JP5038216B2 - Ceramic molded body, ceramic part, method for manufacturing ceramic molded body, and method for manufacturing ceramic part - Google Patents

Description

  The present invention relates to a ceramic molded body having a conductor embedded therein, a ceramic component, a method for manufacturing a ceramic molded body, and a method for manufacturing a ceramic component, and for example, a ceramic molded body capable of constituting a passive component having excellent high-frequency characteristics. The present invention relates to a ceramic part, a method for producing a ceramic molded body, and a method for producing a ceramic part.

  When manufacturing passive components using a dielectric substrate, a conductor pattern is formed on a green sheet containing ceramic powder and resin by laminating and integrating them, then molding and firing. (For example, refer to Patent Documents 1 and 2).

  In this case, since the conductor pattern is formed in a convex shape on the green sheet, no pressure is applied to the vicinity of the periphery of the conductor pattern when the green sheet is laminated. The end portion is crushed and the electrical characteristics of the conductor pattern are deteriorated. In addition, because of these problems, since the thickness of the conductor pattern cannot be increased, there is a limit to lowering the resistance value, and there is a limit to improving high-frequency characteristics.

  Therefore, conventionally, in order to solve the above-described drawbacks, a conductive paste is printed on a substrate such as a resin film or a green sheet, and then a slurry composed of a ceramic powder and a resin is applied, followed by cationic solidification. There has been proposed a method of embedding a conductor pattern in a green sheet by immersing it in a bath to form a gelled green sheet (for example, see Patent Document 1).

  In another conventional example, a method of mixing a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin in a conductor paste is proposed in order to suppress deformation of the conductor pattern (see, for example, Patent Document 2). .

  In still another conventional example, a coil-shaped metal wire is installed in a casting mold, and further, a ceramic slurry is filled in the casting mold, and the metal wire is encapsulated with the ceramic slurry. Thereafter, by drying, an electronic component in which a coil made of a metal wire is included in a ceramic molded body is obtained (for example, see Patent Document 3).

Japanese Patent Laid-Open No. 2005-1279 JP-A-8-167537 JP-A-11-126724

  By the way, when a slurry containing ceramic powder and a thermoplastic resin and a conductor paste containing a thermoplastic resin are used, cracks occur in the vicinity of the conductor in the ceramic molded body due to the large shrinkage that occurs when the slurry dries. As a result, there is a problem in the integration of the ceramic molded body and the conductor, or the green sheet becomes uneven due to the influence of the convex shape of the conductor. In addition, since the thermoplastic resin contained in the conductor paste is easily dissolved in a solvent, there is a problem that when forming a ceramic molded body, the conductor is dissolved in the ceramic and the pattern shape of the conductor is broken.

  Moreover, in patent document 1, it is necessary to perform formation of the conductor pattern on a green sheet, application | coating of a slurry, immersion to a cationic coagulation bath, and drying for every layer, and a man-hour is accompanied by multilayering of a conductor pattern. There is a problem of increasing.

  In Patent Literature 2, since a conductor pattern formed by printing on a green sheet is laminated and integrated and then pressed, pressure is applied in the vicinity of the periphery of the conductor pattern as in Patent Literatures 1 and 2. However, there is a risk of peeling after lamination.

  The proposed example described in Patent Document 3 is convenient for embedding elements such as resistors and coils in a ceramic molded body, but has a problem that it cannot be applied to multilayer conductor patterns.

  The present invention has been made in consideration of such problems, and there is no peeling or collapse of the conductor pattern, the thickness of the conductor pattern can be increased, the resistance value can be reduced, and the high-frequency characteristics can be easily improved. An object of the present invention is to provide a ceramic molded body, a ceramic part, a method for manufacturing a ceramic molded body, and a method for manufacturing a ceramic part.

  First, the present inventors produced a ceramic molded body (ceramic molded body according to a reference example) having the following configuration before obtaining the ceramic molded body according to the present invention.

  That is, a conductor paste containing a metal powder and a binder (thermosetting resin precursor) is patterned and then cured, and the thermosetting resin precursor, ceramic powder and solvent are mixed. The ceramic molded body which concerns on the reference example which has a ceramic molded part obtained by hardening | curing, after supplying a slurry so that a conductor molded part may be coat | covered was obtained.

  However, it has been found that the ceramic molded body according to this reference example has the following problems.

  In the ceramic molded body according to the reference example, the slurry in which the thermosetting resin precursor, the ceramic powder, and the solvent are mixed is supplied so as to cover the conductor molding portion. The binder in the molded part may be dissolved. In order to suppress this, a conductor paste using a thermosetting resin precursor (for example, a resol type phenol resin) as a binder is cured to form a conductor molding part. There is a problem in that it is difficult to control the dimensions and the plate slippage.

  Regardless of whether a thermosetting resin precursor or thermoplastic resin precursor is used as the binder contained in the conductor paste, it suppresses cracking of ceramic parts after firing and peeling at the electrode-ceramic interface. In order to achieve this, it is necessary to match the firing shrinkage ratio of the conductor molding part with the ceramic molding part. For example, when manufacturing high-frequency circuit components (filters, couplers, baluns, antennas, etc.), it is desirable to thicken the inner layer conductor and to make the edge of the inner layer conductor rectangular or semicircular for the purpose of reducing conductor loss at high frequencies. However, in order to obtain such an inner layer conductor, it is necessary that the printed film thickness of the conductor paste is thick and the edge of the printed pattern is rectangular or semicircular.

  In order to increase the printed film thickness of the conductive paste and make the edges of the printed pattern rectangular or semicircular, it is necessary to reduce the amount of binder in the conductive paste as much as possible in order to suppress the fluidity of the printed pattern. On the other hand, if the amount of the binder in the conductor paste is reduced, the firing shrinkage rate of the conductor molding portion becomes small, and it becomes difficult to match the firing shrinkage rate with the ceramic molding portion.

  Furthermore, if a low melting point metal (Ag, Cu, Au, etc.) is used for the conductor molded part, the firing shrinkage start temperature of the conductor molded part tends to be lower than the firing shrinkage start temperature of the ceramic molded part, and thus firing shrinkage starts. With the aim of raising the temperature, agglomerated powder or coarse powder is used as the metal powder contained in the conductor paste, but in this case, the interface between the conductor molded part and the ceramic molded part tends to become rough, resulting in a high-frequency circuit. When used as a component, there was a problem that the conductor loss deteriorated.

  Accordingly, the ceramic molded body according to the first aspect of the present invention is a slurry in which a conductor paste containing a metal powder and a binder is patterned and then cured, and a resin, ceramic powder and solvent are mixed. A ceramic molded body having a ceramic molded part obtained by curing after being supplied so as to cover the conductor molded part, and a firing shrinkage rate adjusting film at an interface between the conductor molded part and the ceramic molded part Is formed.

  In the first aspect of the present invention, the firing shrinkage rate adjusting film may be an organic film (CVD or printing) or an inorganic film (CVD or sputtering). In this case, the organic film included in the baking shrinkage rate adjusting layer may be a phenol resin, an epoxy resin, a polyurethane resin, or a polyparaxylylene resin. Alternatively, the inorganic film included in the firing shrinkage rate adjusting layer may be a silica film.

  In the first aspect of the present invention, the ceramic molding part may be obtained by curing the slurry after applying the slurry so as to cover the conductor molding part molded on the substrate.

  In the first aspect of the present invention, the metal powder contained in the conductor paste is at least one powder of silver (Ag), gold (Au), and copper (Cu) based metals, and is contained in the conductor paste. The binder may be a thermoplastic resin precursor or a thermosetting resin precursor. In this case, the thermosetting resin precursor contained in the conductor paste may be a phenol resin.

  In the first aspect of the present invention, the resin contained in the slurry may be a thermosetting resin precursor and a polyurethane resin precursor.

  Next, the ceramic component according to the second aspect of the present invention is obtained by firing the ceramic molded body according to the first aspect of the present invention described above.

  Next, a method for producing a ceramic molded body according to a third aspect of the present invention includes a conductor forming step of patterning a conductor paste containing metal powder and a binder, and then forming a conductor molding portion formed by curing, and the conductor A firing shrinkage rate adjusting film forming step for forming a firing shrinkage rate adjusting film on part or all of the surface of the molding part, and a slurry in which a thermosetting resin precursor, ceramic powder and a solvent are mixed, A slurry supply step for supplying the conductive molded portion together with the adjustment layer, and a slurry curing step for producing a ceramic molded body by curing the slurry into a ceramic molded portion. .

  In the third aspect of the present invention, the firing shrinkage rate adjusting film may be an organic film (CVD or printing) or an inorganic film (CVD or sputtering). In this case, in the firing shrinkage rate adjusting film forming step, the organic film may be formed on a part or all of the surface of the conductor molding portion by a CVD method or a printing method. Alternatively, the inorganic film may be formed on a part or all of the surface of the conductor molding portion by a CVD method or a sputtering method.

  In the third aspect of the present invention, the thermosetting resin precursor used in the slurry may be a polyurethane resin precursor.

  In the third aspect of the present invention, the conductor forming step forms the conductor molded portion on a base, and the firing shrinkage adjustment film forming step is performed on the conductor molded portion formed on the base. The firing shrinkage rate adjusting film may be formed, and in the slurry supplying step, the slurry may be applied onto the base together with the firing shrinkage rate adjusting layer so as to cover the conductor molding portion.

  In the third aspect of the present invention, the conductor forming step forms a conductor molded portion on the film, and the firing shrinkage ratio adjusting film forming step is performed on the conductor molded portion formed on the film. A firing shrinkage rate adjustment film is formed, and in the slurry supplying step, the conductor formed portion and the film on which the firing shrinkage rate adjustment film is formed are placed in a casting mold, and the slurry is cast into the casting mold. You may make it.

  In this case, in the slurry supply step, when the film is installed in the casting mold, the film and the other film are combined with the surface on which the conductor molding portion and the firing shrinkage adjustment film are formed, and the other film. The film may be opposed, and a spacer may be interposed between the film and the other film, and the slurry may be poured into a space formed by the spacer. Further, the peeling force of the release agent applied to the surface of the film may be different from the release force of the release agent applied to the surface of the other film.

  In the third aspect of the present invention, the metal powder contained in the conductor paste is at least one powder of silver (Ag), gold (Au), and copper (Cu) based metals, and is contained in the conductor paste. The binder may be a thermoplastic resin precursor or a thermosetting resin precursor. In this case, the thermosetting resin precursor contained in the conductor paste may be a phenol resin. Furthermore, a self-reactive resole resin may be used.

  Next, a method for manufacturing a ceramic component according to a fourth aspect of the present invention is a method for manufacturing a ceramic component, comprising: a step of manufacturing a ceramic molded body; and a step of firing the manufactured ceramic molded body. The step of producing a ceramic molded body includes a conductor forming step of patterning a conductor paste containing a metal powder and a binder, and then forming a conductor molded portion, and a part or all of the surface of the conductor molded portion. A step of forming a firing shrinkage rate adjusting film on the surface, and a slurry in which a thermosetting resin precursor, a ceramic powder and a solvent are mixed, and the conductor molding part are coated together with the firing shrinkage rate adjusting layer. A slurry supply step for supplying the ceramic molded body, and a slurry curing step for producing a ceramic molded body by curing the slurry into a ceramic molded portion. And wherein the Rukoto.

  As described above, according to the ceramic molded body, the ceramic part, the ceramic molded body manufacturing method, and the ceramic part manufacturing method according to the present invention, the conductor pattern is not peeled or collapsed, and the thickness of the conductor pattern is increased. Therefore, it is possible to easily reduce the resistance value and improve the high frequency characteristics.

  Embodiments of a ceramic molded body, a ceramic part, a ceramic molded body manufacturing method, and a ceramic part manufacturing method according to the present invention will be described below with reference to FIGS.

[First Embodiment]
First, as shown in FIG. 1, the ceramic molded body according to the first embodiment (hereinafter referred to as the first ceramic molded body 10 </ b> A) covers the conductor molded portion 12 and the conductor molded portion 12. The formed ceramic molded part 13 and the firing shrinkage rate adjusting film 14 formed at the interface between the conductor molded part 12 and the ceramic molded part 13 are included.

  The first ceramic molded body 10A can be manufactured as follows. That is, as shown in FIG. 2A, a conductor paste 15 containing at least one kind of resin and silver (Ag), gold (Au), or copper (Cu) -based metal is molded and cured into a predetermined shape to form a conductor. After forming the portion 12, the firing shrinkage rate adjusting film 14 is formed on the entire surface of the conductor molding portion 12.

  Thereafter, as shown in FIG. 2B, the conductor molding portion 12 having the surface on which the firing shrinkage rate adjusting film 14 is formed is placed in the casting mold 16, and the gel casting containing the thermosetting resin precursor, the ceramic powder, and the solvent is used. A first ceramic molded body 10A is obtained by casting a slurry (hereinafter referred to as slurry 18) into a casting mold 16 and then curing to form a ceramic molded portion 13 (see FIG. 2C). The casting mold 16 has no problem as long as the slurry 18 does not leak even if a part of the structure shown in cross section is open.

  The resin used for the conductor paste 15 may be either a thermoplastic resin precursor or a thermosetting resin precursor, but is preferably a thermosetting resin precursor. In this case, the thermosetting resin precursor is preferably a self-reactive resol type phenol resin.

  The thermosetting resin precursor used for the slurry 18 is preferably a polyurethane resin precursor.

  Further, an organic film or an inorganic film can be used as the firing shrinkage rate adjusting film 14.

  The conductor molding part 12 is obtained by forming a pattern of the conductor paste 15 by a printing method and then curing.

  Here, this preferable manufacturing method of the first ceramic molded body 10A will be described with reference to FIGS.

  First, as shown in FIG. 3A, the conductor paste 15 is patterned on the film 20 by a printing method and then cured to form the conductor molding portion 12 on the film 20. Thereafter, the surface of the conductor molding portion 12 on the film 20 (in this case, the upper surface and the side surface) is coated with the firing shrinkage rate adjusting film 14. When an organic film is used as the firing shrinkage adjustment film 14, it can be formed by, for example, CVD (chemical vapor deposition) or printing, and when an inorganic film is used, it can be formed by, for example, sputtering. During film formation by CVD or sputtering, a portion on the film 20 where the conductor molding portion 12 does not exist is masked to inhibit the formation of the baking shrinkage rate adjusting film 14 other than the conductor molding portion 12. Is preferred.

  Thereafter, as shown in FIG. 3B, the film 20 is placed in the casting mold 16 and the slurry 18 is cast into the casting mold 16, and then cured to form the ceramic molding portion 13. Thereby, the first ceramic molded body 10A is obtained (see FIG. 3C). In this case, as shown in FIG. 4A, since the first ceramic molded body 10A (the conductor molded body 12 is embedded) is placed on the film 20, the first ceramic molded body 10A is used as the film. By releasing from 20, the first ceramic molded body 10A in which the conductor molded portion 12 is embedded in the ceramic molded portion 13 is obtained as shown in FIG. 4B.

  The first ceramic molded body 10A may have a tape shape as a whole. In this case, as shown in FIG. 5, a plurality of first ceramic molded bodies 10A may be laminated to form a first laminated body 60, and the plurality of conductor molded portions 12 may be embedded in a three-dimensional structure.

  In addition, when laminating | stacking the said 1st ceramic molded object 10A, the adhesive paste which consists of an organic binder, ceramic powder, a plasticizer, and a solvent may be apply | coated and dried.

  Further, in the plurality of first ceramic molded bodies 10 </ b> A, a part of the solvent contained in the slurry 18 may remain. In this case, the cured first ceramic molded body 10A has flexibility. Therefore, even if a hard and fragile thermosetting resin precursor is used as a binder, it can be transported between processes as a flexible tape molded body, and a plurality of first ceramic molded bodies 10A can be laminated. In addition, there are no defects such as voids between the layers (improved layerability). The pressure and temperature at the time of stacking are appropriately set in consideration of delamination, deformation of the stacked body, and stacking deviation.

  In order to improve the releasability of the first ceramic molded body 10A from the casting mold 16, it may be as shown in FIGS. 6A to 7B. That is, as shown in FIG. 6A, after the conductor paste 15 is patterned on the film 20 by a printing method, it is cured to form the conductor molding portion 12 on the film 20, and further the firing shrinkage on the surface of the conductor molding portion 12 A rate adjusting film 14 is formed.

  Thereafter, as shown in FIG. 6B, when the film 20 on which the conductor molding portion 12 and the firing shrinkage rate adjusting film 14 are formed is placed in the casting mold 16, the film 20 and the other film 22 are connected to the conductor molding portion 12. The surface on which the film is formed and the other film 22 are opposed to each other, and a spacer 24 is interposed between the film 20 and the other film 22. And after pouring the slurry 18 in the space formed in the spacer 24, you may make it obtain the 1st ceramic molded object 10A by hardening and setting it as the ceramic molded part 13 (refer FIG. 6C). In this case, as shown in FIG. 7A, since the first ceramic molded body 10A is surrounded by the film 20, the other film 22 and the spacer 24, the first ceramic molded body 10A becomes the casting mold 16. It can be easily released from the casting mold 16 without being unnecessarily attached.

  Furthermore, if the release force of the release agent applied to the surface of the film 20 on which the conductor molding part 12 is formed differs from the release force of the release agent applied to the surface of the other film 22, it is always The film 20 (or 22) is easily peeled off, and release from the film 20 (or 22) is facilitated. FIG. 7B shows a state where the first ceramic molded body 10 </ b> A is released from the film 20, the other film 22, and the spacer 24.

  And the ceramic component (henceforth a 1st ceramic component) which concerns on 1st Embodiment can be obtained by drying 10 A of 1st ceramic molded bodies mentioned above, and baking after that.

  In the first ceramic molded body 10A (and the first laminated body 60) and the first ceramic component described above, the conductor molded portion 12 (electrode pattern or the like) is not peeled or collapsed by the conductor paste 15, and the thickness of the electrode pattern or the like is further reduced. Therefore, the resistance value can be reduced and the high frequency characteristics can be easily improved.

  In particular, since the firing shrinkage rate adjusting film 14 is interposed at the interface between the conductor molding part 12 and the ceramic molding part 13, the following effects are produced.

(1) The first ceramic molded body 10A supplies the slurry 18 in which the thermosetting resin precursor, the ceramic powder, and the solvent are mixed so as to cover the conductor molded part 12, but the conductor molded part 12 Since the firing shrinkage ratio adjusting film 14 is formed on the surface, the binder of the conductor molding portion 12 is not dissolved regardless of the type of the solvent of the slurry 18. Therefore, the shape of the conductor molding portion 12 (the shape at the time of printing) can be maintained, and the thickness control, the outer dimension control, and the plate slippage control of the printed matter (conductor pattern) by the conductor paste 15 are facilitated.

(2) Regardless of whether a thermosetting resin precursor or a thermoplastic resin precursor is used as the binder contained in the conductor paste 15, cracks in the ceramic parts after firing and peeling at the electrode-ceramic interface In general, it is necessary to match the firing shrinkage rate of the conductor molding portion 12 with the ceramic molding portion 13. However, in the first ceramic molded body 10 </ b> A, the firing shrinkage rate adjusting film 14 is formed on the surface of the conductor molding portion 12. Since the firing shrinkage rate adjusting film 14 absorbs the difference between the firing shrinkage rate of the conductor molding portion 12 and the firing shrinkage rate of the ceramic molding portion 13, cracks in the ceramic parts after firing and the electrode-ceramic interface are formed. Can be prevented from peeling off. Therefore, without worrying about the difference in firing shrinkage between the conductor molding part 12 and the ceramic molding part 13, for the purpose of thickening the printed film thickness of the conductor paste 15 and making the edge of the printing pattern rectangular or semicircular, The fluidity of the printed pattern can be suppressed (the amount of binder in the conductor paste is minimized). For example, high-frequency circuit components (filters, couplers, baluns, etc.) that reduce conductor loss at high frequencies can be easily produced. be able to.

(3) When a low melting point metal (Ag, Cu, Au, etc.) is used for the conductor molding part 12, the firing shrinkage start temperature of the conductor molding part 12 tends to be lower than the firing shrinkage start temperature of the ceramic molding part 13. For the purpose of raising the firing shrinkage start temperature, aggregated powder or coarse powder is used as the metal powder contained in the conductor paste 15, but in this case, the interface between the conductor molded part 12 and the ceramic molded part 13 becomes rough. easy. However, in the first ceramic molded body 10 </ b> A, since the firing shrinkage rate adjusting film 14 is interposed between the conductor molded portion 12 and the ceramic molded portion 13, the roughness of the interface is absorbed by the fired shrinkage rate adjusting film 14. Even when used as a high-frequency circuit component, the conductor loss does not deteriorate.

(4) In the first ceramic molded body 10A, a thermosetting resin precursor is used as the resin contained in the conductor molded portion 12, but the above-described (1) is used even if a thermoplastic resin precursor is used as the resin. ) To (3) can be obtained.

  Next, examples of the first ceramic molded body 10A, the first ceramic component, the method of manufacturing the first ceramic molded body 10A, and the method of manufacturing the first ceramic component will be described with reference to FIGS.

  In this embodiment, a casting mold 16 shown in FIG. 8 is used.

  The casting mold 16 can produce a plurality of (for example, three) first ceramic molded bodies 10A at a time.

  As shown in FIG. 8, the casting mold 16 includes one base 30, a plurality of plate members (first plate member 32 a to fourth plate member 32 d) placed on the base 30, and a fourth And an upper plate 34 placed on the plate member 32d.

  Furthermore, the base 30 has several (for example, three) rod members 36 on the upper surface thereof and on the portion adjacent to the first side surface and the portion adjacent to the second side surface (side surface facing the first side surface). Is provided. Each bar member 36 is provided on the upper surface of the base 30 so that the axial direction is the normal direction of the upper surface of the base 30.

  The first plate member 32a to the fourth plate member 32d and the upper plate 34 are provided with through holes for positioning (hereinafter referred to as positioning holes 38) in portions corresponding to the rod members 36 of the base 30, respectively. When the plate member 32 a to the fourth plate member 32 d and the upper plate 34 are placed on the base 30 in order, the bar member 36 of the base 30 is inserted through each positioning hole 38.

  The first film 20 and the spacer 24 are provided between the first plate member 32a and the second plate member 32b, between the second plate member 32b and the third plate member 32c, and between the third plate member 32c and the fourth plate member 32d. And the laminated body of the 2nd film 22 is inserted. A plurality of electrode patterns 40 are formed on the upper surface of the first film 20 by forming and curing the conductor paste 15, and a firing shrinkage rate adjusting film 14 is further formed on the surface of the electrode pattern 40.

  In the first film 20, the second film 22, and the spacer 24, the first ceramic molded body 10A produced in the casting mold 16 is unnecessarily attached to the first plate member 32a to the fourth plate member 32d of the casting mold 16. In particular, the first film 20 determines the shape of the lower surface of the first ceramic molded body 10A to be produced, and the second film 22 is the first ceramic molded body 10A to be produced. The shape of the upper surface of the is determined. The spacer 24 is formed in a substantially frame shape having an opening, and determines the area and height of the first ceramic molded body 10A. In the example of FIG. 8, the electrode pattern 40 formed on the first film 20 is formed in a substantially frame shape so as to surround the group from three sides. The spacer 24 may be made of the same material as the first film 20 and the second film 22, for example. The first film 20, the second film 22, and the spacer 24 are coated with a release agent on each surface so that the manufactured first ceramic molded body 10A can be easily separated.

  The first film 20, the second film 22, and the spacer 24 are provided with positioning holes 42, 46, and 44 in portions corresponding to the rod members 36 of the base 30.

  Further, a U-shaped notch 48 for injecting the slurry 18 is formed in the upper plate 34, and the second plate member 32b to the fourth plate member 32d also correspond to the U-shaped notch 48, respectively. A through-hole (hereinafter referred to as an injection hole 50) for injecting the slurry 18 is formed in the part.

  The first film 20, the second film 22, and the spacer 24 are also formed with notches 52 and injection holes (not shown) at portions corresponding to the injection holes 50 of the second plate member 32b to the fourth plate member 32d. ing.

  Therefore, when assembling the casting mold 16, for example, it is performed as follows.

  First, the first plate member 32 a is placed on the upper surface of the base 30. At this time, the rod member 36 of the base 30 is inserted through the positioning hole 38 of the first plate member 32a and placed. Then, the 1st film 20, the spacer 24, and the 2nd film 22 are accumulated and mounted on the 1st board member 32a. At this time, the rod member 36 of the base 30 is inserted and placed in the positioning holes 42, 44 and 46 of the first film 20, the spacer 24, and the second film 22. Hereinafter, similarly, the second plate member 32b is placed, the first film 20, the spacer 24, and the second film 22 are placed on the second plate member 32b, and further, the third plate member 32c. The first film 20, the spacer 24, and the second film 22 are placed on the third plate member 32c, and the fourth plate member 32d is placed. A plate 34 is placed. Thereby, the casting mold 16 is completed.

  In the casting mold 16, the first plate member 32a and the second plate member 32b, the second plate member 32b and the third plate member 32c, between the third plate member 32c and the fourth plate member 32d, respectively. A hollow portion surrounded by the film 20, the spacer 24, and the second film 22 is formed.

  Next, a method for producing the first ceramic molded body 10A and the first ceramic component using the casting mold 16 will be described with reference to FIGS.

  First, in step S <b> 1 of FIG. 9, the conductor paste 15 is printed on the first film 20 to form a plurality of electrode patterns 40.

  Specifically, the first film 20 is PET (polyethylene terephthalate) whose surface is coated with a silicone release agent. In order to suppress shrinkage and distortion during the heat curing of the conductor paste 15, the first film 20 is preliminarily annealed at a temperature of 150 ° C. for 10 minutes or more.

  Thereafter, a positioning hole 42 is formed in the first film 20 so that positioning at the time of lamination onto the casting mold 16 can be performed. Next, the conductor paste 15 is printed in a predetermined region on the upper surface of the first film 20 with reference to the positioning holes 42 to form a plurality of electrode patterns 40. The conductor paste 15 is, for example, a thermosetting silver (Ag) paste containing a resol type phenol resin. The Ag powder in the conductor paste 15 is a powder whose particle size is adjusted in order to bring close the firing shrinkage temperature characteristics upon simultaneous firing with the dielectric.

  Next, in step S2 of FIG. 9, the electrode pattern 40 formed on the first film 20 is heat-cured. That is, in order to cure the thermosetting Ag paste, a heat treatment is performed at 120 ° C. for 1 hour.

  Thereafter, in step S3, the surface of the electrode pattern formed on the first film 20 (in this case, the upper surface and the side surface) is coated with the firing shrinkage rate adjusting film 14. When an organic film is used as the firing shrinkage adjustment film 14, it can be formed by, for example, CVD (chemical vapor deposition) or printing, and when an inorganic film is used, it can be formed by, for example, sputtering.

  Thereafter, in step S4 of FIG. 9, the casting mold 16 is assembled, and the first film 20 on which the electrode pattern 40 and the firing shrinkage adjustment film 14 are formed is placed in the casting mold 16 together with the second film 22 and the spacer 24. . In the casting mold 16 of FIG. 8, the first plate member 32a and the second plate member 32b, the second plate member 32b and the third plate member 32c, between the third plate member 32c and the fourth plate member 32d, respectively. A film 20 is installed. Of course, the spacer 24 and the second film 22 are also laminated on the first film 20.

  On the other hand, in step S5 and step S6 of FIG. 9, a slurry 18 to be injected into the casting mold 16 is prepared.

  First, in step S5, a ceramic slurry is prepared. The ceramic slurry has a ceramic powder obtained by mixing titanium oxide or barium oxide powder and borosilicate glass as a sintering aid. That is, the ceramic slurry is 100 parts by weight of the above ceramic powder, 15 to 40 parts by weight of aliphatic dibasic acid ester, 0.5 to 10 parts by weight of triacetin, and 0.5 to 5 parts of polycarboxylic acid copolymer. It consists of a mixture with an organic dispersion medium consisting of 10 parts by weight (polycarboxylic acid acts as an organic dispersant).

  Thereafter, in step S6, 1 to 10 parts by weight of a modified product of polymethylene polyphenyl polyisocyanate as a gelling agent and 0.05 to 2.7 parts by weight of ethylene glycol as a gelling agent, and 6-dimethylamino as a reaction catalyst. After adding 0.03-0.3 weight part of -1-hexanol, it stirs and the slurry 18, ie, the slurry 18 for gel casting, is prepared.

  Next, in step S <b> 7, the slurry 18 is poured (cast) into the casting mold 16. Specifically, the slurry 18 is injected through the injection hole 50 (see FIGS. 8 and 10) of the fourth plate member 32 d exposed from the U-shaped notch 48 of the upper plate 34 in the casting mold 16. By this injection, the slurry 18 is filled in the plurality of hollow portions in the casting mold 16. Since the slurry 18 is a gel casting slurry, the slurry 18 is cured as it is in a state of being filled in the hollow portion to become the ceramic molded portion 13. As a result, for example, three first ceramic molded bodies 10 </ b> A are produced in the casting mold 16.

  Thereafter, in step S8, the casting mold 16 is disassembled, and the first ceramic molded body 10A is peeled off from the first film 20, the spacer 24, and the second film 22. Thus, the first ceramic molded body 10A, that is, the first ceramic molded body 10A (also referred to as ceramic tape 10A) in which the conductor molded portion 12 (with the firing shrinkage ratio adjusting film 14 formed on the surface) is embedded is completed. (See FIG. 10).

Next, in step S9 of FIG. 9, a plurality of ceramic tapes 10A are laminated to produce a first laminate 60 (see FIG. 10). At this time, pressure lamination is performed at a pressure of 5 to 100 kgf / cm ^{2 in} a state where the reactive functional groups of the ceramic tape 10A do not completely react (at room temperature, after 1 hour to 48 hours have elapsed after casting). The applied pressure is appropriately selected according to the strength of the ceramic tape 10A and the allowable stacking deviation.

When the pressing force at the time of lamination is small, the laminating deviation is small, but delamination of the fired body is likely to occur due to poor adhesion at the time of lamination. On the other hand, when the pressing force at the time of lamination is large, the above-mentioned delamination occurs. However, deformation and breakage due to the lamination pressure of the ceramic tape 10A are likely to occur. However, if it is the range of the applied pressure mentioned above, a stacking shift and delamination can be suppressed and it is preferable. If necessary, the integrity may be enhanced by applying a pressure of 50 to 400 kgf / cm ^{2 following} the pressurization of 5 to 100 kgf / cm ² . Moreover, it is preferable to laminate | stack, heating at 60 to 80 degreeC.

  Alternatively, the ceramic tape 10A is sufficiently cured, or after drying, the same inorganic powder, butyral resin, acrylic resin, butyl carbitol acetate solvent and / or aliphatic dibasic acid ester, etc. as the ceramic tape 10A It is also preferable to laminate after applying or printing the adhesive paste mixed with the solvent on the ceramic tape 10A.

  By doing in this way, the adhesiveness of ceramic tape 10A mutual can improve, and the above-mentioned delamination can be controlled. In addition, when using an adhesive paste, the solvent in the reaction hardening tape may remain, or the solvent may be dried in advance at a temperature of 60 ° C to 100 ° C. Since the reaction-cured tape after drying the solvent has a significant decrease in plasticity and is difficult to handle, a plasticizer (DOP or DBP) is added to the slurry before reaction-curing for the purpose of imparting plasticity to the dried ceramic tape 10A. It is more preferable to add 1 to 10 parts by weight.

  Next, after the first stacked body 60 is dried in step S10 of FIG. 9, the stacked body is divided into a plurality of chips 62 in step S11 (see FIG. 10).

  Thereafter, in step S12, terminal electrodes are formed on the surface and side surfaces of each chip 62 by printing.

  In step S13, each chip 62 is fired to complete the ceramic component according to the example.

  Here, the preferable aspect of each structural member is demonstrated.

[Conductive paste 15: First embodiment]
The conductor paste 15 preferably contains an uncured material such as epoxy or phenol as a binder, but particularly preferably contains a resol type phenol resin. As for the metal powder, a simple substance or alloy of metal such as Ag, Pd, Au, Pt, Cu, Ni, Rh, or an intermetallic compound can be used. The oxygen partial pressure, temperature, and firing shrinkage temperature characteristics during firing are selected as appropriate. The firing shrinkage temperature characteristic is appropriately controlled not only by the metal powder composition but also by the particle size, specific surface area, and aggregation degree of the metal powder. As for the binder content in the conductive paste 15, for example, in the case of Ag powder, the range of 1% to 10% of the weight of the metal powder is used, but considering the firing shrinkage rate of the ceramic member and the printability during screen printing, A range of 3-6% is preferred.

  As described above, the conductor paste 15 is heat-cured after printing, but the curing conditions differ depending on the type of the curing agent. For example, in the case of the resol type phenol resin used in the first embodiment, the conductive paste 15 is 120 ° C. Cure for 10-60 minutes.

  After the electrode pattern 40 is cured by the conductive paste 15, the surface of the cured electrode pattern 40 is coated with the firing shrinkage adjustment film 14, and then the first film 20 (in this case, a PET film) is placed on the casting mold 16. However, when installing a PET film in a casting mold, in order to suppress the waviness of the PET film, vacuum suction and gluing are performed on the mold plates (first plate member 32a to third plate member 32c) having desired parallelism and flatness. And adsorbed by means such as electrostatic adsorption.

[Firing shrinkage adjustment film 14]
As described above, an organic film or an inorganic film can be used as the firing shrinkage rate adjusting film 14. In the case of an organic film, it is preferably a thermosetting resin precursor, and for example, a self-reactive phenolic resin, epoxy resin, polyurethane resin, or polyparaxylylene resin can be used. In the case of an inorganic film, a silica film can be used.

[Casting Die 16 (Mold): First Embodiment]
As the template (first plate member 32a to third plate member 32c), a plate member corresponding to the suction means is used. For example, in the case of vacuum adsorption, regardless of the material such as metal, ceramic, resin, etc., use a porous plate or a plate with a large number of holes for adsorption. It is preferable to use a plate made of a material that does not change in quality even when the paste is wiped off, etc., and in the case of electrostatic adsorption, a plate made of a material that is easily electrostatically adsorbed with PET is preferably used.

  The casting mold 16 has a path through which the slurry 18 circulates, and the first film in which the electrode pattern 40 is formed between the mold plates so that the slurry 18 after the casting hardening has a plate shape with a desired thickness. 20, a second film 22 (with or without an electrode pattern) and a spacer 24 are installed, and the first film 20 and the second film 22 are parallelly opposed, In addition, it is preferable that an appropriate interval is set between the first film 20 and the second film 22.

  As the first film 20, the second film 22, and the spacer 24, a PET film, a metal plate / ceramic plate coated with a release agent, a Teflon (registered trademark) resin plate, or the like can be used.

  Then, a slurry 18 containing a reaction-curing resin is poured into the casting mold 16 and cured.

[Slurry 18: First embodiment]
The slurry 18 includes oxide ceramics such as alumina, stabilized zirconia, various piezoelectric ceramic materials, and various dielectric ceramic materials, nitride ceramics such as silicon nitride and aluminum nitride, and carbides such as silicon carbide and tungsten carbide, depending on applications. It consists of an inorganic component such as ceramic powder or ceramic powder containing a glass component as a binder, and an organic compound that induces a chemical reaction between the dispersant and the gelling agent or the gelling agent.

  The slurry 18 includes an organic dispersion medium and a gelling agent in addition to the inorganic component powder, and may include a dispersant and a catalyst for adjusting viscosity and solidification reaction. The organic dispersion medium may or may not have a reactive functional group. However, the organic dispersion medium particularly preferably has a reactive functional group.

  The following can be illustrated as an organic dispersion medium which has a reactive functional group.

  That is, the organic dispersion medium having a reactive functional group is a liquid substance that can be chemically bonded to the gelling agent to solidify the slurry 18 and can form a highly fluid slurry 18 that can be easily cast. Two things need to be satisfied.

  In order to chemically bond with the gelling agent and solidify the slurry 18, a reactive functional group, that is, a functional group capable of forming a chemical bond with the gelling agent such as a hydroxyl group, a carboxyl group, or an amino group is included in the molecule. It is necessary to have. The dispersion medium need only have at least one reactive functional group, but in order to obtain a more solidified state, it is preferable to use an organic dispersion medium having two or more reactive functional groups. Examples of liquid substances having two or more reactive functional groups include polyhydric alcohols and polybasic acids. In addition, the reactive functional group in a molecule | numerator does not necessarily need to be the same kind of functional group, and a different functional group may be sufficient as it. Moreover, there may be many reactive functional groups like polyglycerol.

  On the other hand, in order to form a highly fluid slurry 18 that is easy to cast, it is preferable to use a liquid material having a viscosity as low as possible, and in particular, a material having a viscosity at 20 ° C. of 20 cps or less. Is preferred. Since the polyhydric alcohols and polybasic acids described above may have high viscosity due to the formation of hydrogen bonds, even if the slurry 18 can be solidified, it may not be preferable as a reactive dispersion medium. Therefore, it is preferable to use esters having two or more ester groups such as polybasic acid esters and acid esters of polyhydric alcohols as the organic dispersion medium. In addition, it is effective to use polyhydric alcohol and polybasic acid for strength reinforcement as long as they do not greatly thicken the slurry 18. This is because esters are relatively stable, but can be sufficiently reacted with a highly reactive gelling agent and have a low viscosity, so the above two conditions are satisfied. In particular, an ester having a total carbon number of 20 or less can be suitably used as a reactive dispersion medium because of its low viscosity.

  Specific examples of the organic dispersion medium having a reactive functional group that may be contained in the slurry 18 include ester-based nonions, alcohol ethylene oxides, amine condensates, nonionic special amide compounds, modified polyester compounds, carboxyls. Examples thereof include a group-containing polymer, a maleic polyanion, a polycarboxylic acid ester, a multi-chain polymer nonionic system, a phosphoric acid ester, a sorbitan fatty acid ester, an alkylbenzenesulfonic acid Na, and a maleic acid compound. Examples of the non-reactive dispersion medium include hydrocarbon, ether, toluene and the like.

[Gelling agent: first embodiment]
The gelling agent contained in the slurry 18 reacts with the reactive functional group contained in the dispersion medium to cause a solidification reaction, and the following can be exemplified.

  That is, it is preferable that the viscosity of the gelling agent at 20 ° C. is 3000 cps or less. Specifically, it is preferable to solidify the slurry 18 by chemically bonding an organic dispersion medium having two or more ester groups and a gelling agent having an isocyanate group and / or an isothiocyanate group.

  Specifically, this reactive gelling agent is a substance that can chemically bond with the dispersion medium and solidify the slurry 18. Accordingly, the gelling agent only needs to have a reactive functional group capable of chemically reacting with the dispersion medium in the molecule. For example, a prepolymer (three-dimensionally cross-linked by adding a monomer, oligomer, or cross-linking agent) For example, any of polyvinyl alcohol, an epoxy resin, a phenol resin, etc. may be sufficient.

  However, as the reactive gelling agent, from the viewpoint of ensuring the fluidity of the slurry 18, it is preferable to use a material having a low viscosity, specifically, a material having a viscosity at 20 ° C. of 3000 cps or less.

  In general, since prepolymers and polymers having a large average molecular weight have high viscosity, in this example, monomers or oligomers having a molecular weight smaller than these, specifically, a monomer or oligomer having an average molecular weight (by GPC method) of 2000 or less are used. It is preferable. Here, “viscosity” means the viscosity of the gelling agent itself (viscosity when the gelling agent is 100%), and a commercially available gelling agent diluted solution (for example, an aqueous solution of the gelling agent). It does not mean the viscosity of.

  The reactive functional group of the gelling agent is preferably selected as appropriate in consideration of the reactivity with the reactive dispersion medium. For example, when an ester having a relatively low reactivity is used as the reactive dispersion medium, a highly reactive isocyanate group (—N═C═O) and / or an isothiocyanate group (—N═C═S). It is preferred to select a gelling agent having

  Isocyanates are generally reacted with diols and diamines. However, diols are often highly viscous as described above, and diamines are too reactive so that the slurry 18 is cast before casting. May solidify.

  Also from such a viewpoint, it is preferable to solidify the slurry 18 by a reaction between a reactive dispersion medium composed of an ester and a gelling agent having an isocyanate group and / or an isothiocyanate group. In order to obtain it, it is preferable to solidify the slurry 18 by a reaction between a reactive dispersion medium having two or more ester groups and a gelling agent having an isocyanate group and / or an isothiocyanate group. In addition, it is effective to use diols and diamines for reinforcing the strength as long as the amount does not greatly increase the viscosity of the slurry 18.

  Examples of the gelling agent having an isocyanate group and / or an isothiocyanate group include MDI (4,4′-diphenylmethane diisocyanate) -based isocyanate (resin), HDI (hexamethylene diisocyanate) -based isocyanate ( Resin), TDI (tolylene diisocyanate) based isocyanate (resin), IPDI (isophorone diisocyanate) based isocyanate (resin), isothiocyanate (resin) and the like.

  In consideration of chemical characteristics such as compatibility with the reactive dispersion medium, it is preferable to introduce another functional group into the basic chemical structure described above. For example, when making it react with the reactive dispersion medium which consists of ester, it is preferable to introduce a hydrophilic functional group from the point which improves the compatibility with ester and improves the homogeneity at the time of mixing.

  The gelling agent molecule may contain a reactive functional group other than an isocyanate group or an isothiocyanate group, or an isocyanate group and an isothiocyanate group may be mixed. Furthermore, a large number of reactive functional groups may be present, such as polyisocyanate.

  In addition to the components described above, various additives such as an antifoaming agent, a surfactant, a sintering aid, a catalyst, a plasticizer, and a property improver may be added to the slurry 18.

  The slurry 18 described above can be produced as follows.

  (A) An inorganic powder is dispersed in a dispersion medium to form a slurry 18, and then a gelling agent is added.

  (B) The slurry 18 is produced by simultaneously adding and dispersing the inorganic powder and the gelling agent in the dispersion medium.

  Considering workability at the time of casting and coating, the viscosity of the slurry 18 at 20 ° C. is preferably 30000 cps or less, and more preferably 20000 cps or less. The viscosity of the slurry 18 depends not only on the viscosity of the reactive dispersion medium and the gelling agent described above, but also on the type of powder, the amount of the dispersant, and the concentration of the slurry 18 (powder volume% with respect to the total volume of the slurry 18). Can be adjusted.

  However, the concentration of the slurry 18 is usually preferably 25 to 75% by volume, and more preferably 35 to 75% by volume in consideration of reducing cracks due to drying shrinkage. It has a dispersion medium, a dispersant, a reaction cured product, and a reaction catalyst as organic components. Among these, for example, it is solidified by a chemical reaction between the dispersion medium and the gelling agent or the gelling agent.

[Second Embodiment]
Next, a ceramic molded body according to a second embodiment (hereinafter referred to as a second ceramic molded body 10B) will be described with reference to FIGS.

  As shown in FIG. 11, the second ceramic molded body 10 </ b> B is formed with a firing shrinkage rate adjusting film 14 on the surface (upper surface and side surface) of the conductor molded portion 12, and further, a thermosetting resin precursor, ceramic powder, The slurry 18 mixed with the solvent is applied so as to cover the upper surface and the side surface of the conductor molded portion 12 (on which the firing shrinkage rate adjusting film 14 is formed), and then cured to form the ceramic molded portion 13. Can be obtained. In addition, when the thickness of the second ceramic molded body 10B is as thin as 0.05 mm or less, it is difficult to perform the method by casting into a mold. Therefore, the method of coating on the substrate is preferable.

  Here, the manufacturing method of the 2nd ceramic molded object 10B and a 2nd ceramic component is demonstrated concretely, referring FIG. 12A-FIG. 14C.

  First, as shown in FIG. 12A, a release agent (not shown) is applied to the upper surface of the substrate 64 such as a film, and then the conductor paste 15 is patterned on the upper surface of the substrate 64 by, for example, a printing method. The patterned conductor paste 15 is heat-cured to form the conductor molding portion 12 on the base 64.

  Thereafter, the surface of the conductor molding portion 12 formed on the base 64 (in this case, the upper surface and the side surface) is coated with the firing shrinkage rate adjusting film 14. When an organic film is used as the firing shrinkage adjustment film 14, it can be formed by, for example, CVD (chemical vapor deposition) or printing, and when an inorganic film is used, it can be formed by, for example, CVD or sputtering. .

  Thereafter, as shown in FIG. 12B, a slurry 18 in which a thermosetting resin precursor, a ceramic powder, and a solvent are mixed is applied on a base 64 so as to cover the conductor molding portion 12. As a coating method, there are a dispenser method, a method shown in FIGS. 13A and 13B, a spin coating method, and the like. In the method shown in FIGS. 13A and 13B, a base body 64 (base body 64 on which the conductor molding portion 12 is formed) is installed between a pair of guide plates 66a and 66b, and then the slurry 18 is coated with the conductor molding portion 12. In this way, after applying on the base 64, the blade-shaped jig 68 is slid (slid) on the upper surfaces of the pair of guide plates 66a and 66b to remove the excess slurry 18. By adjusting the height of the pair of guide plates 66a and 66b, the thickness of the slurry 18 can be easily adjusted.

  Thereafter, as shown in FIG. 14A, the slurry 18 applied on the substrate 64 is cured (room temperature curing, dry curing, etc.) to form the ceramic molded portion 13.

  Thereafter, as shown in FIG. 14B, the second ceramic molded body 10B is completed by peeling and removing the base body 64.

  Further, as shown in FIG. 14C, by firing the second ceramic molded body 10B, the second ceramic component 72 having the ceramic fired body 70 in which the conductor molded portion 12 is embedded is completed.

  Here, the preferable aspect of each structural member is demonstrated.

[Conductive paste 15: Second embodiment]
Since it is the same as that of the first embodiment, overlapping description is omitted, but the conductor paste 15 in the second embodiment is made of resin and silver (Ag), gold (Au), and copper (Cu). Contains at least one powder of metal. The resin used for the conductor paste 15 is preferably a thermosetting resin precursor. In this case, the thermosetting resin precursor is preferably a self-reactive resol type phenol resin.

  As described above, the conductor paste 15 is heat-cured after printing, but the curing conditions differ depending on the type of the curing agent. For example, in the case of the resol type phenol resin used in the second embodiment, the temperature of the conductor paste 15 is 80. It can be cured at ˜150 ° C. for 10 minutes to 60 minutes.

[Baking Shrinkage Adjustment Film 14: Second Embodiment]
Also in the second embodiment, an organic film or an inorganic film can be used as the firing shrinkage rate adjusting film 14. In the case of an organic film, it is preferably a thermosetting resin precursor, and for example, a self-reactive phenolic resin, epoxy resin, polyurethane resin, or polyparaxylylene resin can be used. In the case of an inorganic film, a silica film can be used.

[Slurry 18: Second Embodiment]
Since it is the same as that of the first embodiment, overlapping description is omitted, but the ceramic powder contained in the slurry 18 in the second embodiment is alumina, stabilized zirconia, various piezoelectric ceramics depending on applications. It includes oxide ceramics such as materials and various dielectric ceramic materials, nitride ceramics such as silicon nitride and aluminum nitride, carbide ceramic powders such as silicon carbide and tungsten carbide, and glass components as binders.

  The thermosetting resin precursor contained in the slurry 18 has a gelling agent having an isocyanate group or an isothiocyanate group and a polymer having a hydroxyl group.

  Among the application methods described above, when the slurry 18 is applied onto the substrate 64 by the dispenser method or the method shown in FIGS. 13A and 13B, the viscosity of the slurry 18 is preferably relatively high. The viscosity of the slurry 18 may be the same as that of the first embodiment. However, if the slurry 18 has a low viscosity, the shape retention after coating is low, and the thickness variation due to flow tends to occur. Therefore, the viscosity of the slurry 18 is preferably 200 cps to 2000 cps.

  Therefore, the viscosity of the slurry 18 can be increased by using a resin having a large molecular weight as the polymer having a hydroxyl group. As an example, since the butyral resin has a large molecular weight, it is suitable for increasing the viscosity of the slurry 18. Of course, since the viscosity of the slurry 18 can be controlled by the molecular weight of the polymer, the resin used as the polymer may be appropriately selected according to the coating method.

  The above-mentioned butyral resin is generally a polyvinyl acetal resin, but since OH groups derived from the raw material polyvinyl alcohol resin remain in the resin, this OH group reacts with the isocyanate group or isothiocyanate group of the gelling agent. It is considered a thing.

  In particular, when a butyral resin is added in excess of the amount necessary for the reaction with an isocyanate group or an isothiocyanate group, the butyral resin remaining after the reaction acts as a thermoplastic resin, which is a drawback of the thermosetting resin. The characteristic that the adhesiveness is deteriorated can be improved. As a result, for example, as shown in FIG. 15, when the second laminated body 74 is formed by laminating a plurality of second ceramic molded bodies 10B, the adhesiveness of each second ceramic molded body 10B is improved. The inconvenience that the second ceramic molded body 10B is peeled off during the manufacturing process can be avoided, and the yield of the ceramic parts 72 by the second laminate 74 of the plurality of second ceramic molded bodies 10B can be improved.

  In addition, as the polymer having a hydroxyl group, an ethyl cellulose resin, a polyethylene glycol resin, or a polyether resin can be preferably used.

  Also in the second ceramic molded body 10B (and the second laminated body 74) and the second ceramic component 72 described above, the firing shrinkage rate adjusting film 14 is interposed between the conductor molded portion 12 and the ceramic molded portion 13. The same effects as (1) to (4) in the first ceramic molded body 10A described above are exhibited. Therefore, the conductor molding part 12 (electrode pattern or the like) is not peeled or collapsed by the conductor paste 15, and the conductor molding part 12 (electrode pattern or the like) can be thickened to reduce the resistance value and improve the high frequency characteristics. It can be easily achieved.

  Here, as the resin contained in the slurry 18, the problems of the conventional ceramic molded body using a thermoplastic resin precursor, the first ceramic molded body 10A and the second ceramic molded body 10B (hereinafter collectively referred to as the present embodiment). (Problem solving) will be described.

  Conventionally, when the slurry containing the thermoplastic resin precursor is dried and contracted, a gap or a crack is generated at the interface with the conductor molding portion, or the green sheet becomes uneven.

  On the other hand, in the present embodiment, the thermosetting resin precursor is included in the slurry 18, the thermosetting resin precursor is cured at the time of drying to form a three-dimensional network structure, and the shrinkage is reduced. Is solved.

  In this case, it is desirable to select a solvent having a low vapor pressure at a temperature at which the thermosetting resin precursor is cured as the solvent used in the slurry 18 to reduce shrinkage due to solvent drying during thermosetting. When a resin that cures at room temperature is used, operations and equipment are particularly simplified.

  Polyurethane resin has advantages such as easy control of elasticity after curing and also enables a flexible molded body. Considering the handling in the subsequent process, a hard molded body may not be suitable, and the thermosetting resin is generally hard because it has a three-dimensional network structure, but the polyurethane resin can also be a flexible molded body, In particular, a tape-shaped molded body is desirable because flexibility is often required. Further, a thermoplastic resin may be included for controlling the slurry properties.

  Conventionally, when a conductive paste containing a thermoplastic resin is applied to a slurry, it is dissolved in the solvent of the slurry and the pattern shape is destroyed.

  On the other hand, in the present embodiment, since the firing shrinkage ratio adjusting film 14 is formed on the surface of the conductor molding portion 12, even if the conductor paste 15 contains a thermoplastic resin precursor, solvent resistance is achieved. The pattern shape is not broken.

  Conventionally, a ceramic molded part using a thermoplastic resin as a binder is likely to have a density variation of the ceramic molded part, and therefore, the dimensional variation of the fired ceramic sintered body is large, and the embedded conductor molded part is fired. Variations in dimensions also increase. In many electronic parts, the dimensions of the conductor determine the characteristics and performance of the part. For example, in a stripline filter with a built-in conductor, the center frequency of the filter is determined by the size of the resonance electrode.

  On the other hand, in the present embodiment, since the firing shrinkage rate adjusting film 14 is formed on the surface of the conductor molding portion 12 and the thermosetting resin precursor is included in the slurry 18, firing variation can be reduced. .

  For example, the size after firing of the second ceramic molded body 10B is mainly determined by the raw density of the second ceramic molded body 10B excluding the conductor molded portion 12 (ceramic molded portion 13). This is because the structure of the ceramic fired body 70 of the second ceramic component 72 has very few voids, whereas the ceramic molded part 13 has many voids, and the amount of voids determines the amount of shrinkage during firing. is there.

  The slurry containing the thermoplastic resin precursor as a binder obtains a ceramic molded body by drying the solvent, but the coating ratio (ratio of the slurry volume and the molded body volume after molding) during drying is large. The work ratio causes variation in the density of the compact.

  However, when the thermosetting resin precursor is used as a binder for the slurry 18 as in the present embodiment, the coating ratio can be reduced because the resin is cured while containing the solvent, and the raw density can be reduced. Variation can be reduced. As a result, the dimensional variation after firing is reduced, and the dimensional variation of the embedded conductor molding portion 12 can be reduced.

  The ceramic molded body, the ceramic part, the ceramic molded body manufacturing method, and the ceramic part manufacturing method are not limited to the above-described embodiments, and various configurations can be adopted without departing from the gist of the present invention. Of course.

It is sectional drawing which shows a 1st ceramic molded object. FIG. 2A is a cross-sectional view showing a state in which a firing shrinkage rate adjusting film is formed on the surface of a pattern of a conductor molding portion using a conductor paste, and FIG. FIG. 2C is a cross-sectional view showing a state in which the slurry injected into the casting mold is cured to form a first ceramic molded body. FIG. 3A is a cross-sectional view showing a state in which a firing shrinkage ratio adjusting film is formed on the surface of the pattern of the conductor molding portion made of a conductor paste on the film, and FIG. FIG. 3C is a cross-sectional view showing a state where the slurry is injected, and FIG. 3C is a cross-sectional view showing a state where the slurry injected into the casting mold is cured to form a first ceramic molded body. 4A is a cross-sectional view showing a state in which the first ceramic molded body is released from the casting mold together with the film, and FIG. 4B is a cross-sectional view showing a state in which the first ceramic molded body is released from the film. It is sectional drawing which shows the state which laminated | stacked the 1st ceramic molded body and comprised the 1st laminated body. FIG. 6A is a cross-sectional view showing a state in which a firing shrinkage rate adjusting film is formed on the surface of a pattern of a conductor molding portion made of a conductor paste on a film, and FIG. 6B shows a film placed in a casting mold together with other films and spacers. FIG. 6C is a cross-sectional view showing a state in which the slurry is injected into the casting mold, and FIG. 6C is a cross-sectional view showing a state in which the slurry injected into the casting mold is cured to form a first ceramic molded body. FIG. 7A is a cross-sectional view illustrating a state in which the first ceramic molded body is released from the casting mold together with the film, the other film, and the spacer, and FIG. 7B is a release of the first ceramic molded body from the film, the other film, and the spacer. It is sectional drawing which shows the state which carried out. It is a disassembled perspective view which shows the casting type | mold used when producing a 1st ceramic molded object. It is a process block diagram which shows the procedure which produces a 1st ceramic molded object and a 1st ceramic component. It is explanatory drawing which shows the procedure to step S7-step S11 of FIG. It is sectional drawing which shows a 2nd ceramic molded object. FIG. 12A is a process diagram showing a state in which a firing shrinkage ratio adjusting film is formed on the surface of the pattern of the conductor molding portion by the conductor paste on the substrate, and FIG. 12B is a slurry coating on the substrate so as to cover the conductor molding portion. It is process drawing which shows the state performed. FIG. 13A is a perspective view showing an example of a method for applying slurry onto a substrate, and FIG. 13B is a side view thereof. FIG. 14A is a process diagram showing a state where the slurry applied on the substrate is cured, FIG. 14B is a process diagram showing a state where the substrate is peeled to form a second ceramic molded body, and FIG. 14C is a second ceramic molding. It is process drawing which shows the state which sintered the body and was set as the 2nd ceramic component. It is sectional drawing which shows the state which laminated | stacked the 2nd ceramic molded body and comprised the 2nd laminated body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10A ... 1st ceramic molded object 10B ... 2nd ceramic molded object 12 ... Conductor molded object 13 ... Ceramic molded part 14 ... Firing shrinkage rate adjustment film | membrane 15 ... Conductor paste 16 ... Casting type | mold 18 ... Slurry 20 ... Film (1st film)
22 ... Other films (second film)
24 ... Spacer 40 ... Electrode pattern 60 ... First laminate 64 ... Substrate 70 ... Ceramic fired body 72 ... Ceramic component 74 ... Second laminate

Claims (22)

Conductor paste containing metal powder and binder is formed into a pattern, and then hardened conductor molded part,
A ceramic molded body having a ceramic molded portion obtained by curing a slurry obtained by mixing a resin, ceramic powder and a solvent so as to cover the conductor molded portion,
A ceramic molded body, wherein a firing shrinkage rate adjusting film is formed at an interface between the conductor molded portion and the ceramic molded portion. The ceramic molded body according to claim 1,
The ceramic molded body, wherein the firing shrinkage rate adjusting film is an organic film (CVD or printing) or an inorganic film (CVD or sputtering). In the ceramic molded body according to claim 2,
The ceramic molded body, wherein the organic film included in the firing shrinkage rate adjusting film is a phenol resin, an epoxy resin, a polyurethane resin, or a polyparaxylylene resin. In the ceramic molded body according to claim 2,
The ceramic molded body, wherein the inorganic film contained in the firing shrinkage rate adjusting layer is a silica film. In the ceramic molded body according to any one of claims 1 to 4,
The ceramic molded part is obtained by curing the slurry after applying the slurry so as to cover the conductor molded part molded on a substrate. In the ceramic molded body according to any one of claims 1 to 5,
The metal powder contained in the conductor paste is a powder of at least one of silver (Ag), gold (Au), and copper (Cu) based metals,
The ceramic molded body, wherein the binder contained in the conductor paste is a thermoplastic resin precursor or a thermosetting resin precursor. In the ceramic molded body according to claim 6,
The ceramic molded body, wherein the thermosetting resin precursor contained in the conductor paste is a phenol resin. In the ceramic molded body according to any one of claims 1 to 7,
The said resin contained in the said slurry is a thermosetting resin precursor, Comprising: The ceramic molded object characterized by being a polyurethane resin precursor.   The ceramic component formed by baking the ceramic molded body of any one of Claims 1-8. Conductor forming step of forming a conductor paste containing metal powder and a binder, and then forming a conductor molding portion formed by curing;
A firing shrinkage rate adjusting film forming step of forming a firing shrinkage rate adjusting film on a part or all of the surface of the conductor molding part,
A slurry supply step of supplying a slurry in which a thermosetting resin precursor, a ceramic powder, and a solvent are mixed so as to cover the conductor molding portion together with the firing shrinkage rate adjustment layer;
A method for producing a ceramic molded body, comprising: a slurry curing step for producing a ceramic molded body by curing the slurry to form a ceramic molded portion. In the manufacturing method of the ceramic forming object according to claim 10,
The method for producing a ceramic molded body, wherein the firing shrinkage rate adjusting film is an organic film (CVD or printing) or an inorganic film (CVD or sputtering). In the manufacturing method of the ceramic molded body of Claim 11,
In the firing shrinkage ratio adjusting film forming step, the organic film is formed on a part or all of the surface of the conductor molding portion by a CVD method or a printing method. In the manufacturing method of the ceramic molded body of Claim 11,
In the firing shrinkage rate adjusting film forming step, the inorganic film is formed on a part or all of the surface of the conductor molding part by a CVD method or a sputtering method. In the manufacturing method of the ceramic molded body of any one of Claims 10-13,
The method for producing a ceramic molded body, wherein the thermosetting resin precursor used in the slurry is a polyurethane resin precursor. In the manufacturing method of the ceramic forming object according to claim 10,
The conductor forming step forms the conductor molding part on a base,
In the firing shrinkage rate adjusting film forming step, the firing shrinkage rate adjusting film is formed on the conductor molding portion formed on the substrate,
In the slurry supplying step, the slurry is applied onto the base body so as to cover the conductor forming portion together with the firing shrinkage rate adjusting layer. In the manufacturing method of the ceramic forming object according to claim 10,
The conductor forming step forms a conductor molding part on the film,
The firing shrinkage rate adjustment film forming step forms the firing shrinkage rate adjustment film on the conductor molding portion formed on the film,
In the slurry supply step, the film on which the conductor forming portion and the firing shrinkage rate adjustment film are formed is placed in a casting mold, and the slurry is cast in the casting mold. Production method. The method for producing a ceramic molded body according to claim 16,
In the slurry supply step, when the film is installed in the casting mold,
The film and the other film are opposed to the other film and the surface on which the conductor molding portion and the baking shrinkage rate adjusting film are formed, and a spacer is sandwiched between the film and the other film. Install
A method for producing a ceramic molded body, wherein the slurry is poured into a space formed by the spacer. In the manufacturing method of the ceramic molded body of Claim 17,
A method for producing a ceramic molded body, wherein a peeling force of a release agent applied to the surface of the film is different from a release force of a release agent applied to the surface of the other film. In the manufacturing method of the ceramic molded body of any one of Claims 10-18,
The metal powder contained in the conductor paste is a powder of at least one of silver (Ag), gold (Au), and copper (Cu) based metals,
The binder contained in the conductor paste is a thermoplastic resin precursor or a thermosetting resin precursor. The method for producing a ceramic molded body according to claim 19,
The method for producing a ceramic molded body, wherein the thermosetting resin precursor contained in the conductor paste is a phenol resin. The method for producing a ceramic molded body according to claim 20,
The method for producing a ceramic molded body, wherein the thermosetting resin precursor contained in the conductor paste is a self-reactive resol resin. Producing a ceramic molded body;
A method for producing a ceramic component comprising a step of firing the produced ceramic molded body,
The step of producing the ceramic molded body includes
Conductor forming step of forming a conductor paste containing metal powder and a binder, and then forming a conductor molding portion formed by curing;
A firing shrinkage rate adjusting film forming step of forming a firing shrinkage rate adjusting film on a part or all of the surface of the conductor molding part,
A slurry supply step of supplying a slurry in which a thermosetting resin precursor, a ceramic powder, and a solvent are mixed so as to cover the conductor molding portion together with the firing shrinkage rate adjustment layer;
A method for producing a ceramic component, comprising: a slurry curing step for producing a ceramic molded body by curing the slurry to form a ceramic molded portion.

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