically, FIG. 3 is an enlarged cross-sectional view in which a portion near the first metallicon layer 100L in FIG. 2 is enlarged. Here, FIG. 3A is an enlarged cross-sectional view showing a state immediately after the completion of the permeation process, and FIG. 3B is an enlarged view showing a state immediately after the resin component removal process is finished. It is sectional drawing. In FIG. 3, the details of the layer structure of the laminated body 10A are omitted.

Moreover, although description was abbreviate | omitted in FIG. 2 (and FIGS. 5-8 mentioned later), as shown in FIG. 3 (and FIG. 4 mentioned later), the top surface 102S of the metallicon layer 100 originates in a metal spraying process. It has irregularities. On the other hand, when forming the metallicon layer 100 by the metal spraying process, a masking tape or a spacer is usually disposed on the upper end surface 102T and the lower end surface 102B side. For this reason, the upper end surface 102T and the lower end surface 102 are normally smooth surfaces. However, when metal spraying is performed without using masking tape or spacers, the upper end surface 102T and the lower end surface 102 also have irregularities resulting from the metal spraying process. That is, in the multilayer capacitor manufacturing method of the present embodiment, the surface (a part or the entire surface) of the metallicon layer 100 has irregularities resulting from the metal spraying process after the metallicon layer forming step is completed. Here, the unevenness resulting from the above-described metal spraying treatment is usually in the range of about 5 μm to 70 μm in terms of arithmetic average roughness Ra. In addition, arithmetic average roughness Ra is measured on condition of the following using a contact-type surface shape measuring apparatus (DEKTAK 6M, ULVAC, Inc. make).
Scanning distance: 3000 μm
Scanning time: 30 seconds (9000 points)
Resolution: 0.333 μm / sample
Needle pressure: 15mg

  Immediately after completing the infiltration step as shown in FIG. 3 (A), the uncured resin component 110UC is substantially infiltrated and filled in all the voids P of the first metallicon layer 100L. In addition, the uncured resin component 110UC also covers the upper surface 12T and the lower surface 12B (not shown in FIG. 3) of the laminate 10A. Furthermore, the uncured resin component 110UC also covers the surface of the first metallicon layer 100L.

  Here, the entire body 10A (cleaning object 120) having the metallicon layer 100 including the uncured resin component is brought into contact with the cleaning liquid while being entirely covered with the uncured resin component 110UC. Thereby, as illustrated in FIG. 3B, the uncured resin component 110UC present in the vicinity of the surface (the upper end surface 102T, the lower end surface 102B, and the top surface 102S) of the metallicon layer 100 is removed. 3B, the uncured resin component 110UC remains only in the gap P1 in the region surrounded by the alternate long and short dash line B and the end face 12L in the first metallicon layer 100L. The uncured resin component 110UC present in the void P2 outside the region is washed away from the first metallicon layer 100L by the cleaning liquid. Further, the uncured resin component 110UC does not exist on the upper surface 12T and the lower surface 12B of the laminated body 10A, and the upper end surface 102T, the lower end surface 102B, and the top surface 102S of the metallicon layer 100. As described above, by bringing the cleaning object 120 into contact with the cleaning liquid, the curing object 122 illustrated in FIG. 3B can be obtained.

  The method for bringing the cleaning object 120 into contact with the cleaning liquid is not particularly limited, and a known method can be used as appropriate. As such a method, for example, a method of immersing and cleaning the cleaning object 120 in a cleaning tank filled with a cleaning liquid (immersion cleaning method), a method of shower cleaning the cleaning object 120, and a cleaning object The method of exposing 120 to the vapor | steam of a washing | cleaning liquid, the method of wiping or rubbing the surface of the washing | cleaning process target object 120 with the cloth or sponge which soaked the washing | cleaning liquid, etc. are mentioned, Two or more types may be combined suitably. Moreover, about a washing | cleaning liquid, it can select suitably according to the uncured resin component 110UC to be used. Examples of the cleaning liquid include organic solvents such as acetone and toluene, chlorine-based cleaning agents, fluorine-based cleaning agents, bromine-based cleaning agents, and the like, and two or more types may be appropriately combined.

  After completing the resin component removal step, the curing step is performed. In the curing step, the uncured resin component 110UC remaining in the first metallicon layer 100L and the uncured resin component 110UC remaining in the second metallicon layer 100R are cured. The method of the curing process can be appropriately selected according to the uncured resin component 110UC to be used. For example, if the uncured resin component 110UC is a thermosetting resin component, the curing object 122 may be heat-treated. By passing through the curing step, a core member including the first metallicon layer 100L including the cured resin component, the second metallicon layer 100R including the cured resin component, and the laminate 10 can be obtained.

  FIG. 4 is a schematic cross-sectional view showing an example of a state immediately after the completion of the curing process, that is, an example of a core member. Specifically, the curing process object 122 shown in FIG. It is the expanded sectional view shown about the core member obtained by implementing a hardening process. 4 has substantially the same structure as the object to be cured 122 shown in FIG. 3B, but is a resin component (cured resin 110C) obtained by curing the uncured resin component 110UC present in the gap P1. ) Is different only in that it has changed.

  Various post-processes can be performed on the core member 124. As such a post process, for example, a cleaning process for cleaning the core member 124 or the intermediate product after the core member 124 is processed, and the intermediate product after the core member 124 or the core member 124 is processed into a predetermined size such as a final product. A cutting step of cutting the metallicon layer 100, a connecting terminal mounting step of attaching a connecting terminal to the external electrode having at least the metallicon layer 100, and a case where the external electrode is composed of two or more layers. The process etc. which further form the layer which consists of an electroconductive member so that it may cover can be implemented suitably. A multilayer capacitor including at least the first metallicon layer 100L including the cured resin component, the second metallicon layer 100R including the cured resin component, and the multilayer body 10 is appropriately performed as necessary. Can be obtained. In addition, the post process excluding the cutting process may be performed in a state where the core member 124 or an intermediate product obtained by post-processing the core member 124 is separated into a predetermined size such as a final product, and the curing process is finished. You may implement in the state of the size immediately after.

  Here, in the present specification, the “intermediate product obtained by post-processing the core member 124” means a member obtained by performing some post-processing on the core member 124, for example, the surface of the metallicon layer 100 of the core member 124. Examples thereof include a member further provided with a conductive paste layer and / or a plating layer. However, the “post-processing” does not include a process (for example, a cutting process and a cleaning process) in which the cross-sectional structure of the core member 124 illustrated in FIG. 4 is substantially maintained as it is.

  Further, when the multilayer capacitor is manufactured, if the metallicon layer forming step, the infiltration step, the resin component removing step, and the curing step are performed in this order, the metallicon layer forming step and the infiltration step are performed immediately before the metallicon layer forming step. Between the permeation process and the resin component removal process, between the resin component removal process and the curing process, or between the curing process and the various post-processes described above, other processes are performed as necessary. Also good.

  In the multilayer capacitor manufacturing method of this embodiment, the metallicon layer forming step, the permeation step, the resin component removal step, and the curing step are performed in this order. Therefore, it is not necessary to perform a polishing process for polishing the top surface 102S of the metallicon layer 100 or a masking process for covering the upper surface 12T and the lower surface 12B of the laminate 10 with a mask material during or before and after these processes. A state in which the surface of the metallicon layer 100 is exposed can be obtained. For this reason, even if a polishing process is not performed on the metallicon layer 100, a conductive member (conductive paste layer, plated layer, plate-like terminal, etc.) is provided on the metallicon layer 100 as necessary, or external electrodes Even when the connection line and the connection line are connected, the electrical connection between the metal layer 20 and the circuit / power supply outside the multilayer capacitor can be ensured reliably and easily. That is, in the multilayer capacitor manufacturing method of the present embodiment, processing for each chip or each mother element is necessary, and therefore polishing processing and masking processing that greatly reduce productivity can be omitted.

  Further, the polishing step and the resin component removal step are common in that both are steps that are performed to exclude unnecessary resins, and the masking step needs to be performed in combination with the polishing step. It is a process. However, in the polishing process and the masking process, processing for each chip or each mother element is required, whereas in the resin component removal process, batch processing for collectively processing a plurality of chips or a plurality of mother elements is performed. Very easy. Therefore, the manufacturing method of the multilayer capacitor of this embodiment has high productivity.

  Furthermore, since the uncured resin component 110UC exists only in the gap P2 of the metallicon layer 100 at the time of performing the curing step, it is possible to suppress the cured resin 110C from adhering to and remaining on the surface of the multilayer capacitor. For this reason, it is possible to prevent various problems caused by the cured resin 110C adhering to and remaining on the surface of the multilayer capacitor, for example, mounting defects when the multilayer capacitor is surface-mounted on a printed board.

  Next, a specific example of the multilayer capacitor produced by the multilayer capacitor manufacturing method of the present embodiment will be described with reference to the drawings. 5 to 8 are schematic cross-sectional views showing an example of the multilayer capacitor produced by the multilayer capacitor manufacturing method of the present embodiment. 5-8, description is abbreviate | omitted about the metal layer 20 and the resin layer 30 which comprise the laminated body 10A, and the structure (void | gaps P and cured resin 110C) in the metallicon layer 100. FIG.

  Here, the multilayer capacitor 200A (200) shown in FIG. 5 has substantially the same cross-sectional structure as the core member 124 shown in FIG. That is, the multilayer capacitor 200A is provided in a region (end surface 12L) of the multilayer body 10A and an end surface (all end surfaces) that is substantially parallel to the thickness direction of the metal layer 20 on the surface of the multilayer body 10A, and the gap The first metallicon layer 100L having P and the second metallicon layer 100R provided in the other region (end surface 12R) of the end surface (all end surfaces) and having the void P are included. And among the space | gap P of 100 L of 1st metallicon layers and 100R of 2nd metallicon layers, it exists in the vicinity of the surface (the top surface 102S, the upper end surface 102T, and the lower end surface 102B) of the 1st metallicon layer 100L and the 2nd metallicon layer 100R. And a cured resin filled so as to seal a void other than the void P2 (that is, the void P1).

  Here, in the multilayer capacitor 200A shown in FIG. 5, the pair of external electrodes 210A (210) provided on both sides in the width direction of the multilayer body 10A is configured only from the metallicon layer 100 including the cured resin 110C. One of the pair of external electrodes 210 functions as a positive electrode side and the other functions as a negative electrode side.

  The external electrode 210 may be composed of only the metallicon layer 100 containing the cured resin 110C as illustrated in FIG. 5, but from a practical point of view, the external electrode 210 may be formed on the metallicon layer 100 containing the cured resin 110C. A layer or member made of a conductive member may be provided as necessary. In this case, it is preferable to provide a conductive paste layer and / or a plating layer so as to cover at least the surface of the metallicon layer 100 containing the cured resin 110C.

  In this case, (1) like the multilayer capacitor 200B (200) shown in FIG. 6, the conductive paste layer 130 is provided so as to cover the surface of the metallicon layer 100 containing the cured resin 110C and the surface of the laminated body 10A in the vicinity thereof. (2) The plating layer 140A (140) is formed so as to cover the surface of the metallicon layer 100 containing the cured resin 110C, as in the multilayer capacitor 200C (200) shown in FIG. The external electrode 210C (210) having the provided layer structure, or (3) the surface of the metallicon layer 100 containing the cured resin 110C and the laminated body 10A in the vicinity thereof, such as the multilayer capacitor 200D (200) shown in FIG. A conductive paste layer 130 is provided so as to cover the surface, and a method is further provided so as to cover the surface of the conductive paste layer 130. And external electrodes 210D (210) can be exemplified having a layer structure in which a key layer 140B (140). Moreover, when the number of layers of the external electrode 210 is two or more, layer configurations other than those illustrated in FIGS. 6 to 8 can be appropriately employed.

  In the conventional multilayer capacitor as exemplified in Patent Documents 1 and 2, the external electrode is provided in contact with the metallicon layer having a smooth surface by polishing the surface and the surface of the metallicon layer. And a plating layer or a conductive paste layer (hereinafter referred to as “second layer”). On the other hand, in the multilayer capacitors 200B, 200C, and 200D illustrated in FIGS. 6 to 8, the external electrodes 210B, 210C, and 210D are in contact with the metallicon layer 100 including the cured resin 110C and the surface of the metallicon layer 100. And at least a second layer to be provided. Then, as illustrated in FIG. 4, the surface of the metallicon layer 100 containing the cured resin 110 </ b> C is left with the irregularities formed during the thermal spraying process. In addition to this, the gap P2 near the surface is not filled with the cured resin 110C, and a recess due to the gap P2 is also formed on the surface of the metallicon layer 100 including the cured resin 110C. Accordingly, these irregularities and recesses exhibit an anchor effect when a second layer is further provided. Therefore, compared with the adhesion strength between the metallicon layer and the second layer in the external electrode as exemplified in Patent Documents 1 and 2 described above, the cured resin in the external electrodes 210B, 210C and 210D exemplified in FIGS. The adhesion strength between the metallicon layer 100 containing 110C and the second layer can be made higher. In particular, when the second layer is the conductive paste layer 130, the adhesion strength improvement by the anchor effect is very large.

  Moreover, in the conventional multilayer capacitors as exemplified in Patent Documents 1 and 2, the top surface of the metallicon layer is polished, but the upper end surface and the lower end surface are not polished. For this reason, it is inevitable that the cured resin adheres and remains on the upper end surface and the lower end surface of the metallicon layer. Therefore, it is difficult to form a plating layer directly on the upper end surface and the lower end surface of the metallicon layer, particularly by electrolytic plating or hot dipping. However, in the multilayer capacitor manufacturing method of the present embodiment, as illustrated in FIG. 4, substantially no resin component adheres or remains on the upper end surface 102 </ b> T and the lower end surface 102 </ b> B of the metallicon layer 100. Therefore, the plated layer 140 can be directly formed on these surfaces by electrolytic plating or hot dipping.

  On the other hand, a conductive paste layer that is usually used as a layer constituting an external electrode includes a large amount of resin and thus has flexibility. For this reason, the conductive paste layer has a function (thermal stress relaxation function) for relaxing thermal stress applied to the multilayer capacitor when heat is applied to the multilayer capacitor, such as during surface mounting. In addition, in the subsequent process after the formation of the conductive paste layer constituting the external electrode, when the plating layer is formed as the layer constituting the external electrode or when alkali cleaning is performed, the conductive paste layer is plated. This prevents the liquid or alkaline cleaning liquid from penetrating into the metallicon layer.

  However, in the multilayer capacitor 200 of the present embodiment, the cured resin 110C exists in the gap P1 of the metallicon layer 100. For this reason, the metallicon layer 100 containing the cured resin 110C can bear a part or all of the thermal stress relaxation function of the conductive paste layer. In addition, even if plating treatment or alkali cleaning is performed after the formation of the conductive paste layer 130, the plating solution or the alkali cleaning solution is applied to the connection portion between the metallicon layer 100 and the metal layer 20 through the gap P. Can be blocked from reaching. For this reason, it is possible to suppress the occurrence of connection failures such as disconnection and thinning of the connection portion.

  Therefore, in the multilayer capacitor 200 of the present embodiment, when it is assumed that heat is applied to the multilayer capacitor 200 and / or when the multilayer capacitor 200 is manufactured, the metal is eroded such as a plating solution or an alkaline cleaning solution. Even when a liquid that is likely to be used is used, the thickness of the conductive paste layer 130 constituting the external electrodes 210B and 210D is made thinner, or the conductive paste layer 130 is omitted from the external electrodes 210B and 210D. It is also easy to do. Therefore, in the multilayer capacitor manufacturing method of the present embodiment, it is easier to further improve the productivity from the viewpoint as described above.

  The conductive paste layer 130 is formed by a conductive paste layer forming step of forming a conductive paste layer so as to cover at least the surface of the metallicon layer 100 containing the cured resin 110C. Specifically, the conductive paste layer 130 can be formed by applying a conductive paste. Here, the conductive paste may be applied to the surface of the metallicon layer 100, or may be applied to the surface of the layer (upper layer) formed on the surface of the metallicon layer 100. In this case, as illustrated in FIGS. 6 and 8, the conductive paste may be applied so as to cover the surface of the stacked body 10 </ b> A in the vicinity of the metallicon layer 100. In this case, since the plating layer 140 having high wettability with solder can be formed corresponding to the surface of the conductive paste layer 130, the plating layer 140B is formed on the lower surface 12B side of the laminate 10A as illustrated in FIG. It can be formed so as to cover a part of. For this reason, when performing surface mounting in which soldering is performed by the reflow method using the multilayer capacitor 200D shown in FIG. 8, it is easy to make the electrical connection with the terminal on the printed circuit board more reliable. The conductive paste used for forming the conductive paste layer 130 can be used without particular limitation as long as it is a known conductive paste, but representative examples include those containing Ag or Cu as fillers. it can.

  When the plating layer 140 is provided as a layer constituting the external electrode 210, the plating layer 140 constitutes the outermost layer of the external electrode 210 like the external electrode 210C shown in FIG. 7 or the external electrode 210D shown in FIG. It is preferable to do. Since the plated layer 140 has high wettability with respect to solder, when it is necessary to solder the external electrodes 210C and 201D, the electrical connection between the multilayer capacitors 200C and 200D and an external circuit / power source is more reliable and It becomes easy.

  The plating layer 140 is formed by a plating layer forming step of forming a plating layer so as to cover at least the surface of the metallicon layer 100 containing the cured resin 110C. Specifically, the plating layer 140 is formed by immersing the core member 124 or an intermediate member obtained by post-processing the core member 124 in a plating solution and depositing a plating material. The metal material constituting the plating layer 140 is not particularly limited, and examples thereof include metals such as Sn, Cu, and Ni, alloys containing Sn, and alloys such as brass, but are alloys containing Sn or Sn. It is preferable. Further, as the plating method, either an electroless plating method or an electrolytic plating method may be used, but it is preferable to use an electrolytic plating method in which only a conductive portion is plated. Also, hot dipping may be used.

  Next, in the case of manufacturing the multilayer capacitor 200 illustrated in FIGS. 5 to 8, an example of main processes among various post-processes after the curing process will be described. First, when the multilayer capacitor 200A shown in FIG. 5 is manufactured, the rod-shaped core member 124 extending from the front side of the paper to the back side of the paper in FIG. 4 after the curing process is finished is formed in a chip shape corresponding to the size of the final product. A cutting step is performed to cut into pieces. Next, a cleaning process for cleaning the core member 124 cut into chips is performed. Thereby, the multilayer capacitor 200A is obtained.

  In the case of manufacturing the multilayer capacitor 200B shown in FIG. 6, the conductive paste layer forming process is performed on the rod-shaped core member 124 after the curing process is completed, and then the multilayer capacitor 200A is manufactured. The cutting process and the cleaning process are sequentially performed in the same manner as described above. Thereby, the multilayer capacitor 200B is obtained. In the case of manufacturing the multilayer capacitor 200C shown in FIG. 7, after finishing the curing process, the plating layer forming process is performed on the rod-shaped core member 124, and then the multilayer capacitor 200A is manufactured. Then, the cutting process and the cleaning process are sequentially performed. Thereby, the multilayer capacitor 200C is obtained. Further, when the multilayer capacitor 200D shown in FIG. 8 is manufactured, the conductive paste layer forming step and the plating layer forming step are sequentially performed on the rod-shaped core member 124 after the curing step is finished, and thereafter The cutting process and the cleaning process are sequentially performed in the same manner as in the case of manufacturing the capacitor 200A. Thereby, the multilayer capacitor 200D is obtained.

  In addition, although the washing | cleaning process is implemented after finishing a cutting process in the example mentioned above, it may be implemented at arbitrary timings after a hardening process (after obtaining the core member 124), and arbitrary before a hardening process. You may carry out at the timing of. Here, when the cleaning process is performed at an arbitrary timing after the curing process, that is, at least one selected from the core member 124 manufactured through the curing process and the intermediate product obtained by post-processing the core member 124. When performing the washing | cleaning process which wash | cleans a seed member, well-known washing | cleaning methods, such as immersion washing | cleaning, shower washing | cleaning, and steam washing | cleaning, can be employ | adopted and it can also implement in combination of 2 or more types. As for the cleaning liquid, various known cleaning liquids such as an alkaline aqueous solution, an acidic aqueous solution, a neutral aqueous solution, pure water, and an organic solvent can be used, and two or more types can be used in combination. These points are the same when the cleaning step is performed before the curing step.

  In the case of cleaning the core member 124 or the intermediate product after the core member 124 is cleaned, when high cleaning properties are required, the core member 124 or the intermediate product after the core member 124 is post-processed is brought into contact with an alkaline aqueous solution. It is preferable to perform an alkali cleaning step for cleaning, and it is more preferable to perform the alkali cleaning step after a cutting step for cutting into chips. Here, in order to obtain high detergency, it is preferable that the alkaline aqueous solution has a higher pH and / or liquid temperature. However, the higher the pH and / or the liquid temperature, the more the alkaline aqueous solution penetrates to the vicinity of the connection portion between the metallicon layer 100 and the metal layer 20 at the time of cleaning, and the connection portion is eroded, resulting in poor connection. However, in the multilayer capacitor 200 of the present embodiment, since the void P1 of the metallicon layer 100 is sealed with the cured resin 110C, it is easy to prevent the alkaline aqueous solution from entering the vicinity of the connection portion. For this reason, even if it wash | cleans using alkaline aqueous solution, generation | occurrence | production of the connection defect of the metallicon layer 100 and the metal layer 20 can be suppressed.

  On the other hand, the laminate 10 includes two types, a thin film laminate type and a film laminate type. Here, the resin layer 30 (resin thin film formed by a vapor deposition method such as a vacuum deposition method) constituting the thin film laminate type laminate 10 is the resin layer 30 ( Compared with resin film), the film thickness is very thin. Therefore, when the multilayer capacitor 200 is manufactured by using the thin film multilayer type laminate 10, when the core member 124 or an intermediate product obtained by post-processing the core member 124 is cut into a chip shape, the resin layer 30 is formed in the vicinity of the cut surface. There arises a problem that the metal layer 20L and the metal layer 20R located on both sides of the (resin thin film) are electrically connected. In this case, the insulation necessary for functioning as a capacitor cannot be ensured. Therefore, it is preferable to carry out an alkali cleaning step after the cutting step for cutting into chips, and to etch away the metal layer 20 in the vicinity of the cut surface that causes a decrease in insulation.

  From this point of view, when the thin film multilayer capacitor 200 is manufactured, it is preferable to perform the alkali cleaning step after the cutting step of cutting into chips. In this case, the metal layer 20 needs to be made of a metal material that can be etched with an alkaline aqueous solution. Examples of such a metal material include metals such as aluminum and zinc, and alloys such as aluminum alloys and zinc alloys. As the alkaline cleaning liquid, an aqueous solution containing an alkali metal such as sodium hydroxide can be used, and various additives such as a surfactant may be further added as necessary. Moreover, when performing alkali cleaning for the purpose of etching the metal layer 20 in addition to normal cleaning, the pH of the alkali cleaning liquid is preferably in the range of about 11 to 14 from the viewpoint of securing etching ability.

  Next, other embodiments and manufacturing methods of the laminate 10 will be described. As described above, the laminate 10 includes two types, a film laminate type and a thin film laminate type. As illustrated in Patent Documents 1 to 3 and the like, the film laminate type laminate 10 is formed by vacuum deposition, sputtering, or CVD (Chemical Vapor Deposition) on at least one surface of the film-like resin layer 30 (resin film). The production method / structure is not particularly limited as long as it is produced through at least a process of laminating a film with a metal film on which a metal layer 20 is formed by a vapor phase film formation method such as a method. It can be adopted as appropriate.

  FIG. 9 is a schematic cross-sectional view showing an example of a principle manufacturing method of the film laminate type laminate 10. The metallized film 300 shown in FIG. 9 includes a resin film 310 and a metal film 320 provided on the upper surface 310T of the resin film 310. The metal film 320 is provided so as to cover the upper surface 310T excluding a region (upper surface 310TE) in the vicinity of one end side in the width direction of the resin film 310. Here, the metallized film 300A (300) shown in the middle part of FIG. 9 and the metallized film 300B (300) shown in the lower part of FIG. When manufacturing the laminated body 10 of the film lamination type, the metallized film 300A and the metallized film 300B are alternately overlapped and laminated in the arrangement state shown in FIG. By laminating the resin film 310 shown, a film laminate is obtained. Then, the laminated body 10 can be obtained by heat-pressing this film laminated body. In the film laminate type laminate 10, the thickness of the resin layer 30 (the thickness of the resin film 310) is usually about 1 μm to 5 μm, and the thickness of the metal layer 20 (the thickness of the metal thin film) is several tens nm to several hundreds nm. Degree.

  In addition, as exemplified in Patent Document 4 and the like, the thin film stack type laminate 10 includes a resin layer forming step of forming the resin layer 30 by a vapor deposition method and a metal layer 20 by a vapor deposition method. The manufacturing method / structure is not particularly limited as long as it is manufactured through at least a process of alternately repeating the metal layer forming step for forming the metal layer, and a known manufacturing method / structure can be appropriately employed. Note that examples of the vapor phase film forming method used in the resin layer forming step and the metal layer forming step include a vacuum deposition method, a sputtering method, and a CVD method. In the thin film laminate type laminate 10, the thickness of the resin layer 30 (the thickness of the resin thin film) is usually about 0.1 μm to 2.0 μm, and the thickness of the metal layer 20 (the thickness of the metal thin film) is several nm to several About 100 nm.

The thin film laminate type laminate 10 can be manufactured, for example, by the following procedure. First, the ^{2 × 10 -2 Pa~1 × 10 -2} Pa approximately reduced pressure environment, the surface of the supporting substrate, the polymerizable monomer molecules of the vaporized electron beam curing deposited-deposited by heating Not A cured resin film is formed. Then, the uncured resin film is cured by irradiation with an electron beam. Then, by repeating the formation and curing of the uncured resin film a plurality of times, a first surface layer having a thickness several to several hundred times that of the resin layer 30 is formed.

  Then, a metal is vacuum-deposited in the state masked by apply | coating fluorine oil to a part of surface of the 1st surface layer (1st metal layer formation process). Thereby, the metal layer 20L is formed in the part except the part masked with the fluorine oil among the surfaces of the first surface layer.

  Next, the polymerizable monomer molecules evaporated by heating are attached and deposited to form an uncured resin film, and the uncured resin film is irradiated with an electron beam and cured (resin layer forming step). . Thereby, the resin layer 30 is formed. Subsequently, a metal is vacuum-deposited in a state where fluorine oil is applied to a part of the surface of the resin layer 30 and masked (second metal layer forming step). Thereby, the metal layer 20 </ b> R is formed on the surface of the second resin layer 30 except for the portion masked with the fluorine oil. Here, in the width direction of the resin layer 30, a masking position (second masking position) when performing the first metal layer forming step and a masking position (second masking position when performing the second metal layer forming step). Sufficiently away from the masking position).

  Subsequently, the resin layer forming step is performed again to form the second resin layer 30. Thereafter, the process of performing the first metal layer forming step, the resin layer forming step, the second metal layer forming step, and the resin layer forming step in this order is repeated a plurality of times. Then, after finishing any one of these four steps, the second surface layer is formed in the same manner as the first surface layer. Thereby, a large-sized laminated body, that is, a large-sized laminated body in which the laminated body 10 illustrated in FIG. 1 is continuously connected in the width direction can be obtained. And if this large-sized laminated body is cut | disconnected along a 1st masking position and a 2nd masking position, the laminated body 10 illustrated in FIG. 1 can be obtained.

  The large-sized laminate may be cut at a position slightly outside the section surrounded by the first masking position and the second masking position. A dummy layer that does not function as a capacitor may be provided immediately after the formation of the first surface layer and immediately before the formation of the second surface layer. This dummy layer also has a structure in which the metal layers 20 and the resin layers 30 are alternately laminated. However, the masking position when forming all the metal layers 20 constituting the dummy layer is the same position in the width direction of the laminate 10. Provided. For this reason, the metal layers 20 located on both sides of the resin layer 30 always function as electrodes having the same polarity. Therefore, the dummy layer does not have a function as a capacitor. Further, the constituent material of the surface layer and the constituent material of the resin layer 30 may be the same or different.

  FIG. 10 is a schematic cross-sectional view showing another example of the multilayer body used in the method for manufacturing the multilayer capacitor of the present embodiment, and specifically shows an example of the cross-sectional structure of the multilayer body 10 of the thin film multilayer type. . A laminated body 10B shown in FIG. 10 includes a first surface layer 40, a first dummy layer 42, a capacitor layer 44, a second dummy layer 46, and a second surface in this order from the lower surface 12B side to the upper surface 12T side. The layer 48 has a laminated layer structure, and the layer structure is substantially symmetric with respect to the thickness direction. For convenience of explanation, in FIG. 10, the capacitor layer 44 is shown as a portion having a thickness of about 1/3 of the total thickness of the laminated body 10B, but normally the capacity is maximized as much as possible. Therefore, it is a portion having a thickness substantially equal to the total thickness of the laminate 10B. Further, in the drawing, a black portion is made of a metal material, and a white portion is made of a resin material.

  Here, the first dummy layer 42, the capacitor layer 44, and the second dummy layer 46 are arranged in the thickness direction of the stacked body 10B with the metal layer 20 (black belt-like line in the figure) and the resin layer 30 (in the figure). And a white belt-like line sandwiched between two black belt-like lines).

  And each metal layer 20D which comprises the 1st dummy layer 42 and the 2nd dummy layer 46 is interrupted | disconnected by the center part with respect to the length direction (left-right direction of FIG. 10) of the laminated body 10B, and end surface 12R The conduction from the side to the end surface 12L side or the opposite direction is cut off. Hereinafter, a region where the metal layer 20D is partially cut off is referred to as a conduction cut-off region 50C. Therefore, for example, even if the end surface 12R side of the laminate 10B is a positive electrode and the end surface 12L side is a negative electrode, the resin layer 30 located on the right side of the conduction cut-off region 50C is between the two metal layers 20D functioning as the positive electrode. The resin layer 30 located on the left side of the conduction cutoff region 50C is located between the two metal layers 20D functioning as the negative electrode. Therefore, the first dummy layer 42 and the second dummy layer 46 do not function as a capacitor.

  The first dummy layer 42 and the second dummy layer 46 do not function as a capacitor and may be omitted. However, the first dummy layer 42 and the second dummy layer 46 can be provided according to the manufacturing convenience when the stacked body 10B is manufactured.

  On the other hand, similarly to the two first dummy layers 42 and the second dummy layer 46, the capacitor layer 44 is also formed by alternately laminating a plurality of metal layers 20 and resin layers 30 in the thickness direction of the laminate 10B. Has a structure. However, the capacitor layer 44 is different from the first dummy layer 42 and the second dummy layer 46 in the position where the metal layer 20 is disconnected. That is, one of the two metal layers 20R and 20L provided so as to sandwich the resin layer 30 is electrically connected to the end surface 12L side with respect to the length direction of the stacked body 10B. The other metal layer 20L is partially cut off by the conduction cut-off region 50R provided closer to the end face 12R side with respect to the length direction of the stacked body 10B. . Such a configuration is the same for the other metal layers 20 constituting the capacitor layer 44. Specifically, when each metal layer 20 constituting the capacitor layer 44 is given a serial number from the lower surface 12B side to the upper surface 12T side, the capacitor layer 44 is 2a-th (or 2a-1-th). The metal layer 20 is disconnected by the conduction cutoff region 50R, and the 2a-1th (or 2a-th) metal layer 20 is disconnected by the conduction cutoff region 50L. Here, a is an integer of 1 or more.

  For this reason, for example, when the end surface 12R side of the laminate 10B is a positive electrode and the end surface 12L side is a negative electrode, it is located between the conduction cutoff region 50R and the conduction cutoff region 50L in the length direction of the laminate 10B. In addition, the resin layer 30 constituting the capacitor layer 44 is arranged between the resin layers 30, that is, the dielectric layers, and one of the two metal layers 20 functions as a positive electrode and the other functions as a negative electrode. Will be located. Therefore, the capacitor layer 44 functions as a capacitor.

  The conduction cut-off regions 50C, 50R, and 50L correspond to the masked regions that are performed before the metal layer 20 is formed. The conduction cutoff region 50L corresponds to the first masking position, and the conduction cutoff region 50R corresponds to the second masking position. That is, the laminate 10B shown in FIG. 10 was produced by cutting the positions C1 and C2 slightly outside the section X surrounded by the large-sized laminate with the first masking position and the second masking position. Is.

  As a material constituting the metal layer 20, a known metal material can be used as long as it is a conductive metal material, and examples thereof include Al, Zn, Cu, Ag, Ni, and alloys thereof. Of these, Al is particularly preferable.

  Moreover, as a material which comprises the resin layer 30, a well-known resin material can be utilized if it functions as a dielectric material. Here, examples of the material constituting the resin layer 30 constituting the thin film laminate 10 include acrylic resins and vinyl resins. Among these, acrylic resins are particularly preferable. Moreover, as a resin raw material utilized for film-forming of the resin layer 30, the polymerizable monomer which hardens | cures by providing at least 1 sort (s) of physical stimulus selected from light and heat, such as a radiation and an ultraviolet-ray, and superposition | polymerization A polymerizable monomer that is cured by using an additive such as an initiator or a crosslinking accelerator, or a polymerizable monomer that is cured by using both a physical stimulus and an additive in combination can be appropriately used. On the other hand, as the resin layer 30 constituting the film laminate type laminate 10, a commercially available resin film such as a polyethylene terephthalate film, a polyphenylene sulfide film, or a polyethylene naphthalate film can be appropriately used.

  The multilayer capacitor 200 manufactured by the multilayer capacitor manufacturing method of the present embodiment described above can be used as a circuit board capacitor including at least one capacitor. In addition, the multilayer capacitor 200 of the present embodiment can be used as a capacitor for an electronic device including at least one capacitor. In this case, a circuit board including the multilayer capacitor 200 can be used for the electronic device. Such an electronic device is not particularly limited as long as it is a known electronic device using a capacitor. For example, various OA devices such as an audio device and a copying machine, various communication devices such as a mobile phone or a smartphone, a liquid crystal display, and the like Various display devices, computers, or lighting equipment.

10, 10A, 10B: Laminated body 12L: End face (one region of all end faces)
12R: End face (other area of all end faces)
12T: Upper surface 12B: Lower surface 20, 20L, 20R, 20D: Metal layer 30: Resin layer 40: First surface layer 42: First dummy layer 44: Capacitor layer 46: Second dummy layer 48: Second Surface layers 50C, 50L, 50R: Conduction blocking region 100: Metallicon layer 100L: First metallicon layer 100R: Second metallicon layer 102S: Top surface 102T: Top surface 102B: Bottom surface 110C: Cured resin 110UC: Uncured resin component 120 : Cleaning object 122: Curing object 124: Core member 130: Conductive paste layers 140, 140A, 140B: Plating layers 200, 200A, 200B, 200C, 200D: Multilayer capacitors 210, 210A, 210B, 210C, 210D : External electrodes 300, 300A, 300B: Metallized film 310 : Resin film 310T: Upper surface 310TE: Upper surface (region near the end of the upper surface 310T)
320: Metal film

Claims (12)

A first metallicon layer having voids is formed by spraying metal on a region of an end face that is substantially parallel to the thickness direction of the metal layer in the surface of the laminate in which metal layers and resin layers are alternately laminated. And, in the other region of the end face, a metallicon layer forming step of forming a second metallicon layer having voids by spraying metal,
An infiltration step for infiltrating the uncured resin component into the voids of the first metallicon layer and the voids of the second metallicon layer;
By bringing the laminate having the first metallicon layer containing the uncured resin component and the second metallicon layer containing the uncured resin component into contact with a cleaning liquid,
A resin component removing step of removing the uncured resin component present in the vicinity of the surface of the first metallicon layer and the uncured resin component present in the vicinity of the surface of the second metallicon layer;
A curing step of curing the uncured resin component remaining in the first metallicon layer and the uncured resin component remaining in the second metallicon layer;
At least
A method for producing a multilayer capacitor, comprising producing a multilayer capacitor comprising at least the first metallicon layer containing a cured resin component, the second metallicon layer containing a cured resin component, and the multilayer body. In the manufacturing method of the multilayer capacitor according to claim 1,
A conductive paste layer that forms a conductive paste layer so as to cover at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component The manufacturing method of the multilayer capacitor characterized by further including a formation process. In the manufacturing method of the multilayer capacitor according to claim 1 or 2,
A plating layer forming step of forming a plating layer so as to cover at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component; A method of manufacturing a multilayer capacitor, comprising: In the manufacturing method of the multilayer capacitor according to any one of claims 1 to 3,
The core member including the first metallicon layer including the cured resin component, the second metallicon layer including the cured resin component, and the laminated body, which is manufactured through the curing step, and the core member At least one member selected from an intermediate product post-processed,
A method of manufacturing a multilayer capacitor, further comprising an alkali cleaning step of cleaning by contacting with an alkaline aqueous solution. In the manufacturing method of the multilayer capacitor according to any one of claims 1 to 4,
The laminate is produced through at least a process of alternately repeating a resin layer forming step of forming the resin layer by a vapor deposition method and a metal layer forming step of forming the metal layer by a vapor deposition method. A method for manufacturing a multilayer capacitor. A laminate in which metal layers and resin layers are alternately laminated;
A first metallicon layer provided in one region of an end surface substantially parallel to the thickness direction of the metal layer in the surface of the laminate, and having a void;
A second metallicon layer provided in another region of the end face and having voids;
Of the voids of the first metallicon layer and the second metallicon layer, a cured state filled so as to seal voids other than the voids present in the vicinity of the surfaces of the first metallicon layer and the second metallicon layer. Resin,
A multilayer capacitor comprising at least The multilayer capacitor according to claim 6,
The multilayer capacitor characterized in that the surfaces of the first metallicon layer and the second metallicon layer have irregularities resulting from a metal spraying process. In the multilayer capacitor according to claim 6 or 7,
The laminate is produced through at least a process of alternately repeating a resin layer forming step of forming the resin layer by a vapor deposition method and a metal layer forming step of forming the metal layer by a vapor deposition method. A multilayer capacitor characterized by that. In the multilayer capacitor according to any one of claims 6 to 8,
A conductive paste layer is provided so as to cover at least the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. Characteristic multilayer capacitor. In the multilayer capacitor according to any one of claims 6 to 9,
A plating layer is provided so as to be in direct contact with and at least cover the surface of the first metallicon layer containing the cured resin component and the surface of the second metallicon layer containing the cured resin component. A multilayer capacitor characterized by the above. At least a multilayer capacitor,
The multilayer capacitor is
A laminate in which metal layers and resin layers are alternately laminated;
A first metallicon layer provided in one region of an end surface substantially parallel to the thickness direction of the metal layer in the surface of the laminate, and having a void;
A second metallicon layer provided in another region of the end face and having voids;
Of the voids of the first metallicon layer and the second metallicon layer, a cured state filled so as to seal voids other than the voids present in the vicinity of the surfaces of the first metallicon layer and the second metallicon layer. Resin,
A circuit board having at least At least a multilayer capacitor,
The multilayer capacitor is
A laminate in which metal layers and resin layers are alternately laminated;
A first metallicon layer provided in one region of an end surface substantially parallel to the thickness direction of the metal layer in the surface of the laminate, and having a void;
A second metallicon layer provided in another region of the end face and having voids;
Of the voids of the first metallicon layer and the second metallicon layer, a cured state filled so as to seal voids other than the voids present in the vicinity of the surfaces of the first metallicon layer and the second metallicon layer. Resin,
An electronic device having at least

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