JP2007168294A - Method for manufacturing ceramic structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing simply and efficiently a ceramic structure having recesses of a required pattern formed on its surface and a method for manufacturing simply and efficiently a ceramic structure having voids of a required pattern formed in its internal. <P>SOLUTION: The method for manufacturing the ceramic structure comprises a process of forming the recesses 12 on a ceramic green sheet 1 by pressing a die 10 on the surface of the ceramic green sheet 1 and a process of calcining the ceramic green sheet 1. Regarding formation of the voids in the internal in addition to the recesses 12, a plurality of ceramic green sheets containing the ceramic green sheet 1 are laminated and calcined after the process of forming the recesses on a ceramic green sheet 1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a ceramic structure in which concave portions having a desired pattern are formed on a surface.

  Conventionally, there has been a ceramic structure with a recess formed on the surface, and as its application, for example, an electronic component storage package for storing a semiconductor element or various electronic components, a flow path for various fluids, etc. are expected. Yes.

  FIG. 7 is a process diagram showing a conventional manufacturing method of a ceramic structure having a recess formed on the surface. FIG. 8 is a plan view showing a ceramic green sheet on which a penetration pattern is formed by punching.

  In general, in this method of manufacturing a ceramic structure, as shown in FIG. 7A, a through pattern 101 is formed by punching at a predetermined location of a ceramic green sheet 100. Next, as shown in FIG. 7B, a green body 100 on which the through pattern 101 is formed and another green sheet 102 are laminated to form a laminated body 103, and the laminated body 103 is fired. A ceramic structure having a recess formed on the surface is obtained.

  However, in this manufacturing method, for example, when the through pattern 101 as shown in FIG. 8 is formed on the green sheet 100 by punching, the green sheet 100 is divided into a plurality of pieces by the through pattern 101, so that the laminate 103 is formed. Workability at the time of performing is reduced. That is, the punching process has a problem that it is difficult to form a concave portion having a free pattern on the green sheet.

  Patent Document 1 describes a ceramic green sheet-resin sheet composite in which a predetermined resin sheet is fitted into a through hole (penetration pattern) formed in a ceramic green sheet. According to this method, since a predetermined resin sheet is fitted into the penetrating pattern, the green sheet by forming the penetrating pattern is not divided into a plurality of parts, and workability when forming a laminate may be reduced. Reduce.

However, since the adhesive force at the interface between the ceramic green sheet and the resin sheet fitted therein is small, deformation occurs when transferring and laminating the ceramic green sheet-resin sheet composite, and the workability is reduced. Is not necessarily enough.
JP 2005-131971 A

The main object of the present invention is to provide a method capable of easily and efficiently producing a ceramic structure in which concave portions having a desired pattern are formed on the surface.
Another object of the present invention is to provide a method capable of easily and efficiently producing a ceramic structure in which a cavity having a desired pattern is formed.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a solution means having the following constitution and have completed the present invention.
(1) A method for producing a ceramic structure, comprising: a step of pressing a mold on a surface of a ceramic green sheet to form a recess in the ceramic green sheet; and a step of firing the ceramic green sheet.
(2) A method for producing a ceramic structure, comprising: a step of cutting a surface of a ceramic green sheet to form a recess in the ceramic green sheet; and a step of firing the ceramic green sheet.
(3) The ceramic structure according to (1) or (2), including a step of laminating and firing a plurality of ceramic green sheets including the ceramic green sheet after the step of forming a recess in the ceramic green sheet. Production method.
(4) After the step of forming a recess in the ceramic green sheet, a step of filling the recess with a resin, and a step of laminating and firing a plurality of ceramic green sheets including the ceramic green sheet filled with the resin The method for producing a ceramic structure according to any one of (1) to (3), wherein the resin is thermally decomposed and removed during firing.
(5) The method for producing a ceramic structure according to (4), wherein the resin contains bubbles.
(6) The method for producing a ceramic structure according to (4) or (5), wherein the resin includes hollow resin beads.
(7) When the volume of the concave portion formed in the ceramic green sheet is V, the occupied volume of the resin filled in the concave portion is 0.8V to 1.1V, immediately before the resin is thermally decomposed. The method for producing a ceramic structure according to any one of (4) to (6), wherein a volume V _{liq. In a} molten state is 0.2 V to 0.6 V.
(8) In the above when the firing time in the resin is removed by thermal decomposition, the temperature T _a ° C. to the weight of the upper side is reduced by 80% resin, the temperature at which the weight of the lower side is reduced 80% T _b ° C. (4) to (4) satisfying the relationship of T _a <T _b ≦ T _c , where T _c ° C. is the temperature at which the weight of the resin binder contained in the ceramic green sheet having the recesses is reduced by 20%. 7) A method for producing a ceramic structure according to any one of the above.

  According to the above (1) and (2), the mold is pressed on the surface of the ceramic green sheet or cut to form the recess in the ceramic green sheet, so that the recess having a free pattern can be easily formed. In addition, since the deformation of the ceramic green sheet can be prevented in advance, there is an effect that the ceramic structure can be manufactured efficiently.

According to the above (3), in addition to the recess, a ceramic structure having a free pattern of cavities inside can be obtained.
According to said (4), since the said recessed part is filled with resin, while the rigidity of a ceramic green sheet improves, the handleability of this ceramic green sheet improves, and several ceramics containing this ceramic green sheet When the green sheets are laminated, equal pressure lamination is possible. As a result, a ceramic structure in which the recesses and cavities are not deformed and delamination can be produced. Furthermore, since the resin is thermally decomposed and removed, a ceramic structure can be efficiently manufactured.

  According to the above (5), since the resin contains bubbles, it is possible to reduce the amount of pyrolyzate generated when the resin is thermally decomposed and removed. As a result, the pyrolyzate is ceramic green. Dissolution of the resin binder contained in the green sheet and contact with the surface of the ceramic due to contact with the sheet can be suppressed, and deformation of the green sheet and generation of cracks and the like due to pressure of the generated decomposition gas can be suppressed.

  According to the above (6), since the resin includes a hollow resin bead that is a rigid body, the rigidity of the green sheet filled with the resin is improved, and even when the resin is laminated at a high pressure, Pressure equalization lamination is possible.

According to (7) above, since the volume V _{liq. In} the molten state immediately before the resin is thermally decomposed satisfies the predetermined relationship, the amount of the thermally decomposed product can be further reduced.
According to the above (8), since the resin can be thermally decomposed in order from the upper part to the lower part, a ceramic structure having a recess or a cavity with high dimensional accuracy can be manufactured.

  An embodiment of a method for producing a ceramic structure according to the present invention will be described in detail with reference to the drawings. FIG. 1 is a process diagram showing a method for manufacturing a ceramic structure according to the present embodiment. FIG. 2 is a plan view showing an example of a ceramic structure manufactured according to this embodiment.

In the method for manufacturing a ceramic structure according to the present embodiment, first, a ceramic green sheet 1 and a mold 10 are prepared as shown in FIG.
<Ceramic green sheet>
The ceramic green sheet 1 is made of, for example, a slurry prepared by adding an additive such as a resin binder or a plasticizer, an organic solvent, or the like to a mixture of ceramic powder and / or glass powder and optionally adding an auxiliary component and mixing. For example, it can be obtained by molding to a predetermined thickness by a molding method such as a doctor blade method, a rolling method, or a pressing method.

(Ceramic powder)
Examples of the ceramic powder include metal or non-metal oxide or non-oxide powder. These powders may be used in a single composition or in the form of a compound alone or in combination. Specifically, for example, Li, K, Mg, B, Al, Si, Cu, Ca, Br, Ba, Zn, Cd, Ga, In, lanthanoid, actinoid, Ti, Zr, Hf, Bi, V, Nb, Examples thereof include oxides such as Ta, W, Mn, Fe, Co, and Ni, carbides, nitrides, borides, and sulfides.

Furthermore, in addition to composite oxides of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , TiO ₂ and alkaline earth metal oxides, ZnO, MgO, MgAl ₂ O ₄ , ZnAl ₂ O ₄ , MgSiO ₃ , Mg ₂ SiO _{4, Zn 2 SiO 4, Zn} 2 TiO 4, SrTiO 3, CaTiO 3, MgTiO 3, BaTiO 3, CaMgSi 2 O 6, SrAl 2 Si 2 O 8, BaAl 2 Si 2 O 8, CaAl 2 Si 2 O 8, Mg ₂ Al ₄ Si ₅ O ₁₈ , Zn ₂ Al ₄ Si ₅ O ₁₈ , AlN, Si ₃ N ₄ , SiC and the like can be mentioned. Furthermore, composite oxides containing at least one selected from Al ₂ O ₃ and SiO ₂ (for example, spinel, mullite, cordierite) and the like can be mentioned, and these can be selected according to the application.

(Glass powder)
Examples of the glass powder include SiO ₂ —B ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —MO (where M is Ca , Sr, Mg, Ba or Zn), SiO ₂ —Al ₂ O ₃ —M ₁ O—M ₂ O system (where M ₁ and M ₂ are the same or different, and Ca, Sr, Mg) , Ba or Zn), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ₁ O—M ₂ O system (where M ₁ and M ₂ are as defined above), SiO ₂ — B ₂ O ₃ —M ₃ O system (where M ₃ is Li, Na or K), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ₃ O system (where M ₃ is as defined above) Including at least one selected from the group consisting of Pb-based glass, Bi-based glass, alkali metal oxides, alkaline earth metal oxides, and rare earth oxides. Glass is preferred. These glasses become amorphous glass when fired, and when fired, lithium silicate, quartz, cristobalite, cordierite, mullite, anorthite, serdian, spinel, garnite, willemite, dolomite, petalite and their Crystallized glass that precipitates at least one type of substituted derivative crystal is used.

The ratio in the case of mixing ceramic powder and glass powder is a ratio used for a normal glass ceramic structure material, and it is preferable that ceramic powder: glass powder = 60: 40 to 1:99 by weight ratio. Examples of the auxiliary component include B ₂ O ₃ , ZnO, MnO ₂ , alkali metal oxides, alkaline earth metal oxides, rare earth metal oxides, and the like, and can be selected according to the application.

  In addition, when the ceramic structure of the present invention is used as a piezoelectric element, crystals of perovskite type structures such as barium titanate and lead zirconate-lead titanate solid solutions can be cited. Zirconate titanate such as lead zirconate (PZT) and lead lanthanum zirconate titanate (PLZT), or lead titanate.

(Resin binder)
Examples of the resin binder include acrylics (acrylic acid, methacrylic acid or homopolymers or copolymers thereof, specifically, acrylic ester copolymers, methacrylic ester copolymers, acrylic ester- Methacrylic acid ester copolymers, etc.), polyvinyl acetal-based, cellulose-based, polyvinyl alcohol-based, polyvinyl acetate-based, polyvinyl chloride, polypropylene carbonate-based homopolymers or copolymers, etc. It is preferable to contain at least one selected from the above.

  Specific examples of the acrylic type include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate. , Isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, isodecyl acrylate, isodecyl methacrylate, etc. These acrylic esters and methacrylates A copolymer containing a carboxylic acid group, an alkylene oxide group, a hydroxyl group, a glycidyl group, an amino group or an amide group as a copolymer component is preferably used as the copolymer having a kill ester as the main chain. Can do.

  Examples of those having a carboxylic acid group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. Examples of those having alkylene oxide include methylene oxide, ethylene oxide, and propylene oxide. As those having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, trimethylolpropane There are triacrylate, trimethylolpropane trimethacrylate, etc., and those having a glycidyl group include glycidyl Examples of those having an amino group or an amide group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-tert-butylaminoethyl acrylate, N-tert- Examples include butylaminoethyl methacrylate, acrylamide, cyclohexyl acrylamide, cyclohexyl methacrylamide, N-methylol acrylamide, and diacetone acrylamide.

  Other copolymerizable acrylonitrile, styrene, ethylene, vinyl acetate, n-vinylpyridone and the like may be copolymerized with these copolymers having acrylic acid ester or methacrylic acid alkyl ester as the main chain.

  Specific examples of the polyvinyl acetal type include polyvinyl butyral, polyvinyl ethylal, polyvinyl propylal, polyvinyl octylal, polyvinyl phenylal, and derivatives thereof.

  Specific examples of the cellulose type include methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, nitrocellulose, and cellulose acetate.

(Plasticizer)
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate (DOP), diheptyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, ethyl phthalyl ethyl glycolate. , Phthalic acid ester systems such as butyl phthalyl butyl glycolate, and aliphatic ester systems such as di-2-ethylhexyl adipate and dibutyl diglycol adipate, and preferably contains at least one selected from these. .

(Organic solvent)
Examples of the organic solvent include terpineol, dihydroterpineol, ethyl carbitol, butyl carbitol, carbitol acetate, butyl carbitol acetate, diisopropyl ketone, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, cyclohexanone. , Cyclohexanol, isophorone, cypropylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl carbitol methyl-3-hydroxyhexanoate, trimethylpentanediol monoisobutyrate, pine oil, mineral spirits, etc. A solvent can be preferably used.

<Type>
The material of the mold 10 is not particularly limited, and examples thereof include a mold and a resin mold. Further, the mold 10 includes a convex portion 11 corresponding to the concave portion formed in the ceramic green sheet 1. The surface of the portion of the convex portion 11 that comes into contact with the ceramic green sheet 1 is preferably subjected to a surface coating treatment in order to improve wear resistance and releasability. Specifically, as a method for improving the wear resistance of the surface of the protrusion 11 on the mold, for example, surface coating treatment with diamond-like carbon (DLC), graphite-like carbon (GLC), or the like is possible. Can be mentioned. Moreover, as a method of improving the mold release property of the surface of the convex part 11 concerning a metal mold | die and a resin type | mold, the surface coating process by a silicone coat, a Teflon (trademark) coat etc. is mentioned, for example.

  The surface roughness (Ry) of the convex portion 11 is preferably 0.5 or less. Thereby, the mold release property of the mold 10 is further improved. On the other hand, when the surface roughness (Ry) is larger than 0.5, the releasability is deteriorated and the surface unevenness of the protrusion 11 may be transferred to the recess of the green sheet 1. The surface roughness (Ry) is a value based on JIS B0601 (surface roughness definition), for example, a value obtained by measuring the surface of the convex portion 11 with “Surf Test SV-3100” manufactured by Mitutoyo Corporation. .

  The height h of the convex portion 11 is preferably 3/4 or less of the thickness of the ceramic green sheet 1. Thereby, a recess can be formed on the surface of the ceramic green sheet 1. On the other hand, if the height h is higher than 3/4 of the thickness of the green sheet 1, the strength of the green sheet 1 may be lowered and deformed, which is not preferable.

  Next, as shown in FIG. 1B, the mold 10 is pressed against the surface of the ceramic green sheet 1 described above. The pressing force when pressing the mold 10 is not particularly limited and can be arbitrarily selected according to the application.

  Further, when pressing the mold 10, it is preferable to fix the back surface of the green sheet 1 to a predetermined fixing base. Thereby, since the green sheet 1 is not displaced during pressing, the mold 10 can be reliably pressed at a predetermined position, and the green sheet 1 is released from the mold 10 at the time of releasing the mold 10 described below. Further, the sheet 1 can be prevented from being deformed by being lifted together. Examples of the fixing method include suction fixing using a suction mechanism provided on a fixing base, and sticking fixing using an adhesive tape or the like. In the present invention, it can be used repeatedly and is preferably suction-fixed in order to be excellent in productivity.

  Next, the pressed mold 10 is released from the green sheet 1 as shown in FIG. Thereby, a concave portion 12 corresponding to the convex portion 11 of the mold 10 is formed on the surface of the ceramic green sheet 1. And the ceramic structure in which the recessed part 12 was formed can be obtained by baking this green sheet 1 on predetermined | prescribed baking conditions. The firing conditions are not particularly limited, and may be appropriately selected depending on the material composition constituting the green sheet 1.

  Here, as described above, in this embodiment, the concave portion is formed by pressing the mold against the surface of the ceramic green sheet, so that the concave portion having a free pattern can be easily formed. Specifically, for example, even a ceramic structure 20 including a concave portion 21 having a pattern as shown in FIG. 2 can be easily formed by pressing a mold having a convex portion corresponding to the concave portion 21 against a green sheet. can do.

  Next, another embodiment according to the present invention will be described in detail with reference to the drawings. FIG. 3 is a process diagram showing a method for manufacturing a ceramic structure according to this embodiment. According to the manufacturing method according to this embodiment, a ceramic structure having a cavity inside in addition to the recess can be obtained. Specifically, first, as shown in FIG. 3A, the ceramic green sheet 1 in which the concave portion 12 described above is formed is prepared. Next, the resin 50 is filled in the recess 12.

<Resin>
The resin 50 improves the rigidity of the green sheet 1 in which the concave portion 12 is formed, and enables pressure equalization lamination when forming the laminate 15 described later. When firing, it can be removed by thermal decomposition. The composition of the resin 50 preferably includes a resin binder and at least one of a plasticizer and a lubricant.

(Resin binder)
As the resin binder, those excellent in thermal decomposability are preferable, and for example, acrylic and α-methylstyrene are preferable. Examples of acrylic resins include homopolymers or copolymers of acrylic acid, methacrylic acid or esters thereof. Specific examples include acrylic ester copolymers, methacrylic ester copolymers, and acrylic acid. Examples include ester-methacrylic acid ester copolymers. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Examples include isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.

  These acrylic resins can be used alone or in appropriate combination of two or more as required. Among these, an isobutyl methacrylate-based (IBMA) or methyl methacrylate-based (MMA) resin binder alone or a copolymer is particularly preferable. In addition, copolymerization with an acrylic resin is possible as long as the thermal decomposability is not impaired, and styrene, α-methylstyrene, acrylonitrile, ethylene, or the like may be appropriately introduced.

(Plasticizer / Lubricant)
Examples of the plasticizer added to impart flexibility and flexibility to the resin 50 are the same as the plasticizer exemplified in the ceramic green sheet 1.
Examples of the lubricant include diethylene glycol, triethylene glycol, polyethylene glycol, diethylene glycol methyl ether, triethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-butyl ether, triethylene glycol-n-butyl ether, ethylene glycol phenyl ether, Ethylene glycols such as ethylene glycol-n-acetate, diethylene glycol monohexyl ether, diethylene glycol monovinyl ether, dipropylene glycol, tripropylene glycol, polypropylene glycol, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, propylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol isoamyl ether, and other propylene glycol systems, glycerin, diglycerin, polyglycerin and other glycerin systems Among them, polyethylene glycol (PEG) and glycerin are preferable.

  Natural wax and synthetic wax may be used as a lubricant. Acrylic resin, which is a general resin binder, depolymerizes monomer units during thermal decomposition and lowers its molecular weight, so a large amount of decomposition gas is generated, whereas many waxes are large molecules during thermal decomposition. Since the gas is decomposed and vaporized with a large molecular weight, the generation amount of the decomposition gas can be reduced, and there is an effect of preventing deformation of the surrounding green sheet or generation of cracks due to the generation pressure of the decomposition gas. Examples of natural waxes include plant waxes such as carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, bayberry wax, ocully wax, esparto wax, jojoba oil, beeswax, insect wax, and whale wax. Animal waxes such as lanolin wax, petroleum waxes such as paraffin wax, microcrystalline wax and petrolatum, mineral waxes such as ozokerite wax, ceresin and montan wax. Of these, carnauba wax, paraffin wax, and microcrystalline wax are preferable. Furthermore, as synthetic wax, for example, oxidized natural wax, amide wax, polyethylene wax, oxidized polyethylene wax, acid-modified polyethylene wax, polypropylene wax, acid-modified polypropylene wax, acid-modified polypropylene wax, Fischer-Tropsch wax, ethylene-vinyl acetate copolymer Examples thereof include a copolymer, an ethylene-acrylic acid copolymer, and an ethylene-methacrylic acid copolymer. Among these, polyethylene wax, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer are preferable, and it is preferable to contain at least one selected from these.

  In addition, it is preferable that the amount of the plasticizer or lubricant exemplified above is small. For example, when a conductor part such as a fine wiring conductor is formed at a site where the resin 50 comes into contact, a resin binder in which a plasticizer or a lubricant of the melted resin 50 is contained in the conductor part during firing is used. This is because there is a possibility of dissolving, and as a result, the strength of the conductor portion is lowered, and the conductor portion may be deformed or disconnected. Also, some of the solid wax and the like need to be careful because some of them cause volume expansion when heated and melted.

(Bubble / hollow resin beads)
The resin 50 preferably further contains bubbles. Thereby, the amount of pyrolyzate generated when the resin 50 is thermally decomposed and removed can be reduced. The air bubbles are preferably uniformly distributed in the resin 50. For example, the resin binder can be included in the resin 50 by making the resin binder porous.

  The method for making the resin binder porous is not particularly limited. For example, a method using phase separation of a polymer solution such as a heat-induced phase separation method or a non-solvent-induced phase separation method, use of a gas generated during polymer formation, heat Utilization of chemical reaction generation gas such as decomposition reaction generation gas, mechanical physics, chemical mixing such as various foaming agents, etc., filling resin beads and using gaps between resin beads Examples thereof include a method of using resin beads such as a method, use of expandable resin beads, use of porous resin beads, use of hollow resin beads, and a microcellular plastic method using carbon dioxide or nitrogen in a supercritical state.

  The resin beads are not particularly limited as long as they exhibit good thermal decomposition behavior upon firing. In the present invention, acrylic resins, α-methylstyrene resins and the like are preferable. The average particle diameter of the (hollow) resin beads is preferably 1 to 20 μm. If the average particle size is less than 1 μm, aggregation of resin beads becomes a problem, and if the average particle size exceeds 20 μm, protrusions are likely to occur on the surface of the filled resin 50. The amount of the resin beads added is an amount that does not cause deformation or cracking of the green sheet due to the melt or gas generated by the resin beads at the time of binder removal. It is good that it is about 50-150 weight part with respect to a part.

  The size of the bubbles is preferably fine on the basis of the pressure equalizing laminate property when forming the laminate 15, and specifically, the average diameter of the bubbles is 500 μm or less, preferably 100 μm or less, more preferably. Is preferably 50 μm or less. For this reason, among the above-described bubble forming methods, it is preferable to use various resin beads such as expandable resin beads, porous resin beads, and hollow beads, or to use a microcellular plastic method. Beads are preferred. Thereby, since the hollow resin beads are rigid bodies, the rigidity of the green sheet 1 in which the recesses 12 are filled with the resin 50 including the hollow resin beads is improved.

  The average diameter of the bubbles is preferably (1/3) t or less with respect to the thickness t of the resin 50 filled in the recess 12. Thereby, when forming the laminated body 15, predetermined pressure equalization lamination | stacking is attained. On the other hand, when the average diameter of the bubbles is larger than the (1/3) t, the rigidity of the resin 50 is lowered, so that it is difficult for the pressure to be transmitted from the resin 50 to the surrounding green sheet when laminated at a high pressure. Therefore, there is a possibility that the pressure uniformity lamination property is lowered. In addition, the thickness t of the resin 50 according to the present invention, that is, the depth of the recess 12 is not particularly limited as long as the above-described pressure equalization lamination is possible.

  The porosity of the resin 50 is about 40 to 80%, preferably about 50 to 70%, for obtaining the above-described effects. The porosity is a percentage of the bubbles contained in the resin 50. For example, the cross section of the resin 50 filled in the recess 12 is observed with a scanning electron microscope, and the ratio of the bubbles in the entire field of view. It can be calculated from

  The resin 50 can be filled in the recess 12 by, for example, screen printing. Specifically, as shown in FIG. 3A, a printing mask 51 on which a predetermined penetration pattern corresponding to the recess 12 is formed is placed on the surface of the green sheet 1, and then the squeegee 52 is placed on the mask 51. As shown in FIG. 3B, the resin 50 is selectively filled into the recess 12 while being pressed against the surface of the resin.

  In addition, when filling, the resin 50 is preferably heated and softened for filling. For this reason, the softening point of the resin is preferably lower than the softening point of the ceramic green sheet 1. Moreover, you may adjust a viscosity with a suitable solvent as needed, and what is necessary is just to dry after filling.

  Next, as shown in FIG. 3C, a laminate 15 is formed by laminating a plurality of green sheets 1 in which the recesses 12 are filled with the resin 50. Specifically, for example, an appropriate adhesive composed of a resin binder, a solvent, and a plasticizer is applied or transferred to the surface of the green sheet, and is pressed and laminated with another green sheet to obtain a laminate 15. .

  Here, in this embodiment, since the resin 50 is filled in the concave portion 12 of the green sheet 1, pressure equalization lamination is possible when the laminate 15 is formed. As a result, the concave portion 12 and FIG. It is possible to obtain the ceramic structure 16 that can suppress the deformation of the cavity 13 shown in d) and does not cause delamination.

  Next, as shown in FIG. 3D, by firing the laminate 15 under a predetermined condition, a ceramic structure 16 that includes the cavity 13 and the concave portion 12 is obtained. The firing temperature can be appropriately selected depending on the relationship with the ceramic material and the like.

In this embodiment, the resin 50 is thermally decomposed and removed during firing. Here, it is preferable that the volume V _{liq. Of} the molten state immediately before the resin 50 is thermally decomposed satisfy the following predetermined relationship. That is, when the volume of the concave portion 12 formed in the ceramic green sheet 1 is V, the occupied volume of the resin 50 filled in the concave portion 12 is 0.8 V to 1.1 V, which is immediately before the resin 50 is thermally decomposed. The volume V _{liq. In the} molten state is preferably 0.2V to 0.6V. Thereby, the pressure equalization lamination | stacking at the time of forming the laminated body 15 is attained, and the quantity of pyrolyzate can be reduced more. The occupied volume means the volume of the resin 50 relative to the volume of the recess 12, and includes the volume of bubbles contained in the resin 50.

This molten state volume V _{liq. Can} be adjusted by, for example, the volume ratio of bubbles introduced into the resin 50. Here, when the ratio of the bubbles in the resin 50 is increased so that V _liq. Is lower than 0.2 V, the strength of the resin 50 may be reduced, and the pressure equalization stackability may be reduced. In addition, when the ratio of bubbles in the resin 50 is reduced so that V _liq. Is higher than 0.6 V, the strength of the resin 50 is increased more than necessary, and the filling property of the resin 50 into the recesses 12 is reduced. There is a risk. Furthermore, when the resin 50 is thermally decomposed, since the void volume of (V-V _liq. ) Is small, it becomes difficult to release the pyrolysis gas of the resin 50 to the outside. There is a risk of cracking or deformation of the surrounding green sheet due to pressure.

  Further, when the laminate 15 is baked and the resin 50 is thermally decomposed and removed, the thermal decomposability of the resin 50 is superior to that of the resin binder contained in the green sheet 1 in which the recesses 12 are formed. It is preferable that it is easy to decompose. As a result, as the resin binder in the green sheet 1 is thermally decomposed (degreasing) and the amount of the residual resin binder in the green sheet 1 is reduced, the strength of the green sheet 1 is reduced and the green sheet 1 becomes brittle. When the resin 50 is thermally decomposed with a delay, the melt of the high-viscosity resin 50 liquefied by heating is heated while being vibrated up and down and left and right accompanying boiling on the surface of the green sheet 1 that has become brittle after degreasing. Since it decomposes, the surface of the green sheet 1 that is in contact with the thermally decomposed portion is partially removed, thereby eliminating the phenomenon that the surface is eroded and destroyed.

  Specifically, the thermal decomposition of the resin 50 starts sequentially from the upper side toward the lower side, and finally the thermal decomposition is completed at the lower side, that is, the upper side of the resin 50 is more than the lower side. It is preferable that it is configured to be easily pyrolyzed. Accordingly, in the first debinding step described below in which the resin binder on the upper side of the resin 50 is thermally decomposed and removed, the concave portion 12 of the green sheet 1 is protected by the resin 50 on the lower side. In the second debinding step, the resin binder on the lower side of the resin 50 is thermally decomposed and removed in the subsequent second debinding step, whereby the resin 50 is melted by the melt of the resin 50. The influence on the green sheet 1 can be minimized. These effects are significant when the filling amount of the resin 50 filling the recess 12 is large.

  As a means for giving a difference in the thermal decomposability of the resin 50 in this way, for example, a method in which the resin 50 is composed of two layers of the upper side and the lower side and the resin material on the upper side and the lower side is changed can be cited. Specifically, the resin 50 that fills the recess 12 is composed of, for example, an upper resin and a lower resin, and the resin binder of the upper resin is selected to be more thermally decomposable than the resin binder of the lower resin. do it. Moreover, you may give a difference in each thermal decomposability by the presence or absence of an above-mentioned bubble.

In particular, the present invention, in the case of removing the resin 50 is thermally decomposed upon sintering of the laminated body 15, the temperature at which the weight of the upper side of the resin 50 is reduced 80% T _a ° C., 80% reduction by weight of the lower side the temperature of the T _b ° C., when the temperature at which the weight of the resin binder in the ceramic green sheets 1 a recess 12 is formed is reduced 20% and the T _c ° C., the relationship T _a <T _b ≦ T _c It is preferable to satisfy.

Thus, after most of the resin 50 is thermally decomposed, the resin binder of the green sheet 1 can start to decompose, and at the stage where the melt of the resin 50 remains, the resin binder of the green sheet 1 Since thermal decomposition has not started, sufficient strength can be maintained. Therefore, the melt of the resin 50 can be prevented from eroding and destroying the green sheet 1 in contact therewith. Moreover, the resin binder of the green sheet 1 can also be fully thermally decomposed by maintaining the temperature exceeding _Tc degreeC for the predetermined time demonstrated below.

For example, the above relationship is obtained by performing differential thermogravimetric thermal analysis (TG / DTA) up to 600 ° C. at a temperature rising rate of 10 ° C./min in a N ₂ atmosphere using a differential high-temperature thermobalance (“TG8120” manufactured by Rigaku Corporation). When performed, the resin binder contained in the ceramic green sheet 1 in which the upper side resin, the lower side resin, and the concave portion 12 are formed preferably satisfies the above relationship. In order to satisfy the above relationship, it is preferable that 99% by weight or more of the resin 50 is thermally decomposed at 600 ° C. or lower.

The temperature profile of the binder removal process at the time of firing is a first temperature profile in which the upper side of the resin 50 is sufficiently thermally decomposed and removed, for example, by maintaining the temperature T _a ° C near the upper side of the resin 50 at 1 to 6 hours. A binder removal step, followed by a second binder removal step in which the lower side of the resin 50 is sufficiently thermally decomposed and maintained by maintaining T _b ° C for 1 to 6 hours, for example, and then a temperature exceeding T _c ° C. For example, it is preferable to carry out by dividing into a third debinding step carried out by maintaining for 1 to 6 hours. The holding time varies within the above range depending on the amount and material of the resin binder.

  Since the concave portion 12 and the internal cavity 13 of the ceramic structure manufactured in this way are formed of a sintered surface having high squareness, flatness, and dimensional accuracy, special planarization treatment such as cutting and surface treatment is performed. There is no need to do it. Therefore, when an electronic component or the like is mounted in the recess 12 or the internal cavity 13, problems such as bonding failure can be prevented. Furthermore, when the ceramic structure is a microchemical chip or the like as a fluid flow path, the flow rate and flow rate can be made constant.

  In addition, since the ceramic structure as designed can be obtained for the radius of curvature, when an electronic component or the like is mounted in the recess 12 or the cavity 13, the effective volume of the recess 12 or the cavity 13 can be maximized. The mounting density of electronic components and the like can be increased. Furthermore, when the cavity 13 is used as a fluid flow path, it is possible to realize a flow rate and a flow velocity as designed.

  If necessary, the inner surface of the recess 12 or the cavity 13 may be subjected to polishing treatment or cutting treatment. Thereby, higher squareness, flatness and dimensional accuracy can be obtained. Further, when the ceramic structure of the present invention is used as a microchemical chip described below, resistance to various chemicals, wettability, water repellency, surface tension, elution of constituent components, surface polarity, surface polarity, Various surface treatments may be performed in consideration of factors that affect the fluid to be treated, such as functional groups.

Another embodiment of the method for producing a ceramic structure according to the present invention includes a step of cutting the surface of the ceramic green sheet to form a recess in the ceramic green sheet, and a step of firing the ceramic green sheet. Features. Even with this configuration, the same effects as those of the embodiment described above can be obtained. The said cutting is not specifically limited, What is necessary is just to perform using the cutting machine which can form the recessed part concerning this invention.
Since the configuration other than the above is the same as that of the embodiment described above, the description thereof is omitted.

  Examples of the use of the ceramic structure of the present invention produced as described above include a microchemical chip. With the progress of microfabrication technology, the development of building a flow system using microfabricated chips, etc., for chemical and biochemical analysis, production operations and reactions is progressing. Microfluidics, μ-TAS (Micro Total Analysis System), MEMS (Micro Electro Mechanical Systems), BioMEMS (Bio Micro Electro Mechanical Systems) and the like are being applied.

  For example, in μ-TAS, a groove is generally formed on the surface of a chip of glass, silicon, ceramic or the like of about 10 centimeters to several centimeters, and a fluid to be treated is flowed into the groove to separate, analyze, react, Production, purification, genetic analysis, etc. Miniaturization of the flow system is effective in reducing the amount of fluid to be processed, speeding up, improving efficiency by increasing the specific surface area, and improving productivity.

  The flow system consists of a flow path, a liquid delivery mechanism such as a pump, a liquid reservoir, a valve, a bent pipe, a branch pipe, a merge pipe, an expansion pipe, a reaction tank, a separation area, a detection flow cell, a heating section, a cooling section, a pH adjustment section, It consists of a laser irradiation unit, a radiation irradiation unit, an inspection unit and the like. In addition, by mounting electrodes, electronic circuits, various sensors, various antennas, etc., electrophoresis of the fluid to be processed, wireless transmission of various data, and the like are possible.

  Furthermore, in order to integrate, integrate, miniaturize, and enhance the functions of machinery, electronics, light, chemistry, biochemistry, etc., a concave structure such as metallized wiring and flow paths is mixed on the same substrate. It is important to use a three-dimensional stacking technique and a technique for forming a plurality of substrates. These techniques are expected to be realized by applying the manufacturing method of the present invention.

  A microchemical chip manufactured by applying the manufacturing method of the present invention is made of ceramic, but a microchemical chip formed of another material excellent in chemical durability, transparency, electrical insulation, etc. You may combine. Examples thereof include glass such as glass and quartz glass, resins such as acrylic resin, polycarbonate and silicone rubber, composite materials thereof, or combinations thereof. These materials take into account factors that affect the fluid to be treated, such as resistance to acids, alkalis, various chemicals, etc., wettability, water repellency, surface tension, elution of constituent components, surface polarity, and surface functional groups. It is preferable to select them.

  The fluid to be treated used in the microchemical chip obtained by applying the production method of the present invention includes pure water, various aqueous solutions, colloidal liquid, suspension, blood, urine, body fluid, nucleic acids (DNA, RNA, etc.) ), Proteins (antigens, antibodies, lectins, adhesins, receptors for various physiologically active substances, peptides, etc.), sugars, cells, various culture solutions, culture extracts, reaction solutions, organic solvents, various chemicals, and mixtures thereof Although a liquid etc. can be used, it is not limited to this.

Examples of uses other than the microchemical chip include the following.
For example,
(A) As shown in FIG. 4, a ceramic structure 18 in which an electric circuit 17 is built in or on the surface,
(B) A waveguide or waveguide circuit board formed by forming a conductor layer on the inner surface of the recess 12 or the cavity 13, or a circuit wiring, a capacitor, an inductance, or the like formed by filling the recess 12 or the cavity 13 with a conductor. Wiring board,
(C) A semiconductor integrated circuit element such as LSI, a piezoelectric vibrator such as a crystal vibrator, a light receiving element such as a photodiode or a CCD element, various sensor elements, using the waveguide circuit board or wiring board of (b), Electronic component storage package for storing various electronic components,
(D) The waveguide of (b), a waveguide circuit, a millimeter wave circuit using a wiring substrate, a millimeter wave radar for automobiles using the millimeter wave circuit,
(E) a fuel cell or a fuel cell reformer in which a flow path for flowing oxygen gas, hydrogen gas, alcohol, hydrocarbon gas, etc. is formed;
(F) an ink jet printer head made of a piezoelectric material, which discharges ink to the outside from the cavity 13 or the flow path formed inside by the piezoelectric effect;
(G) A piezoelectric element such as an actuator made of a piezoelectric material and having a recess 12 or a cavity 13 formed thereon,
(H) a component for optical use in which a conductor layer for mounting an electronic component or the like is formed on the inner surface of the recess 12 or the cavity 13, a substrate, a component for optical use in which an optical path is formed by the recess 12 or the cavity 13, a substrate,
(I) a radio wave absorber in which a plurality of cavities 13 having a fractal structure are formed;
(J) a display component in which a large number of recesses 12 such as a back plate such as a plasma display panel (PDP) and a field emission display (FED) are formed;
Etc.

  In the embodiment described above, the ceramic green sheet 1 in which the concave portion 12 is formed only on the surface has been described. However, the present invention is not limited to this, and the concave portion is formed on both surfaces of the ceramic green sheet. The green sheet may be fired to form a ceramic structure in which concave portions are formed on both sides.

  Moreover, although the said embodiment demonstrated the case of the recessed part 12 formed by pressing the type | mold 10 provided with the convex part 11, this invention is not limited to this, According to the recessed part requested | required A mold having various convex portions can be employed. Specifically, for example, as shown in FIG. 5 (a), a concave portion 32 formed by pressing a mold 30 provided with a convex portion 31 having a curved tip portion, as shown in FIG. 5 (b). The concave part 42 etc. which are formed by pressing the mold | type 40 provided with the convex part 41 in which cross-sectional shape has a substantially triangle are mentioned.

  In the other embodiments described above, the case where the resin 50 is filled in the recesses 12 by screen printing has been described. However, the present invention is not limited to this, for example, as shown in FIG. In addition, the green sheet 1 can be directly filled with the resin 50 with the squeegee 52 without using a printing mask, or using a dispenser (supply nozzle) 53 as shown in FIG. For example, a method of filling the concave portion 12 with the resin 50 may be used.

  Moreover, although the case where the laminated body 15 is constituted only by the green sheet 1 in which the recess 12 is filled with the resin 50 has been described, the present invention is not limited to this, and the green sheet 1 and other green sheets ( A laminate may be formed by laminating with a green sheet in which the recess 12 is not formed. Furthermore, the resin 50 may be composed of only the hollow resin beads described above.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example.

[Example 1]
<Production of green sheet>
11 parts by weight of a binder of a copolymer composition of methyl acrylate and methyl methacrylate per 100 parts by weight of a glass ceramic raw material powder composed of SiO ₂ , Al ₂ O ₃ , CaO, ZnO, B ₂ O ₃ , phthalate as a plasticizer 5 parts by weight of dibutyl acid was added, and toluene was mixed as an organic solvent for 36 hours by a ball mill to prepare a slurry. Using the obtained slurry, it was molded and dried by a doctor blade method to produce a plurality of green sheets having a thickness of 0.7 mm after firing.

<Production of mold>
A mold 10 as shown in FIG. 1 was produced. Specifically, first, a flat die steel was quenched. Next, the main surface to be a die steel mold and the opposite surface were flattened, and then the main surface was ground to form the convex portion 11. The convex portion 11 was formed in such a shape that the concave portion 12 formed by pressing the mold 10 against the surface of the green sheet had a width of 0.2 mm and a depth of 0.2 mm. And the DLC process was given to the whole main surface including this convex part 11. FIG.

<Production of ceramic structure>
The green sheet was placed and fixed on a fixing base (adsorption fixing), the mold 10 was pressed against the surface of the green sheet, and the recess 12 shown in FIG. 1 was formed on the green sheet. A plurality of green sheets were produced, a plurality of green sheets including these green sheets were laminated, and then integrated at a pressure of 4.9 MPa to produce a green sheet laminate.

  Thereafter, the green sheet laminate was debindered and subsequently fired at 950 to 1000 ° C. to produce a ceramic structure having a concave portion on the surface and a hollow structure inside.

[Comparative Example 1]
<Production of ceramic structure using resin sheet>
A first green sheet was produced in the same manner as in Example 1. A through groove having a width of 0.2 mm was produced in the first green sheet, and a second green sheet produced in the same manner as in Example 1 was fitted into the groove except that the thickness was 0.5 mm. .

  Next, a sheet of a resin composition comprising 3 parts by weight of di-2-ethylhexyl phthalate (DOP) and 3.5 parts by weight of polyethylene glycol with respect to 100 parts by weight of an isobutyl methacrylate resin binder was prepared with a thickness of 0.2 mm. This sheet was laminated with the first green sheet in which the second green sheet was fitted in the groove to produce a green sheet laminate.

Next, this green sheet laminate was placed on an Al ₂ O ₃ setter and heated in a mixed atmosphere firing furnace of nitrogen, hydrogen, and steam at 310 ° C., which is around the 80% weight reduction temperature of the resin, for 3 hours. The resin was sufficiently removed by holding.

  After that, the temperature range exceeding 20% weight reduction temperature of the resin binder contained in the green sheet is maintained at 850 ° C. for 3 hours, further debinding is performed, and then baked at 950 to 1000 ° C. A ceramic structure having a recess structure and a hollow structure inside was prepared.

  About each ceramic structure of Example 1 and Comparative Example 1 obtained above, the deformation | transformation of the width | variety of a recessed part was evaluated. The deformation of the width of the recess was observed with a scanning electron microscope. The results are shown in Table 1.

  As is clear from Table 1, the ceramic structure (Example 1) in which the recesses were produced using the mold 10 was easy in workability, and no deformation of the recess width was observed during the operation. On the other hand, in Comparative Example 1 in which the resin sheet was fitted into the through-groove, there was a portion where the groove width was increased by separation from the boundary between the resin sheet and the green sheet in the groove portion.

[Examples 2 to 7]
<Preparation of ceramic structure using resin>
Next, the green sheet with the recesses was filled with resin, and the structure of the recesses or cavities of the ceramic structure was evaluated.
Specifically, first, a green sheet and a concave portion of the green sheet were prepared in the same manner as in Example 1. Next, the green sheet was placed and fixed on a fixing base (adsorption fixing), the mold 10 was pressed against the surface of the green sheet, and the recess 12 shown in FIG. 1 was formed on the green sheet.

  Next, bubbles were introduced into a resin composition comprising 3 parts by weight of di-2-ethylhexyl phthalate (DOP) and 3.5 parts by weight of polyethylene glycol with respect to 100 parts by weight of an isobutyl methacrylate resin binder. A filling resin prepared in a state having an average cell diameter and a melted volume shown in 2 was prepared. A printing mask having an opening substantially the same as the shape of the concave portion 12 is placed on a green sheet, and the filling resin is pressed with a squeegee through the printing mask while heating the filling resin to 60 ° C. Filled with resin.

Subsequently, a plurality of green sheets are integrated by laminating green sheets coated with an adhesive composed of an acrylic resin, a solvent, and a phthalate ester plasticizer at a pressure of 4.9 MPa to produce a green sheet laminate. did. In addition, the occupied volume of the resin was set to 0.8 V to 1.1 V of a void portion that becomes a concave portion of the ceramic green sheet having a volume V (the occupied volume includes the volume of bubbles contained in the hollow resin beads). Moreover, the volume V _{liq. In} the molten state immediately before the resin was thermally decomposed was set to 0.2 V to 0.6 V.

Next, this green sheet laminate was placed on an Al ₂ O ₃ setter and heated in a mixed atmosphere firing furnace of nitrogen, hydrogen, and steam at 310 ° C., which is around the 80% weight reduction temperature of the resin, for 3 hours. The resin was sufficiently removed by holding.

  After that, the temperature range exceeding 20% weight reduction temperature of the resin binder contained in the green sheet is maintained at 850 ° C. for 3 hours, further debinding is performed, and then baked at 950 to 1000 ° C. A ceramic structure having a recess structure and a hollow structure inside was prepared.

[Example 8]
Resin composition comprising 6 parts by weight of DOP and 7 parts by weight of polyethylene glycol, in which resin beads of cross-linked isobutyl methacrylate having an average particle size of 10 μm are added to 100 parts by weight of resin binder of isobutyl methacrylate in the resin composition Bubbles were introduced into the product to prepare a resin in which bubbles were mixed with resin beads having an average bubble diameter and a melted volume. Other conditions were similar to those in Examples 2 to 7, and a ceramic structure was produced.

[Example 9]
In the configuration of the resin filled in the concave portion of the green sheet, a resin having an upper and lower two-layer structure was produced. The filling resin (lower resin) constituting the lower layer part has bubbles in the resin composition consisting of 3 parts by weight of DOP and 3.5 parts by weight of polyethylene glycol with respect to 100 parts by weight of the resin binder of n-butyl methacrylate. It was introduced and filled to a thickness of 0.1 mm.

  On the other hand, the filling resin (upper side resin) in the upper layer portion formed on the lower layer portion is a resin composition comprising 3 parts by weight of DOP and 3.5 parts by weight of polyethylene glycol with respect to 100 parts by weight of the resin binder of isobutyl methacrylate. Bubbles were introduced into the resin and filled to a thickness of 0.1 mm, and a resin-filled green sheet having a bubble average diameter and a molten state volume shown in Table 1 and having a thickness of 0.2 mm was prepared. Other conditions were the same as in Examples 2 to 7 to produce a green sheet laminate.

Then, the green sheet laminate, nitrogen and placed on the Al ₂ O ₃ based setter, hydrogen, a mixed atmosphere firing furnace of steam, 80% weight loss temperature of the resin sheet constituting the upper portion T _a Hold at 310 ° C. near 3 ° C. for 3 hours, sufficiently remove the upper layer resin sheet, and then hold at the lower layer resin sheet 80% weight reduction temperature T _b ° C. near 330 ° C. for 3 hours Then, the lowermost layer resin sheet was sufficiently removed.

Thereafter, the resin binder contained in the green sheet is held at 850 ° C., which is a temperature range exceeding the 20% weight reduction temperature T _c ° C., for 3 hours, further debinding, and subsequently fired at 950 to 1000 ° C. A ceramic structure was prepared.

  About each ceramic structure of Examples 2-9 obtained above, the surface roughness of the bottom face of a recessed part and structural failure were evaluated. Each evaluation method is shown below, and the results are also shown in Table 2.

<Evaluation method of bottom surface roughness>
The surface roughness of the bottom of the recess or cavity is evaluated using a surf test SV-3100 made by Mitutoyo based on the definition of the maximum height Ry defined in Japanese Industrial Standards, and the average value of all measurement sites is calculated. Indicated.
<Evaluation method for structural defects>
The surface of the wall surrounding the recess or cavity was observed with a scanning electron microscope for structural defects.

In each ceramic structure in Examples 2 to 9, by using the mold 10, the concave portions 12 having a desired pattern could be easily formed on the surface. Further, from Table 2, in Examples 2 to 9, the occupied volume of the resin is 0.8 V to 1.1 V of the void portion that becomes the recess of the ceramic green sheet having the volume V (the occupied volume is within the hollow resin beads). (Including the bubble volume included), and the pressure lamination was performed in a state where a resin having a molten state volume V _liq. Of 0.2 V to 0.6 V was fitted, so that deformation was suppressed and excellent dimensions were obtained. A ceramic structure with accuracy could be obtained. Further, an excellent ceramic structure having Ry of 5 μm or less on the bottom surfaces of the recesses and cavities and having less unevenness was obtained.

  In particular, in Example 8, since the resin resin and the bubbles are interposed in the filling resin, the rigidity of the resin sheet itself is improved by the presence of the resin beads which are rigid bodies, and therefore when the layers are laminated at a high pressure However, it was possible to further maintain the uniform pressure lamination and to obtain various results because of the effect of reducing various problems during pyrolysis. Further, in Example 9, the filler resin is formed into an upper and lower two-layer structure having different thermal decomposability, and the binder removal process is performed in multiple stages so that the thermal decomposition of the resin is performed in order from the upper layer portion to the lowermost layer portion Since this happened well, a ceramic structure with a good shape could be obtained.

(A)-(c) is process drawing which shows the manufacturing method of the ceramic structure concerning one Embodiment of this invention. It is a top view which shows an example of the ceramic structure manufactured by one Embodiment of this invention. (A)-(d) is process drawing which shows the manufacturing method of the ceramic structure concerning other embodiment of this invention. It is a top view which shows an example of the ceramic structure manufactured by other embodiment of this invention. (A) And (b) is a schematic sectional drawing which shows the other example of the ceramic green sheet in which the recessed part was formed. It is a schematic explanatory drawing for demonstrating the other method of filling resin into the recessed part of the ceramic green sheet concerning this invention. It is process drawing which shows the conventional manufacturing method of the ceramic structure in which the recessed part was formed in the surface. It is a top view which shows the ceramic green sheet in which the penetration pattern was formed by punching.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ceramic green sheet 10,30,40 Type | mold 11,31,41 Convex part 12,21,32,42 Concavity 13 Cavity 15 Laminated body 16,18,20 Ceramic structure 17 Electric circuit 50 Resin 51 Print mask 52 Squeegee 53 Dispenser

Claims (8)

  A method for producing a ceramic structure, comprising: a step of pressing a mold on a surface of a ceramic green sheet to form a recess in the ceramic green sheet; and a step of firing the ceramic green sheet.   A method for producing a ceramic structure, comprising: a step of cutting a surface of a ceramic green sheet to form a recess in the ceramic green sheet; and a step of firing the ceramic green sheet.   3. The method for manufacturing a ceramic structure according to claim 1, further comprising a step of laminating and firing a plurality of ceramic green sheets including the ceramic green sheet after the step of forming a recess in the ceramic green sheet.   After the step of forming a recess in the ceramic green sheet, the step of filling the recess with a resin, and the step of laminating and firing a plurality of ceramic green sheets including the ceramic green sheet filled with the resin, The method for producing a ceramic structure according to claim 1, wherein the resin is thermally decomposed and removed during firing.   The method for producing a ceramic structure according to claim 4, wherein the resin contains bubbles.   The method for producing a ceramic structure according to claim 4 or 5, wherein the resin includes hollow resin beads. When the volume of the recess formed in the ceramic green sheet is V, the occupied volume of the resin filled in the recess is 0.8V to 1.1V, and the molten state just before the resin is thermally decomposed The method for manufacturing a ceramic structure according to any one of claims 4 to 6, wherein the volume V _liq. Is 0.2V to 0.6V. Wherein the time of the firing time in the resin is removed by thermal decomposition, the temperature T _a ° C. to the weight of the upper side is reduced by 80% resin, the temperature at which the weight of the lower side is decreased to 80% and T _b ° C., the The temperature at which the weight of the resin binder contained in the ceramic green sheet in which the concave portion is formed is reduced by 20% is defined as T _c ° C, and T _a <T _b ≦ T _c is satisfied. The manufacturing method of the ceramic structure of description.

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