JPH02155213A - Manufacture of laminated ceramic electronic part - Google Patents

Abstract

PURPOSE:To peel a base film easily, and to improve laminating properties by transferring an electrode-filled ceramic green sheet in a section, to which a releasable resin is formed, on the base film onto another electrode ink film. CONSTITUTION:Electrode ink films 12 are shaped onto a base film 11. Releasable resins 13 are formed partially onto the electrode ink films 12 of the base film 11 and the base film 11 of the peripheries of the films 12. An silicone resin, fluoroplastics, wax, etc., are used as the releasable resin 13. Dielectric slurry is applied, and dried, thus shaping a ceramic green sheet 14. An electrode-filled ceramic green sheet 21 formed onto the surface of a base film 17a is contact- bonded with the surface of a ceramic green laminate 18 by a pressure disc 23. The electrode-filled ceramic green sheet 21 on the base film 17a is transferred onto the surface of the ceramic green laminate 18 by a hot plate 23, thus forming an electrode-filled ceramic green sheet 26 composed of electrode ink films 24 transferred and a ceramic green sheet 25.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention relates to a method for manufacturing multilayer ceramic electronic components such as multilayer ceramic capacitors, which are widely used in electrical products such as monitors, videotape recorders, and liquid crystal televisions, particularly by a transfer method. It is also widely used in multilayer ceramic substrates and laminated varistors.

It can also be used when manufacturing multilayer ceramic electronic components such as multilayer piezoelectric elements.

BACKGROUND OF THE INVENTION In recent years, in the field of electronic components, as the density of circuit boards has increased, there has been a desire for monolithic ceramic capacitors and the like to be made smaller and have higher performance. Here, the explanation will be given using a multilayer ceramic capacitor as an example.

FIG. 7 is a cross-sectional view of a part of the multilayer ceramic capacitor. In FIG. 7, 1 is a ceramic dielectric layer, 2 is an internal electrode, and 3 is an external electrode. The internal electrodes 2 are alternately connected to two external electrodes 3.

Conventionally, multilayer ceramic capacitors have been manufactured by the following manufacturing method. First, a predetermined electrode ink is printed on a ceramic green sheet cut into a predetermined size, the electrode ink is dried to form an electrode ink film, and the required number of ceramic green sheets with this electrode ink film formed are printed. They were laminated to form a cefmic raw laminate, and this ceramic raw laminate was cut into a desired shape, fired, and completed by attaching external electrodes.

However, with this method of directly printing electrode ink on a green ceramic sheet, when printing electrode ink on a green ceramic sheet, the green ceramic sheet is swollen and corroded by the solvent contained in the electrode ink. I have a problem with friends. Furthermore, the thinner the ceramic raw sheet becomes.

Since pinholes are likely to occur in the raw ceramic sheet itself, there is a problem in that short circuits occur between internal electrodes.

For this reason, several approaches have been taken in the past to try to solve this problem by embedding an electrode ink film inside the green ceramic sheet.

FIG. 8 is a diagram for explaining an example of a conventional method for manufacturing a ceramic green sheet with embedded electrodes. In FIG. 8, 4 is a base film, 6 is an electrode ink film, and 6 is a raw ceramic sheet.

The electrode ink film 5 can be embedded in the green ceramic sheet 6 as shown in FIGS. 8(&) to (C). Such an electrode embedding method is described in Japanese Patent Application Laid-Open No. 56-1082.
As in Japanese Patent Application No. 44, there is a method in which an electrode ink film is printed on a base film, and then a ceramic green sheet is formed thereon by a casting method. As shown in Japanese Patent Publication No. 40-19975, applying electrode ink,
After drying, there is a method of continuously applying a dielectric slurry and peeling it off from the support to obtain an electrode-embedded ceramic green sheet. However, since the electrode-embedded ceramic raw sheets made by these methods are peeled from the base film and laminated, as the thickness of the film becomes thinner, the mechanical strength is extremely reduced. It becomes unmanageable. For this reason, it was not possible to make the layer thinner than 20 microns. In addition, unevenness caused by the electrode ink film was likely to occur on the surface of the electrode-embedded ceramic green sheet.

According to Japanese Patent Publication No. 59-172711, a multilayer ceramic capacitor is manufactured by embedding electrodes formed on a base film in a raw ceramic sheet, laminating the base film together, and firing. However, in order to bake the base film together, it is necessary to use a very thin base film with a thickness of about 1.6 to 14 microns. Furthermore, the amount of base film fired increases in proportion to the number of laminated layers, making delamination more likely to occur. For this reason, the base film needs to be made thinner as the number of layers increases. In addition, a thin base film like lint is difficult to handle and has poor mechanical strength. Therefore, in addition to delamination, this method also poses a problem in lamination accuracy.

Problems to be Solved by the Invention Therefore, in the conventional manufacturing method, even when the electrode-embedded ceramic raw sheet is peeled and laminated after producing the electrode-embedded ceramic raw sheet, the electrode-embedded ceramic raw sheet becomes thin. It was difficult to handle when the ceramic raw material was used, and there was a limit to how thin the raw ceramic sheet could be.

Furthermore, simply pressing and transferring the raw ceramic sheet with embedded electrodes together with the base film has the problem of poor transferability.

In view of the above-mentioned problems, the present invention laminates even thin ceramic raw sheets of 20 microns or less together with the base film, so that it can be handled and transferred while maintaining mechanical strength, and furthermore, the electrode-embedded ceramic raw sheets can be crimped. The present invention provides a method for manufacturing a laminated ceramic electronic component with excellent lamination properties by allowing the base film to be easily peeled off after the base film is peeled off.

Means for Solving the Problems In order to solve the above problems, the method for manufacturing a laminated ceramic electronic component of the present invention provides a method for manufacturing a laminated ceramic electronic component according to the present invention, in which at least the part where the releasable resin is transferred onto the base film on which the electrode ink film is formed. After forming the ceramic slurry partially on the surface of the base film, applying a ceramic slurry and drying it, creating a raw ceramic sheet with embedded electrodes on the base film, and then peeling the raw ceramic sheet with embedded electrodes from the base film. Instead, after pressing onto another ceramic green sheet or another electrode ink film, only the base film is peeled off, and the electrode-embedded ceramic green sheet is removed from the part where the peelable resin is formed on the base film. , it is equipped with a structure in which it is transferred onto another ceramic raw sheet or another electrode.

Effect of the Invention With the above-described configuration, the present invention prevents the occurrence of negative effects such as erosion and swelling of the green ceramic sheet due to the solvent contained in the electrode ink and syjitsu due to drying of the electrode ink. It can be prevented. Also.

After pressing the green ceramic sheet with the electrode ink film embedded onto another ceramic green sheet or another electrode ink film without peeling off the base film, only the base film is peeled off, and the ceramic green sheet with the electrode embedded therein is pressed. By transferring the raw sheets, it becomes easier to handle the electrode-embedded ceramic raw sheets when laminating them, and the lamination accuracy can also be improved. By using a peelable resin, the base film can be easily peeled off after the electrode-embedded raw ceramic sheet is transferred, thereby improving lamination properties. When the electrode ink film surface is covered with the same removable resin, it is possible to suppress the occurrence of coating unevenness during the application of ceramic slurry, and to produce a ceramic green sheet with embedded electrodes with excellent uniformity. Can be done.

EXAMPLE Hereinafter, a method of manufacturing and a method of laminating a multilayer ceramic capacitor according to an example of the present invention will be described with reference to the drawings.

FIG. 1 is a diagram for explaining an example of a method for manufacturing a ceramic raw sheet with dense electrodes embedded therein used for manufacturing the multilayer ceramic electronic component of the present invention.

In FIG. 1, 11 is a base film, 12 is an electrode ink film, 13 is a peelable resin, and 14 is a raw ceramic sheet. Next, a more detailed explanation will be given using FIGS. 1(a) to (0). First, as shown in FIG. 1(a), an electrode ink film 12 is formed on a base film 11. here,
In addition to screen printing, methods for forming the electrode ink film 12 include offset printing (including planography, letterpress, and intaglio), and electrodeposition.

A plating method or the like can be used. Next, Figure 1(b)
As shown in FIG. 2, a releasable resin 13 is partially formed on the base film 11 on and around the electrode ink film 12 formed on the surface of the base film 110 by a method such as coating. Here, the releasable resin 13 specifically refers to silicone resin, fluororesin, wax, etc., and by forming a layer of these resins on the surface of the base film 11, a base that is difficult to wet (has excellent releasability) can be formed. A film surface can be provided. Further, the releasable resin 13 may be formed in a step after the electrode ink film 12 is formed on the base film 11. Moreover, it is not necessarily necessary to form the releasable resin 13 on the electrode ink film 12, and it is sufficient if it is formed on at least the portion of the base film 11 to be transferred. Next, as shown in FIG. 1(C),
A dielectric slurry is applied, and after drying, a green ceramic sheet 14 is formed, and then a green ceramic sheet with embedded electrodes is formed on top of this 5.

FIGS. 2 and 3 are diagrams for explaining how the electrode-embedded ceramic raw sheets of the present invention are laminated. In Fig. 2 and Fig. 3, 15,151L is a peelable resin, 16ti stand, 17,171L is a base film, 18
is a ceramic raw laminate, 19. ISl is an electrode ink film,
20 is a green ceramic sheet, and 21 is a green ceramic sheet with embedded electrodes. This green ceramic sheet 21 with embedded electrodes is composed of an electrode ink film 191L and a green ceramic sheet 2o. In addition, 22 is a heater, 23
is a pressure plate, which can be heated by a heater 22 if necessary. 24 is the transferred electrode ink film, 26
26 is a transferred electrode-embedded ceramic green sheet, which is composed of the transferred electrode ink film 24 and the transferred ceramic green sheet 26. The arrow indicates the direction in which the pressure plate 23 moves. Moreover, the peelable resin 16 is the electrode ink film 1sa (or base film 517a).
and the raw ceramic sheet 2o.

Next, explanation will be given using FIG. 2. First, the pressure plate 23 is placed on the side of the base film 17a on which the electrode-embedded ceramic green sheet 21 is not formed. Here, pressure plate 2
3ti may be heated by the heater 22 if necessary.

On the other hand, the base film 17 and the ceramic raw laminate 18 fixed on the table 1e are placed on the side of the base film 174 on which the electrode embedded ceramic raw sheet 21 is formed.

At this time, it is transferred to the surface of the ceramic raw laminate 18.

The electrode ink film 19 is formed by an appropriate method such as printing. Here, the electrode ink film 19 does not necessarily have to be formed on the surface of the raw ceramic laminate 18.

Furthermore, the base film 17 may also be used as necessary. Next, from the state shown in FIG. 2, the electrode-embedded ceramic raw sheet 21 formed on the surface of the base film 17 &
Crimp. At this time, heat may be applied by the heater 22.

Next, explanation will be given using FIG. 3. This FIG. 3 is a diagram after the electrode-embedded ceramic green sheet 21 shown in FIG. 2 has been transferred. That is, as shown in FIG. 3, the electrode-embedded green ceramic sheet 21 on the base film 17L is transferred to the surface of the ceramic green laminate 18 by the hot platen 23, and thereby the transferred electrode ink film 24 and the transferred electrode ink film 24 are transferred to the surface of the ceramic green laminate 18. A transferred electrode-embedded ceramic green sheet 26 having the same structure as the ceramic green sheet 25 is formed. Here, the releasable resin 15 is a releasable resin 15 that is partially transferred to the electrode-embedded ceramic raw sheet 21! It is separated into L and the removable resin 15 that remains on the base film 17a.

Moreover, FIGS. 4 and 6 are diagrams for explaining modified examples of the lamination. Here, the ceramic raw sheet 201L formed on the base film 17b is pressed onto the surface of the ceramic raw laminate 180 on which the electrode ink film 19 has been formed, and after forming the transferred ceramic raw sheet 26&, the electrode is embedded. The raw ceramic sheet 21 is heat-pressed.

Here, it is also possible to stack multiple layers by repeating the steps shown in FIGS. 2 and 3 and the steps shown in FIGS. 4 and 6.

Next, FIG. 6 is a diagram for explaining another modification of the lamination. In FIG. 6, 27 is a roller, which can be heated by a heater 22a if necessary. When the electrode-embedded ceramic raw sheet 21 passes between the ceramic raw laminate 18 and the roller 27, the electrode-embedded ceramic raw sheet 21 passes through the ceramic raw laminate 18.
The transferred electrode-embedded ceramic green sheet 26 is obtained. According to this method, the electrode-embedded ceramic green sheet can be transferred continuously.

Next, it will be explained in more detail. First, as the electrode ink for forming the electrode ink film, commercially available electrode ink (
Pd paste for internal electrodes of multilayer capacitors) was used, diluted with a solvent to an appropriate viscosity (hereinafter referred to as Pd paste).
(simply called electrode ink).

Next, the electrode 192L (and ceramic raw sheet 20)
As the base film 17a for the
Using a polyethylene terephthalate film (hereinafter referred to simply as the base film) of 40 m
0 mesh stainless steel screen (emulsion layer thickness is 1
0 micron) by screen printing method,
The electrode ink described above was printed continuously at regular intervals. Here, the shape of the electrode used was 3.5 x 1.0 mm. To dry the electrode ink after printing, a far-infrared belt furnace is connected next to the printing machine.
The solvent in the electrode ink was evaporated to form an electrode ink film. In this way, a product corresponding to FIG. 1 (1L) was manufactured.

Next, a releasable resin was partially formed on the base film so as to cover the electrode ink film in the portion to be transferred. Here, the release resin used was diluted silicone resin (silicon release agent manufactured by Shin-Etsu Chemical Co., Ltd.), and the flexographic printing machine (
After printing an area corresponding to the area to be laminated using a rubber letterpress printing machine, heat curing is performed to fix the releasable resin formed on the surface in contact with the base film to the base film. b) The equivalent was produced. In this way, part of the release resin is chemically fixed to the surface of the base film, and part is sandwiched between the electrode ink film and the green ceramic sheet.

Next, how to make dielectric slurry will be explained. First, a thermoplastic resin containing polyvinyl butyral resin is added to a solvent and a plasticizer, and after sufficiently dissolving, a dielectric powder mainly composed of barium titanate with a particle size of approximately 1 micron is dispersed in this, and the dielectric It was made into a slurry.

Next, this dielectric slurry was continuously applied onto a plurality of electrodes. Here, the dielectric slurry was applied using a commercially available continuous coating machine, and the dielectric slurry was dried using a warm air circulation type dryer to produce an electrode-embedded CETSUMIC green sheet. Here, using a micrometer,
When the thickness of only the ceramic raw sheet of the completed electrode-embedded ceramic raw sheet was measured, the thickness of the ceramic raw sheet was 16 microns.

Next, a method of laminating a multilayer ceramic capacitor using this electrode-embedded ceramic green sheet 21 will be described. First, a ceramic raw laminate 18 having a thickness of 200 microns on which no electrodes were formed was fixed together with the base film 17 on the stand 16 shown in FIG. 1. As shown in FIGS. 3 and 4, as many electrode-embedded green ceramic sheets 21 as required to be laminated were transferred onto this layer. Here, the transfer was performed using a pressure plate 23 from the side of the base film 171L under the condition of a pressure of 16 kilograms per square centimeter, and after transferring the electrode-embedded ceramic green sheet 21, the base film 171L was peeled off. . Here, the part of the removable resin formed on the base film surface is heat-cured to the base film, so when transferring the electrode-embedded ceramic green sheet, it remains on the base film side.
Not transcribed.

Thereafter, this process was repeated so that the electrodes were alternately shifted as shown in FIG. 7, so that there were 61 layers of electrodes. Finally, in order to prevent warping during firing and increase mechanical strength, a raw ceramic sheet with no electrodes formed is made to a thickness of 2.
00 micron equivalent was transferred. The thus obtained laminate was cut into chips of 2.4 x 1.6 mm, and then baked at 1300° C. for 1 hour.

Furthermore, in order to examine the influence of the solvent contained in the electrode ink, the electrode ink was printed directly onto the raw ceramic sheet as a conventional example (1). This is done by directly printing the same electrode ink as an internal electrode by screen printing as shown in Figure 8 on a raw ceramic sheet formed on a PET film with the same composition and thickness as mentioned above, and drying it to form an electrode. It was made into a raw ceramic sheet. Next, the raw ceramic sheet on which the electrodes were formed was transferred together with the base film, the base film was peeled off, and the electrodes were transferred and laminated to form 61 layers. In addition, all other conditions were the same as those described above.

Here, the number of samples was n=100. Next, external electrodes were formed using a conventional method, and the rate of seam formation was examined. The results are shown in Table 1 below.

As described above, by using the method for manufacturing multilayer ceramic electronic components according to the present invention, since the electrode ink is dried, both the sheet generation rate and the delamination sin generation rate are greatly improved compared to the conventional method. I understand. In addition, the reason why the method of the present invention has a lower incidence of delamination (delamination) in Table 1 is that by embedding the electrode ink film in the green ceramic sheet, unevenness during lamination caused by the electrode ink film is reduced. This is thought to be due to the fact that the number of cases has decreased.

Next, after forming an electrode ink film on the base film,
We investigated the effect of applying a releasable resin to produce a raw ceramic sheet with embedded electrodes. here.

As a conventional example (2), a raw ceramic sheet with embedded electrodes was produced on a base film coated with a releasable resin and cured. That is, the above-mentioned release resin was applied on the above-mentioned base film in advance, and after curing, the above-mentioned electrode ink was printed to form an electrode ink film, and then an electrode-embedded Cefmic raw sheet was produced in the same manner. Furthermore, as an example in which no releasable resin was used in Conventional Example (3), the electrode ink described above was printed on the base film to form an electrode ink film, and then a raw ceramic sheet with embedded electrodes was produced in the same manner.

Here, regarding the evaluation of the lamination workability (laminability) of the electrode-embedded ceramic raw sheet, it is necessary to consider both adhesiveness and peelability as shown in Table 2 below. In other words, even if only the adhesiveness is excellent, if the electrode-embedded ceramic raw sheet is difficult to peel off from the base film, the lamination properties will be poor. Therefore, the embodiments of the present invention and each conventional example are summarized in Table 2 below. In addition,
In Table 2, the printability of the electrode ink refers to the printability of the electrode ink on the base film.

Adhesion refers to the adhesion when transferring the electrode-embedded ceramic raw sheet to another ceramic raw sheet, and releasability refers to the peelability of the base film after transferring the electrode-embedded ceramic raw sheet to another ceramic raw sheet. .

<Table 2> From Table 2, it can be seen that the method of the present invention is superior in workability compared to conventional examples (2) and (3). In particular, the conventional example (
If a release resin is previously formed on the base film surface as in 2), the electrode ink itself will be repelled by the release resin, resulting in very poor printability.

On the other hand, when laminating raw ceramic sheets with embedded electrodes without using any peelable resin, there is a problem that the base film is difficult to peel off after transfer, resulting in poor workability. For this reason, there is a limit to reducing the time required for lamination.

Furthermore, in the case of Conventional Example (3), the uniformity of the finished ceramic green sheet was poor compared to the method of the present invention. This occurred because in conventional example (3), the dielectric slurry was applied directly to the base film surface on which the electrode ink film was formed, so the wettability of the dielectric slurry to the electrode ink film and the base film surface was different. considered to be a problem.

In addition, in the present invention, since the removable resin is provided only in the laminated parts (transferred parts), even when electrode-embedded ceramic raw sheets are continuously formed on a base film, only the necessary parts can be easily transferred and laminated. This made it possible to manufacture ceramic raw sheets with embedded electrodes with high productivity.

Further, for coating the dielectric slurry, a coating machine capable of continuous coating, such as a reverse coater, gravure coater, bar coater, or doctor blade coater, can be used.

Further, as the resin used in manufacturing the ceramic raw sheet used in the present invention, various thermoplastic resins such as acrylic resin, vinyl resin, cellulose derivative resin, etc. can be used in addition to PVB resin.

In addition, even if the resin is a curable resin or polymerizable resin, by adjusting the curing conditions 1 polymerization conditions appropriately, for example, making it rubber-like, the surface can be made sticky and used as a seed thermoplastic resin. You can also do that.

In the present invention, the transferability can also be improved by using heat, photoelectron beams, microwaves, X-rays, etc. during transfer. By changing the packaging, the type of each resin, the type and amount of plasticizer added, it is possible to increase the speed of lamination while maintaining storage stability.

In addition to the polyethylene terephthalate film, the base film may also be a resin film such as polypropylene or a thin metal film.

Furthermore, the manufacturing method of the present invention can be applied not only to the multilayer ceramic capacitors described in the above embodiments but also to other multilayer ceramic electronic components such as multilayer ceramic substrates and multilayer varistors.

Effects of the Invention As described above, the present invention provides a method of applying a ceramic slurry to a base film on which an electrode ink film is formed, after partially forming a releasable resin on the surface of the base film at least in a portion to be transferred. After drying, a green ceramic sheet with embedded electrodes is produced on the base film, and then the green ceramic sheet with embedded electrodes is crimped onto another green ceramic sheet or another electrode without peeling off from the base film. After that, only the base film is peeled off, and the electrode-embedded green ceramic sheet of the part where the peelable resin is formed on the base film is transferred onto another ceramic green sheet or another electrode ink film, Since the electrode is dried, the negative electrode force of the solvent contained in the electrode ink is reduced, and since the raw ceramic sheet is handled together with the support, it will not be damaged during handling, and the electrode can be placed in the ceramic slurry. The embedding prevents unevenness during lamination, and the use of a peelable resin improves lamination by making it easier to peel off the base film after transferring the υ electrode-embedded ceramic raw sheet. Can be done.

[Brief explanation of the drawing]

FIG. 1 is a diagram for explaining an example of a method for manufacturing a raw ceramic sheet with embedded electrodes for use in manufacturing a laminated ceramic electronic component of the present invention, and FIGS. 2 and 3 are raw ceramic sheets with embedded electrodes of the present invention. 4 and 6 are diagrams for explaining a modification of the lamination, and FIG. 6 is a diagram for explaining yet another modification of the lamination. FIG. 7 is a cross-sectional view of a part of a multilayer ceramic capacitor, and FIG. 8 is a diagram for explaining an example of a conventional method for manufacturing a ceramic green sheet with embedded electrodes. 11... Base film, 12... Electrode ink film, 13... Peelable resin, 14...
・Ceramic raw sheet, 15.15m... Peelable resin, 16. River... Stand, 17, 17a, 17b...
... Base film, 18 ... Ceramic raw laminate % 19,191L River ... Electrode ink film, 20
．． 20 tons...Setsumik raw sheet, 21...
...Ceramic raw sheet with embedded electrodes, 22.22! L
・・・heater, 23・kawa...silence, 24...
Transferred electrode, 25. 25. Transferred ceramic green sheet, 26... Transferred electrode-embedded ceramic green sheet, 27... Heat roller. Name of agent: Patent attorney Shigetaka Awano TL or one person!
! -Base film/Z...- to spear in the ts-Ichibari Ugly A Intestine 14-Zeramitsuku Lord F/2' 16th, 75L □-'! ! I B a M'r MW
16- Meeting 1'1. /'Frue Base Philem! 8- Cerami puffer main laminated body 19- Den' Tomb Ingo Hou z2- Heater o... - Thick l1lr Yamari 24- Enjoy & Copied r; Den'i Inya Kyo 25- Transf
Figure Is... - Italy 1 glandular tree scale 16 - - Base 17, /7 - - Base film lδ゛ - Zeramy 77 principal term 1 body IQ, lqa, ″-゛Peeking Goku Seikokugo Sakura W-Zeramic Main Sheet 2f-(Kiiame Father, Is-Zorami Tsuku Main Sheet t2
-・-11ri23-・-jJa7iL Figure Figure Figure Figure

Claims (2)

[Claims] (1) On a base film on which an electrode ink film is formed, a removable resin is partially formed on the surface of the base film at least in the portion to be transferred, and then a ceramic slurry is applied, and after drying, the base film is coated with a ceramic slurry. A raw ceramic sheet with embedded electrodes is made, and then the raw ceramic sheet with embedded electrodes is crimped onto another raw ceramic sheet or another electrode without being peeled off from the base film, and then only the base film is peeled off. manufacturing a laminated ceramic electronic component, characterized in that the part of the electrode-embedded ceramic green sheet on which the releasable resin is formed on the base film is transferred onto another ceramic green sheet or another electrode ink film; Method. (2) The method for manufacturing a multilayer ceramic electronic component according to claim 1, wherein the peelable resin contains at least one of silicone resin, fluororesin, and wax.