JP2005050921A - Method for manufacturing ceramic electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a ceramic electronic component for effectively preventing deficiency such as deformation and cracks from occurring in a conductor layer and a ceramic layer, by manufacturing the small sized ceramic electronic component by thinning the thickness of the conductor layer. <P>SOLUTION: The ceramic electronic component is manufactured through a step A for depositing a metal plating film at a part having no mask layer on the surface of a substrate partly having the mask layer consisting of DLC or GLC, a step B for transferring the metal plating film on the substrate and integrating the metal plating film with a ceramic green sheet, and a step C for obtaining the ceramic electronic component adhering the conductor layer on the ceramic layer by firing the ceramic green sheet. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a ceramic electronic component such as a capacitor, an inductor, a filter, or a circuit board that is configured by combining a ceramic layer and a conductor layer having a predetermined pattern.
[0002]
[Prior art]
Conventionally, ceramic materials have been used to form electronic components such as capacitors, inductors, filters, and circuit boards.
[0003]
As such a conventional ceramic electronic component, for example, a laminated body in which a plurality of ceramic layers having a predetermined dielectric constant are laminated with a first internal electrode and a second internal electrode alternately interposed therebetween. And a multilayer ceramic capacitor in which a pair of external electrodes electrically connected to the first and second internal electrodes are respectively provided on the side surface and the main surface of the multilayer body are widely known, Such a multilayer ceramic capacitor is arranged between a first internal electrode and a second internal electrode by applying a predetermined voltage between the first internal electrode and the second internal electrode via a pair of external electrodes. The ceramic layer functions as a capacitor by forming a predetermined capacitance.
[0004]
Moreover, the multilayer ceramic capacitor mentioned above is manufactured through the following processes, for example (for example, refer patent document 1).
[0005]
First, an organic binder and an organic solvent are added to and mixed with a predetermined ceramic material powder to prepare a slurry-like inorganic composition, which is formed into a sheet with a predetermined thickness by a conventionally known doctor blade method, etc. Form a sheet.
[0006]
Next, a conductive paste mainly composed of a metal such as nickel is printed and applied in a predetermined pattern on the main surface of the obtained ceramic green sheet by screen printing or the like known in the art, and a plurality of these are stacked to make the ceramic green A laminate of sheets is formed.
[0007]
Subsequently, the laminate is fired at a high temperature to form a conductor paste as an internal electrode and a ceramic green sheet as a ceramic layer. Finally, the conductor paste is applied to the end face of the laminate by a conventionally known dipping method or the like. A multilayer ceramic capacitor is manufactured by coating and baking to form external electrodes.
[0008]
[Patent Document 1]
JP 2000-243650 A
[0009]
[Problems to be solved by the invention]
By the way, in recent years, with the miniaturization of electronic devices, there has been a demand for miniaturization of ceramic electronic components, and in the case of the above-described multilayer ceramic capacitor, various studies for thinly forming individual ceramic layers and internal electrodes have been made. ing.
[0010]
For example, in the above-described conventional multilayer ceramic capacitor, in order to reduce the thickness of the internal electrode, the average particle size of the metal powder contained in the conductor paste used for forming the internal electrode is, for example, about 0.3 μm It is important to make it extremely small.
[0011]
However, when the particle size of the metal powder contained in the conductor paste is extremely small, the dispersibility of the metal powder is deteriorated due to the aggregation of the metal powders in the conductor paste. It has a drawback that it is difficult to obtain a conductor paste having characteristics suitable for printing and the like.
[0012]
Even if a conductor paste having characteristics suitable for screen printing can be obtained by adjusting various components contained in the conductor paste, it is applied thinly on a ceramic green sheet. When firing, there is a disadvantage that the continuity of the internal electrode is significantly lost due to movement of the metal powder in the conductor paste during firing, and in the worst case, the internal electrode is divided. .
[0013]
Therefore, in order to eliminate the above disadvantages, a metal plating film to be an internal electrode is formed in advance on the surface of a base material made of stainless steel or the like, and this is transferred to a ceramic green sheet so that a very thin internal electrode having a thickness of 1 μm or less Can be considered.
[0014]
However, when forming the internal electrode by transferring a previously formed metal plating film to a ceramic green sheet, the thickness of the mask that regulates the deposition area of the metal plating film can be reduced in order to reduce the thickness of the metal plating film. It needs to be thin. It is considered that a cyclized rubber-based photoresist material or the like can be used as a material for such a mask. Such a photoresist material can be applied to a conventionally known screen printing method, spin coating method, curtain coating method, roll coater method, etc. It is extremely difficult to form a photoresist film as thin as 1 μm or less when it is applied to the surface of a substrate by the above method, and it requires a high degree of manufacturing technology, and the cyclized rubber-based photoresist material described above. Since its strength is relatively low and its adhesion to stainless steel forming the base material is not good, the mask peels off from the base material relatively quickly when used continuously. Or a defect such as damage to the mask is induced.
[0015]
The present invention has been devised in view of the above drawbacks, and an object of the present invention is to provide a method of manufacturing a ceramic electronic component that can relatively easily obtain a small ceramic electronic component by reducing the thickness of a conductor layer. It is in.
[0016]
[Means for Solving the Invention]
The method of manufacturing a ceramic component according to the present invention includes a surface of a substrate partially having a mask layer made of diamond-like carbon (DLC) or graphite-like carbon (GLC), at a portion where the max layer is not present. Depositing a metal plating film, transferring the metal plating film on the substrate to a transfer material, integrating the metal plating film with the ceramic green sheet, and firing the ceramic green sheet And C for obtaining a ceramic electronic component having a conductor layer deposited on the ceramic layer.
[0017]
The method for manufacturing a ceramic electronic component according to the present invention is characterized in that an angle of a corner formed between a side surface and a lower surface of the mask layer is 90 degrees or less.
[0018]
Furthermore, in the method for producing a ceramic electronic component according to the present invention, the surface of the substrate on which the metal plating film is deposited has at least titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, and conductive DLC. 1 type, the surface roughness is 0.5 μm or less at the maximum height Ry, and the specific resistance of the substrate surface is 10 ^-3 It is characterized by being Ωcm or less.
[0019]
Furthermore, in the method for producing a ceramic electronic component of the present invention, the firing temperature of the ceramic green sheet in the step C is higher than the recrystallization temperature of the metal forming the metal plating film and lower than the melting point of the metal. It is characterized by.
[0020]
Furthermore, in the method for manufacturing a ceramic electronic component according to the present invention, the base body has a cylindrical shape or a columnar shape, and in the step A, a part of the base plate is plated while rotating the base body about an axis. The metal plating film is deposited and formed by immersing in a liquid and applying an electric field to a plating liquid between the substrate and the plating tank.
[0021]
Furthermore, the method for manufacturing a ceramic electronic component according to the present invention is characterized in that a radius of curvature of the surface of the substrate is 50 mm to 2000 mm.
[0022]
[Action]
According to the present invention, a mask layer that regulates the deposition region of the metal plating film is formed of diamond-like carbon (DLC) or graphite-like carbon (GLC), so that a relatively thin mask layer is formed. In addition to being able to obtain sufficient electrical insulation, it is possible to improve the releasability when the metal plating film is peeled from the substrate, and DLC and GLC are extremely hard, and the substrate is formed of stainless steel or the like. Therefore, even if it is used continuously for a long period of time, the mask layer can be firmly attached to the substrate while maintaining a good state.
[0023]
In addition, when the metal plating film is directly transferred to the ceramic green sheet, the ceramic green sheet hardly adheres to the surface of the mask layer, so that there is an advantage that stable transfer can be repeatedly performed.
[0024]
Further, according to the present invention, if the angle of the corner formed between the side surface and the lower surface of the mask layer is 90 degrees or less, the area of the lower surface of the metal plating film in contact with the substrate is larger than the area of the upper surface. Therefore, when transferring the metal plating film to a ceramic green sheet or the like, the outer peripheral portion of the metal plating film is hardly caught by the max layer, and the metal plating film can be satisfactorily 'missed'. .
[0025]
Furthermore, according to the present invention, the surface of the substrate on which the metal plating film is deposited is formed of at least one of titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, and conductive DLC. The surface roughness of the substrate surface is set to 0.5 μm or less at the maximum height Ry, and the specific resistance is set to 10 ^-3 By setting it to Ωcm or less, when depositing a metal plating film on the surface of the substrate, the current density between the substrate and the plating tank becomes more uniform, and the thickness of the metal plating film can be made more uniform. become able to. In addition, in this case, the hardness of the substrate surface is high and the surface state is extremely smooth, so that the peelability of the metal plating film is also good.
[0026]
Furthermore, according to the present invention, the above-described metal plating film is fired by firing at a temperature higher than the recrystallization temperature of the metal forming the metal plating film and lower than the melting point when firing the ceramic green sheet. The metal plating film is not melted by the heat of time and the metal plating film is not divided, and a conductor layer having excellent continuity can be formed. Here, the metal plating film becomes a conductor layer with excellent continuity, because the metal forming the metal plating film is recrystallized when the ceramic green sheet is fired, so that the metal softens moderately. This is because the ceramic particles in the ceramic green sheet enter the surface of the metal plating film, whereby the adhesion between the metal plating film and the ceramic green sheet is improved, and a ceramic electronic component with few structural defects is obtained.
[0027]
Furthermore, according to the present invention, the substrate on which the metal plating film is deposited is formed into a cylindrical shape or a columnar shape, and in the metal plating film deposition process, a part of the substrate is rotated while rotating the substrate around the axis. The metal plating film is continuously formed by improving the productivity by immersing in the plating liquid and forming the metal plating film by applying an electric field to the plating liquid between the substrate and the plating tank. In addition, the current density between the substrate and the plating tank can be made substantially uniform, and the metal plating film can be formed with a substantially constant thickness.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
[0029]
FIG. 1 is a cross-sectional view showing a multilayer ceramic capacitor as a ceramic electronic component manufactured by a manufacturing method according to an embodiment of the present invention. The multilayer ceramic capacitor 1 shown in FIG. It is composed of an internal electrode 3 as a conductor layer, a ceramic layer 4 and an external electrode 5.
[0030]
The multilayer ceramic capacitor 1 is formed by alternately laminating internal electrodes 3 and ceramic layers 4 having a predetermined dielectric constant to form a rectangular parallelepiped laminate, and the same material as the ceramic layer 4 on both upper and lower surfaces of the laminate. And an external electrode 5 electrically connected to the internal electrode 3 is attached to and formed at both ends of the laminate.
[0031]
The outer shape of the multilayer ceramic capacitor 1 is formed, for example, with a width of 1.2 mm, a length of 2 mm, and a height of 1.2 mm, and the number of stacked ceramic layers 4 and internal electrodes 3 is 30 to 600 layers. Is set.
[0032]
The thickness of the internal electrode 3 is set to about 0.5 μm to 2.0 μm, and the thickness of the ceramic layer 4 is set to about 1.0 μm to 4.0 μm.
[0033]
The material and thickness of the ceramic layer 4, the number of stacked layers, the facing area of the internal electrode 3, and the like are appropriately determined depending on the desired capacitance.
[0034]
The multilayer ceramic capacitor 1 applies a predetermined voltage to the adjacent internal electrodes 3-3 via the external electrodes 5, and applies a predetermined capacitance to the ceramic layer 4 disposed between the internal electrodes 3-3. Function as a capacitor by forming
Next, a method for manufacturing the above-described multilayer ceramic capacitor will be described with reference to FIGS.
[0035]
2 schematically shows a manufacturing apparatus used in the manufacturing method of the present invention, FIG. 3 is a plan view of the substrate 11 used in the manufacturing apparatus of FIG. 2 as viewed from the direction A in FIG. 2, and FIG. It is an expanded sectional view which shows the structure of the base | substrate surface used for this manufacturing apparatus.
[0036]
<Step 1>
First, the metal plating film 9 having a convex curved surface is formed on the surface of the substrate 11 having a convex curved surface.
[0037]
The base 11 has a columnar shape or a cylindrical shape with a radius of curvature of 50 mm to 2000 mm and a length of 50 mm to 1000 mm, for example, by a metal material having conductivity such as stainless steel, iron, aluminum, copper, nickel, titanium, tantalum, and molybdenum. The conductive film 7 is formed on the surface, and a plurality of rectangular regions having a width of 1.2 μm and a length of 2 μm are further exposed on the conductive film 7. Then, a mask layer 8 made of diamond-like carbon (DLC) or graphite-like carbon (GLC) having a thickness of about 1 μm is partially formed.
[0038]
The conductive film 7 is formed of at least one of titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, and conductive DLC, and the surface roughness of the substrate surface is maximum. Ry is set to 0.5 μm or less, more preferably Ry is set to 0.2 μm or less, and the specific resistance is 10 from the viewpoint of current density during electrolytic plating. ^-3 It is set to Ωcm or less.
[0039]
Of these materials, titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, and titanium carbonitride are particularly preferable in consideration of the peelability of the metal plating film 9, and titanium nitride is preferable from the viewpoint of durability. preferable.
[0040]
Here, the surface roughness of the substrate surface is made small because when the thickness of the metal plating film 9 is reduced, the convex portions of the substrate 11 are transferred to the metal plating film 9 to form pinholes in the metal plating film 9. This is because structural defects may occur when this is heat-treated.
[0041]
The conductive film 7 is formed on the surface of the substrate 11 by a well-known thin film forming method such as sputtering, ion plating, chemical vapor deposition (CVD) or the like.
[0042]
On the other hand, the mask layer 8 on the conductive film 7 described above is for restricting the deposition region of the metal plating film 9, and has sufficient electrical insulation so that the metal plating film is not deposited on the surface. For example, the resistance is 10 ⁴ The film is set to Ωcm or more, has a Vickers hardness Hv of 1000 or more, and a friction coefficient μ of 0.3 or less. Examples of the material satisfying such various characteristics include the above-mentioned DLC and GLC.
[0043]
Thus, by forming the mask layer 8 that regulates the deposition region of the metal plating film 9 on the surface of the base 11, the base 11 is immersed in the plating solution 17 without a complicated process such as photoetching. Thus, the metal plating film 9 having a desired pattern can be easily obtained simply by applying an electric field between the plating tank 16 and the productivity of the multilayer ceramic capacitor can be improved.
[0044]
The thickness of the mask layer 8 is arbitrarily set depending on the desired thickness of the metal plating film 9 and is preferably formed to be the same as the metal plating film 9 or slightly thicker than the metal plating film 9. This is to prevent the metal plating film 9 in the middle of deposition from spreading over the mask layer 8.
[0045]
The mask layer 8 made of DLC or GLC is coated with carbon to a predetermined thickness on the surface of the substrate 11 under predetermined film forming conditions by a thin film forming method such as a well-known sputtering method, ion plating method, or CVD method. After depositing and forming, by employing a conventionally known photo-etching method or the like, the obtained film is processed into a predetermined pattern having a plurality of openings corresponding to the deposition region of the metal plating film 9 It is formed.
[0046]
Since such a mask layer 8 is made of DLC or GLC having a high electric resistance, plating does not deposit on the surface of the mask layer 8, and the surface peelability is good and the frictional resistance is also small. When the metal plating film 9 is transferred to the resin film 21 which is a transfer object in the present embodiment, the transfer object is hardly damaged, the durability of the substrate 11 is improved, and it is used repeatedly over a long period of time. However, a high-quality metal plating film 9 can be formed.
[0047]
In this case, the DLC and GLC forming the mask layer 8 are extremely hard and have good adhesion to the substrate 11 formed of stainless steel or the like. 8 can be firmly attached to the base 11 while maintaining a good state.
[0048]
The angle α of the corner formed by the side surface and the lower surface (surface of the base body 11) of the mask layer 8 is set to 90 to 85 degrees, for example.
[0049]
The base 11 described above is rotated around the axis of the rotary shaft 12 at a predetermined rotational speed so that the lower region is immersed in the plating solution 17 or the like held in the plating tank 16. The current density of the base 11 is, for example, 2 A / dm ² ~ 15A / dm ² A predetermined potential difference is provided between the plating tank 16 and the above-described rectangular region of the substrate 11 by electrolytic plating, whereby the metal plating film 9 is formed along the convex curved surface of the substrate 11.
[0050]
Thus, while rotating the cylindrical or columnar substrate 11 around its axis, the substrate 11 is immersed in the plating solution 17 in the plating tank 16 and an electric field is applied to the plating solution 17 between the substrate 11 and the plating tank 16. By forming the metal plating film 9 in this way, the metal plating film 9 can be formed continuously, thereby improving the productivity of the multilayer ceramic capacitor. In addition, in this case, since the current density between the base 11 and the plating tank 17 becomes substantially uniform, the metal plating film 9 can be formed with a substantially constant thickness.
[0051]
The rotating shaft 12 of the base 11 is supported at both ends by bearings (not shown) so that the base 11 does not move vertically and horizontally. By connecting the rotary shaft 12 and the main shaft of the prime mover and transmitting the rotational motion of the prime mover, the base 11 rotates around the axis at a predetermined speed.
[0052]
The rotating shaft 12 of the base 11 is electrically connected to a power supply device 13 via a rotating brush, thereby causing the base 11 to function as a cathode in electrolytic plating.
[0053]
On the other hand, the plating tank 16 holds the plating solution 17 therein, and functions as an anode during electrolytic plating. The inner surface of the plating tank 16 is, for example, arranged substantially concentrically with the outer surface of the substrate 11. A predetermined gap, for example, a gap of 5 to 30 mm, for filling the plating solution 17 is formed between the first and second electrodes 16.
[0054]
As the plating solution 17, when a nickel plating film is formed as the metal plating film 9, for example, a nickel sulfamate plating solution is used. In this case, nickel chloride 30 g / liter, nickel sulfamate 300 g / liter, boric acid 30 g. An aqueous solution having a composition of 1 / liter is used. Here, the pH value of the plating solution 17 is set to 3.0 to 4.2, for example, and the pH value is set to 3.5 to 4.0 in order to keep the internal stress in the metal plating film 9 small. It is preferable to keep it. Further, the temperature of the plating solution 17 is set to, for example, 25 ° C. to 70 ° C., and is preferably set to 45 to 50 ° C. in order to suppress the internal stress in the metal plating film 9 to be small. Here, the above-described plating solution 17 includes, as necessary, a pH buffer composed of boric acid, nickel formate, nickel acetate or the like, a pit inhibitor composed of sodium lauryl sulfate, or an aromatic hydrocarbon such as benzene or naphthalene. Stress reducing agent consisting of chemicals with sulfonic acid, sulfonate, sulfonamide, sulphonimide, etc., curing agent consisting of aromatic sulphonic acid and its derivatives, butynediol, 2-butyne 1.4 diol, ethylene cyanide Needless to say, a smoothing agent composed of hydrin, formaldehyde, coumarin, pyrimidine, pyrazole, imidazole, or the like may be added as appropriate. Specific examples of the stress reducing agent include saccharin, p-toluenesulfonamide, benzenesulfonamide, benzenesulfonimide, sodium benzenedisulfonate, sodium benzenetrisulfonate, sodium naphthalenedisulfonate, naphthalenetri Examples thereof include sodium sulfonate.
[0055]
The plating solution 17 in the plating tank 16 is preferably always flowed in a predetermined direction by the circulation device 14 or the like when performing electroplating in order to obtain a uniform metal plating film 9. In order to deposit the nickel metal plating film 9 with high purity, it is preferable to form the inner surface of the plating tank 18 with a metal material having the same quality as the metal plating film 9.
[0056]
The metal plating film 9 formed on the surface of the base 11 as described above is pulled up from the plating solution by the rotation of the base 11 and then washed and dried by the cleaning means 15.
[0057]
<Process 2>
Next, the metal plating film 9 obtained in step 1 is once transferred onto the resin film 20.
[0058]
As the resin film 20, what formed the adhesive layer 21 of thickness 0.05micrometer-10 micrometers on the main surfaces, such as a polyethylene terephthalate film (PET film) of thickness 20-50 micrometers, for example is used. The pressure-sensitive adhesive layer 21 is formed by, for example, applying an acrylic (solvent), acrylic emulsion (water), butyral, phenol, silicon, or epoxy adhesive (solvent) to the main surface of a PET film or the like. It is preferable to adjust the adhesive strength after drying to be, for example, 0.1 N / cm.
[0059]
Such a resin film 20 is sequentially supplied to the substrate 11 side by the delivery unit 22, and the side on which the adhesive layer 21 is formed is applied to the surface of the substrate 11 on which the metal plating film 9 is formed by the pressure roller 23. For example, the metal plating film 9 is transferred onto the resin film 20 by applying pressure with a pressing force of 10N. Thereafter, the resin film 20 is wound up by the winding unit 24 at the same speed as the peripheral speed of the substrate surface.
[0060]
At this time, if the angle α of the corner formed between the side surface and the lower surface of the mask layer 8 is 90 degrees or less, the area of the lower surface of the metal plating film 9 in contact with the substrate 11 is larger than the area of the upper surface. Therefore, when the metal plating film 9 is transferred to the resin film 20 or the like, the outer peripheral portion of the metal plating film 9 is hardly caught by the max layer 8 and the “plating” of the metal plating film 9 is improved. Can do.
[0061]
The adhesive layer 21 is made of a material that is reliably pyrolyzed at a relatively low temperature. Specifically, even if it adheres to the metal plating film 9, it is an acrylic (solvent) that decomposes thermally upon firing. Type), acrylic emulsion type (water type), and butyral type adhesives are preferred, and among these, it is particularly preferred to use acrylic adhesives with good peelability. The pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer 21 is, for example, 0.005 N / cm to 1.0 N / cm, and from the viewpoint of transferability, a pressure of 0.01 N / cm to 1.0 N / cm is used. In particular, from the viewpoint of releasability, it is preferable to use one having a density of 0.01 N / cm to 0.2 N / cm.
[0062]
Further, as the pressure roll 23, a surface portion formed of an elastic material such as urethane rubber coat, neoprene rubber coat, natural rubber coat, etc. so that the resin film 20 can be uniformly pressed against the base 11. It is preferable to use it.
[0063]
<Step 3>
Next, the metal plating film 9 is transferred onto the main surface of the ceramic green sheet 26 by further transferring the ceramic green sheet 26 onto the resin film 20 to which the metal plating film 9 has been transferred.
[0064]
The ceramic green sheet 26 is supplied to the joining position with the resin film 20 while being supported on a resin film 25 made of, for example, a PET film having a thickness of 12 μm to 100 μm. Both resin films 20 and 25 are overlapped so as to be in contact with the plating film 9, and this portion is heated at a temperature of about 70 ° C. by a heater provided in the pressure roller 27, and the resin film 25 is added. The ceramic green sheet 26 is transferred to the metal plating film 9 side by applying pressure to the resin film 20 side with a pressing force of about 100 N by the pressure roller 27. Thereafter, the resin film 25 from which the ceramic green sheet 26 has been peeled off is stored in the storage portion. 29 is wound up.
[0065]
In this case, the metal plating film 9 is formed in a convex curved surface on the surface of the base 11 having a convex curved surface, and internal stress (tensile stress) is generated in the metal plating film 9 when the metal plating film 9 is deposited. However, when the metal plating film 9 is peeled from the substrate 11, the convex-curved metal plating film 9 is deformed in a flattening direction. Therefore, when this is transferred to the main surface of the ceramic green sheet 26, Inconveniences such as deformation and cracks occurring in the ceramic green sheet 26 and the metal plating film 9 and delamination and cracks during firing are effectively prevented, and the productivity of the multilayer ceramic capacitor 1 is improved. Can do.
[0066]
Further, in this way, if the metal plating film 9 is once transferred onto the resin film 20 and then transferred onto the ceramic green sheet 26, the ceramic green sheet 26 is formed on the surface of the substrate on which the hard material is formed. Since there is no direct contact with the mask layer 8, the metal plating film 9 can be satisfactorily transferred to the ceramic green sheet 26 without damaging the ceramic green sheet 26 by contact with the mask layer 8. it can.
[0067]
The ceramic green sheet 26 supported on the resin film 25 is formed to have a thickness of 1 μm to 20 μm, for example, and a predetermined ceramic slurry obtained by adding and mixing an organic solvent, an organic binder, etc. to the ceramic material powder. It is obtained by coating the main surface of the resin film 25 by a conventionally known coating method or printing method so that the thickness after firing is about 2 μm, and then drying it.
[0068]
Further, as the pressure roller 27, the surface portion is coated with a urethane rubber so that the ceramic green sheet 26 can be evenly pressed against the metal plating film 9, similarly to the pressure roller 23 described above. It is preferable to use a material formed of a resilient material such as neoprene rubber coat or natural rubber coat.
[0069]
<Step 4>
Next, a plurality of ceramic green sheets 26 with the metal plating film 9 obtained in the above-described step 3 are prepared, and these are pressed and laminated together to form a laminate.
[0070]
Such a laminate is, for example, temporarily pressure-bonded at a pressure of 0.9 MPa while being heated at a temperature of 60 ° C., and then the laminate is heated at a temperature of 70 ° C. and a pressure of 50 MPa by a conventionally known hydrostatic pressure press or the like. The ceramic green sheet 26 with the metal plating film 9 to be formed is bonded to each other.
[0071]
<Step 5>
Finally, the laminate obtained in step 4 is cut into a predetermined shape, and these are fired at a high temperature, thereby forming the ceramic green sheet 26 as the ceramic layer 4 of the multilayer ceramic capacitor, and the metal plating film 9 as the internal electrode 3. Eggplant.
[0072]
Here, the firing temperature of the laminated body is set to a temperature lower than the melting point of the metal forming the metal plating film 9 and higher than the recrystallization temperature of the metal.
[0073]
For example, when the metal plating film 9 is made of nickel, the recrystallization temperature of nickel is 500 to 550 ° C., and the melting point of nickel is 1450 ° C. Therefore, the laminate is fired at a temperature of 1300 ° C., for example.
[0074]
By firing the metal plating film 9 at a temperature lower than the melting point of the metal forming the plating film 9 in this way, the disadvantage that the metal plating film 9 melts and the metal plating film 9 is divided during firing is ensured. The internal electrode 3 which is prevented and has excellent continuity can be formed.
[0075]
In this case, the firing temperature of the laminate is set higher than the recrystallization temperature of the metal forming the metal plating film 9, so that the recrystallization of the metal forming the metal plating film 9 during firing is performed. As the metal proceeds, the metal softens moderately, and the ceramic particles in the ceramic green sheet 26 enter the surface of the metal plating film 9, thereby improving the adhesion between the metal plating film 9 and the ceramic green sheet 26. A multilayer ceramic capacitor with few structural defects can be obtained.
[0076]
<Step 6>
Finally, a conductive paste for external electrodes is applied to both ends of the multilayer body, fired, and further subjected to plating to form external electrodes 5, thereby completing a multilayer ceramic capacitor 1 as a product.
[0077]
The present invention is not limited to the above-described embodiments, and various changes and improvements can be made without departing from the scope of the present invention.
[0078]
For example, in the above-described embodiment, the ceramic green sheet 26 is further transferred onto the resin film 20 to which the metal plating film 9 has been transferred so that the ceramic green sheet 26 and the metal plating film 9 are integrated. Instead of this, the metal plating film 9 transferred from the substrate 11 onto the resin film 20 may be transferred onto the surface of the ceramic green sheet 26 held on the resin film 25 (see FIG. 5). Alternatively, the metal plating film 9 deposited on the substrate 11 may be directly transferred to the main surface of the ceramic green sheet 26 held on the resin film 25 (see FIG. 6). In particular, when the other embodiment shown in FIG. 6 is adopted, the ceramic green sheet 26 hardly adheres to the surface of the DLC or GLC on which the mask layer 8 is formed on the substrate 11, so that stable transfer is possible. There is also an advantage that it can be repeated.
[0079]
In the above-described embodiment, by applying a ceramic slurry on the resin film 20 to which the metal plating film 9 has been transferred, and drying the ceramic slurry to form a ceramic green sheet in which the metal plating film 9 is embedded, The ceramic green sheet and the metal plating film 9 may be integrated.
[0080]
Furthermore, in the above-described embodiment, an example in which a nickel plating film is deposited and formed as the metal plating film 9 has been described. However, a metal plating film made of a metal material other than nickel, for example, copper, silver, gold, platinum, palladium, A metal plating film 9 made of chromium or an alloy of these metal materials may be deposited and formed.
[0081]
Further, in the above-described embodiment, the case where a multilayer ceramic capacitor is manufactured has been described as an example. However, ceramic electronic components other than the multilayer ceramic capacitor, for example, other ceramic electronic components such as an inductor, a filter, and a circuit board are manufactured. Needless to say, the present invention can be applied to cases.
[0082]
【The invention's effect】
According to the present invention, a mask layer that regulates the deposition region of the metal plating film is formed of diamond-like carbon (DLC) or graphite-like carbon (GLC), so that a relatively thin mask layer is formed. In addition to being able to obtain sufficient electrical insulation, it is possible to improve the releasability when the metal plating film is peeled from the substrate, and DLC and GLC are extremely hard, and the substrate is formed of stainless steel or the like. Therefore, even if it is used continuously for a long period of time, the mask layer can be firmly attached to the substrate while maintaining a good state.
[0083]
In addition, when the metal plating film is directly transferred to the ceramic green sheet, the ceramic green sheet hardly adheres to the surface of the mask layer, so that there is an advantage that stable transfer can be repeatedly performed.
[0084]
Further, according to the present invention, if the angle of the corner formed between the side surface and the lower surface of the mask layer is 90 degrees or less, the area of the lower surface of the metal plating film in contact with the substrate is larger than the area of the upper surface. Therefore, when transferring the metal plating film to a ceramic green sheet or the like, the outer peripheral portion of the metal plating film is hardly caught by the max layer, and the metal plating film can be satisfactorily 'missed'. .
[0085]
Furthermore, according to the present invention, the surface of the substrate on which the metal plating film is deposited is formed of at least one of titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, and conductive DLC. The surface roughness of the substrate surface is set to 0.5 μm or less at the maximum height Ry, and the specific resistance is set to 10 ^-3 By setting it to Ωcm or less, when depositing a metal plating film on the surface of the substrate, the current density between the substrate and the plating tank becomes more uniform, and the thickness of the metal plating film can be made more uniform. become able to. In addition, in this case, the hardness of the substrate surface is high and the surface state is extremely smooth, so that the peelability of the metal plating film is also good.
[0086]
Furthermore, according to the present invention, the above-described metal plating film is fired by firing at a temperature higher than the recrystallization temperature of the metal forming the metal plating film and lower than the melting point when firing the ceramic green sheet. The metal plating film is not melted by the heat of time and the metal plating film is not divided, and a conductor layer having excellent continuity can be formed. Here, the metal plating film becomes a conductor layer with excellent continuity, because the metal forming the metal plating film is recrystallized when the ceramic green sheet is fired, so that the metal softens moderately. This is because the ceramic particles in the ceramic green sheet enter the surface of the metal plating film, whereby the adhesion between the metal plating film and the ceramic green sheet is improved, and a ceramic electronic component with few structural defects is obtained.
[0087]
Furthermore, according to the present invention, the substrate on which the metal plating film is deposited is formed into a cylindrical shape or a columnar shape, and in the metal plating film deposition process, a part of the substrate is rotated while rotating the substrate around the axis. The metal plating film is continuously formed by improving the productivity by immersing in the plating liquid and forming the metal plating film by applying an electric field to the plating liquid between the substrate and the plating tank. In addition, the current density between the substrate and the plating tank can be made substantially uniform, and the metal plating film can be formed with a substantially constant thickness.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a multilayer ceramic capacitor as a ceramic electronic component manufactured by a manufacturing method according to an embodiment of the present invention.
FIG. 2 is a diagram schematically showing a configuration of a manufacturing apparatus used in the manufacturing method of the present invention.
3 is a plan view of a base body 11 used in the manufacturing apparatus of FIG. 2 when viewed from the direction A in FIG. 2;
4 is an enlarged cross-sectional view showing a structure of a substrate surface used in the manufacturing apparatus of FIG. 3;
FIG. 5 is a diagram schematically showing a configuration of a manufacturing apparatus used in a manufacturing method according to another embodiment of the present invention.
FIG. 6 is a diagram schematically showing a configuration of a manufacturing apparatus used in a manufacturing method according to another embodiment of the present invention.
[Explanation of symbols]
1 ... Multilayer ceramic capacitor (ceramic electronic component)
2 ... Insulating layer
3 ... Internal electrode (conductor layer)
4 ... Ceramic layer
5 ... External electrode
7 ... conductive film
8 ... Mask layer
9 ... Metal plating film
11 ... Substrate
12 ... Rotating shaft
13 ... Power supply
14 ... Circulation device
15 ... Drying section
16 ... Plating tank (anode)
17 ... Plating solution
20 ... Resin film
21 ... Adhesive layer
22 ... Delivery section
23 ... Pressure roller
24 ... Winding part
25 ... Resin film
26 ... Ceramic green sheet
27 ... Pressure roller
28 ... Supply section
29 ... Storage part

Claims (6)

A step A of depositing a metal plating film on the surface of the substrate partially having a mask layer made of diamond-like carbon (DLC) or graphite-like carbon (GLC) at a portion where the max layer does not exist;
Transferring the metal plating film on the substrate to a transfer material and integrating the metal plating film with a ceramic green sheet; and
And a step C of obtaining a ceramic electronic component having a conductor layer deposited on a ceramic layer by firing the ceramic green sheet. 2. The method of manufacturing a ceramic electronic component according to claim 1, wherein an angle of a corner formed between the side surface and the lower surface of the mask layer is 90 degrees or less. The surface of the substrate on which the metal plating film is deposited is made of at least one of titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, and conductive DLC, and has a maximum surface roughness. 3. The method of manufacturing a ceramic electronic component according to claim 1, wherein Ry is 0.5 μm or less, and a specific resistance of the substrate surface is 10 ⁻³ Ωcm or less. 2. The ceramic electronic component according to claim 1, wherein a firing temperature of the ceramic green sheet in the step C is higher than a recrystallization temperature of the metal forming the metal plating film and lower than a melting point of the metal. Manufacturing method. The substrate has a cylindrical or columnar shape, and in the step A, while rotating the substrate around an axis, a part of the substrate is immersed in a plating solution of the plating tank, and the substrate and the plating tank 5. The method of manufacturing a ceramic electronic component according to claim 1, wherein the metal plating film is deposited and formed by applying an electric field to the plating solution between the two. 6. The method of manufacturing a ceramic electronic component according to claim 5, wherein a radius of curvature of the surface of the substrate is 50 mm to 2000 mm.

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