JPH0764077B2 - Manufacturing method of pore-forming ceramics sintered body - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a pore-forming ceramics sintered body, and more specifically, a pore-forming ceramics sintered body in which pores do not contain a sintering residue. The present invention relates to a method for manufacturing a bound body.

(Prior Art) As a method for producing a pore-forming ceramics sintered body,
For example, there is a method described in JP-A-63-99955. In this manufacturing method, a pattern is formed with a photopolymerizable photosensitive resin, the pattern is sandwiched between ceramic green sheets and laminated integrally, and the laminated body is fired to cause the resin pattern to disappear by thermal decomposition. By doing so, a pore-forming ceramics sintered body is obtained.

Further, Japanese Patent Application Laid-Open No. 63-4959 discloses a ceramic ink jet head in which an ink flow path is formed by using a photosensitive resin sheet in the same manner as described above.

(Problems to be Solved by the Invention) However, when the void-forming ceramics sintered body is manufactured by the above method, the thermal decomposition temperature of the pattern of the cured photopolymerizable photosensitive resin is the organic binder of the green sheet. Since it is higher than the thermal decomposition temperature of 1, the organic binder of the green sheet is first thermally decomposed during firing. Thus, when the organic binder of the green sheet is thermally decomposed first, at the time when the pattern of the photosensitive resin is thermally shrunk, the ceramic powder of the matrix has not yet started to shrink and becomes extremely brittle. Therefore, the ceramic powder around the pattern is stripped off as the pattern shrinks. Therefore, the obtained pore-forming ceramics sintered body has a problem that it contains a sintering residue of the same component as the matrix ceramics inside the pores. For example, in the case of the above ceramic inkjet head, the sintering residue is Therefore, there is a problem that the ink is easily clogged.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a pore-forming ceramic sintered body that does not contain a sintering residue in the pores.

(Means for Solving the Problems) The method for producing a void-forming ceramics sintered body of the present invention comprises forming a fine line pattern made of a photosensitive resin composition on the surface of a green sheet containing an insulating ceramic material as a main component. , An organic material that melts or decomposes at a temperature lower than the organic binder in the green sheet, a sublimable material that sublimes at a temperature lower than the thermal decomposition start temperature of the organic binder, and a temperature higher than the thermal decomposition end temperature of the organic binder. After filling the pore forming material consisting of any one or more of the powder materials which are pyrolyzed by the above between the fine line patterns, the fine line pattern is eliminated to form a pore pattern made of the pore forming material. The present invention is characterized in that a plurality of green sheets having this hole pattern are laminated, pressure-bonded and fired, whereby the above object is achieved.

Hereinafter, the present invention will be described in detail with reference to the drawings.

According to the present invention, first, a fine line pattern 2 made of a photosensitive resin composition is formed on the surface of a green sheet 1 as shown in FIG.

The green sheet 1 used in the present invention is a molded product mainly composed of ceramic powder before firing and has an insulating property after firing. As the above ceramic powder,
For example, alumina, zirconia, Agnesia, sialon, spinel, mullite, crystallized glass, silicon carbide,
Powder of silicon nitride, aluminum nitride, etc. and MgO-SiO ₂
-CaO based, B ₂ O ₃ -SiO _{2 system, PbO-B 2 O 3 -SiO} 2 system, CaO-SiO
₂ -MgO-B ₂ O ₃ based glass frit powder such as _{PbO-SiO 2 -B 2 O 3} -CaO based and the like, used in combination either alone or two or more kinds.

The green sheet 1 may be manufactured by any method, for example, the above-mentioned ceramic powder may be press-molded. However, as described later, the green sheet 1 has a void formed of a hole-forming material on its surface. After forming the hole pattern 3a, a plurality of layers are laminated and pressure-bonded, and it is necessary that the hole pattern 3a be completely wrapped with the ceramic powder at the time of pressure-bonding. Therefore, it is preferable to have some flexibility. Therefore, the green sheet 1 is preferably formed by a molding method such as injection molding, extrusion molding, compression molding, or casting molding in which a mixture of the above ceramic powder, an organic binder and, if necessary, a solvent is molded. It is preferable to form the mixture in the form of a slurry on a substrate such as a film or a glass plate by applying a doctor blade and then drying the mixture, that is, forming by a so-called doctor blade method. Examples of the organic binder include polymeric materials such as polyvinyl butyral, polyvinyl alcohol, poly (meth) acrylate, cellulose, dextrin, polyethylene wax, starch and casein, and plasticizers such as dioctyl phthalate, dibutyl phthalate and polyethylene glycol. can give. Examples of the solvent include methanol, ethanol, butanol, propanol, methyl ethyl ketone, acetone, ethyl acetate, toluene,
Water etc. can be given. The addition amount of the organic binder and the solvent may be appropriately determined depending on the manufacturing conditions of the green sheet, etc.
Usually, it is suitable to add the organic binder in the range of 5 to 30 parts by weight and the solvent in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the ceramic powder.

The fine line pattern 2 is preferably formed by laminating a photosensitive resin composition on the surface of the green sheet 1, superimposing a photomask having a predetermined fine line pattern, and exposing and developing. It is possible to form a fine line pattern having a line width of about 1 μm by using an electron beam, an X-ray or the like.

As the above-mentioned photosensitive resin composition, those commercially available as a dry film photoresist are preferably used. When the green sheet 1 contains an organic solvent-soluble organic binder, the green sheet is subjected to solvent development. Therefore, it is preferable to use an alkali development type dry film photoresist, and when the green sheet 1 contains a water-soluble organic binder, the alkali development may destroy the green sheet. Therefore, it is preferable to use a solvent-developing type dry film photoresist. In order to form the fine line pattern 2 on the surface of the green sheet 1 with such a dry film photoresist, it is possible to adopt various methods that have been conventionally used for producing a circuit board or the like. Alkali-developing type dry film photoresist is pressure-bonded or heat-melted onto it, and a photomask with a fine line pattern is laid on top of it and exposed by activating light rays with a high pressure mercury lamp etc. After curing the composition, remove the photomask,
A method of developing with an alkaline aqueous solution in which sodium carbonate, sodium hydroxide, potassium hydroxide or the like is dissolved is preferably adopted. Further, a method of forming a fine line pattern of the photosensitive resin composition on an indicator such as a glass plate, a stainless plate or an aluminum plate and transferring the fine line pattern on the surface of the green sheet is also adopted.

When the formation of the fine line pattern 2 by the above-mentioned photosensitive resin composition is completed, the hole forming material 3 is filled between the fine line patterns 2 on the surface of the green sheet 1 as shown in FIG. The pore-forming material 3 is an organic material that melts or decomposes at a lower temperature than the organic binder in the green sheet 1, a sublimable material that sublimes at a temperature lower than the thermal decomposition start temperature of the organic binder, and the organic bond. It is composed of any one or more of powder materials which are thermally decomposed at a temperature higher than the thermal decomposition end temperature of the agent.

The above-mentioned organic material may be one that melts or decomposes at a lower temperature than the organic binder in the green sheet 1,
For example, paraffin wax, microstarine wax, polymethylstyrene, polymethylmethacrylate,
Polybutylene, polystyrene, etc. are used. Particularly, when the organic binder of the green sheet is polyvinyl butyral, paraffin wax, microwax and the like are suitable. Void forming material 3 made of this organic material
Various filling methods can be adopted as a method of filling the space between the fine line patterns 2 of the photosensitive resin composition. For example, when the organic material is wax, the wax is heated to a temperature higher than the melting point to form a molten state, At the same time, the green sheet 1 is preheated to a temperature above the melting point of the wax and below the temperature at which the organic binder does not deteriorate, and the above-mentioned molten wax is applied to the green sheet 1, and a squeegee, spatula, etc.
It is preferable to push the wax between the fine wire patterns 2 while stretching the wax at a pressure of -20 kg / cm ² and to solidify it by cooling, drying or the like. The organic material such as wax remaining on the fine line pattern 2 is preferably removed by wiping it off.

The sublimable material used as the pore-forming material 3 is vaporized at a temperature lower than the thermal decomposition start temperature of the organic binder in the green sheet 1 without undergoing a heat-melting process, or left naturally. A solid powder that is vaporized by source pressure, such as naphthalene, benzoic acid, anthraquinone, anthranilic acid, isophthalnitrile, 2,3-dichloro-1,4-naphthoquinone, α-naphthol, p-phenylphenol, p
-Powder such as nitrophenol. They are,
Methanol, ethanol, butanol, propanol,
It is used as a paste by mixing it with a solvent such as cyclohexanol, terpineol, methyl ethyl ketone, acetone, ethyl acetate, toluene, xylene, benzene, ether and water. Various methods can be adopted as a method of filling the paste-like sublimable material between the fine line patterns 2. For example, the paste-like sublimable material is applied onto the green sheet 1, and a squeegee, a spatula, or the like is used. Using 0.
A method in which the paste-like material is stretched at a pressure of 1 to ²⁰ kg / cm ² and pressed between the fine wire patterns 2 is preferably adopted.

The powder material used as the pore-forming material 3 may be one that is thermally decomposed at a temperature higher than the thermal decomposition end temperature of the organic binder in the green sheet 1, but is decomposed and vaporized without melting. Preferred are carbon powders such as graphite, carbon black, and glassy carbon, and powders of melamine, polyimide, isophthalic acid, terephthalic acid, tetrafluoroethylene resin, and the like. These are methanol, ethanol, butanol,
Propanol, cyclohexanol, terpineol,
It is used as a paste by mixing with a solvent such as methyl ethyl ketone, acetone, ethyl acetate, toluene, xylene, benzene, ether, and water. Such a pasty material may be filled between the fine line patterns 2 in the same manner as the above-mentioned organic material or pasty sublimable material.

As described above, when the work for filling the space between the fine wire patterns 2 with the pore forming material 3 made of one or more of the organic material, the sublimable material, and the powder material is completed, FIG.
As shown in (3), the fine line pattern 2 is peeled off to form a hole pattern 3a made of a hole forming material on the surface of the green sheet 1.

The fine line pattern 2 is peeled off by spraying a developing solution or the like used for development, regardless of whether the hole forming material 3 is an organic material, a sublimable material or a powder material. Since the photosensitive resin composition of No. 2 is cured by irradiation with actinic rays, it does not easily peel off under the developing conditions at the time of forming the fine line pattern. Therefore, it is preferable to lengthen the developing time, increase the temperature of the developing solution, or increase the concentration of the developing solution according to the degree of curing of the photosensitive resin composition to peel off. When the thin line pattern 2 is peeled off in this manner, the hole pattern 3a of the hole forming material having an inverted shape of the thin line pattern, that is, a gap shape of the thin line pattern is formed on the surface of the green sheet 1. In addition, when the material for forming pores is a paste of the powder material of the above-mentioned high temperature decomposition type, after forming the pore pattern 3a, it is held at 50 to 160 ° C. for 10 to 60 minutes, if necessary, in the paste. It is preferable to solidify the residual solvent by scattering.

When the formation of the hole pattern 3a is completed as described above,
As shown in FIG. 1 (d), a plurality of green sheets 1 having the hole patterns 3a are laminated and pressure-bonded to form a laminated body 4, and the laminated body 4 is further degreased and fired. A ceramic sintered body A having pores 5 as shown in FIG. 1 (e) is obtained.

The number of laminated green sheets 1 may be appropriately determined according to the size of the target pore-forming ceramics sintered body, but if it is too thick, it becomes difficult to press-bond and the pore pattern is formed.
Since 3a is less likely to be wrapped by the green sheet 1, the thickness of the green sheet 1 and the hole pattern 3a is 10μ.
In the case of the m-order, it is preferable to stack about 50 to 1000 sheets. Then, in order to obtain a thicker product, it is sufficient to stack a plurality of laminated bodies that have been laminated and pressure-bonded once and then pressure-bond them again.

The pressure bonding conditions may be appropriately determined, but when the hole pattern 3a is formed of the organic material described above, the temperature condition is 20 to 16
The temperature is within the range of 0 ° C and the hole pattern 3a is not softened, and the pressure condition is 1 to 10 kg / cm ^{2 at} a pressure of 1 to 10
It is appropriate to carry out split pressure bonding. Also, the case of forming the holes pattern 3a with a paste of sublimable material described above, at a temperature no greater vapor pressure of sublimable material, to crimp 10 minutes under a pressure of 1 to 100 kg / cm ² When the hole pattern 3a is formed of the above-mentioned powder material paste, it is suitable to perform pressure bonding at 20 to 160 ° C. under a pressure of 1 to 100 kg / cm ² for 1 to 10 minutes.

The hole patterns 3a may be formed on both sides of the green sheet 1. In that case, the green sheet 1 having the hole patterns 3a and the green sheet not having the hole patterns 3a are alternately laminated and pressure-bonded to each other. You just have to form the body.

The laminated body 4 laminated and pressure-bonded under the above conditions is heated in a heating furnace to be degreased and fired. However, when the hole pattern 3a is formed of the organic material described above, degreasing is performed before degreasing. At a temperature lower than the temperature, that is, at a temperature at which the organic binder of the green sheet 1 is not decomposed, the organic material of the hole pattern 3a is thermally decomposed to form the holes 5. Also, when the hole pattern 3a is formed of the above-described sublimable material, the sublimable material is vaporized before degreasing to form the holes 5. As a method of vaporizing, various methods such as heating at a temperature lower than the decomposition start temperature of the organic binder of the green sheet 1, depressurization of 1 Torr or less, action of these heating and depressurizing, or leaving at room temperature are adopted. When the pores 5 are thus formed before degreasing, the organic binder of the green sheet 1 is not thermally decomposed at the stage of forming the pores, and the ceramic powder is in a state of being strongly bonded by the organic binder. Therefore, the ceramic powder around the holes 5 does not collapse and enter the holes 5. On the other hand, when the pore pattern 3a is formed of the above-mentioned high temperature decomposition type powder material, the powder material is thermally decomposed to form the pores 5 in the firing step after degreasing, so the pores before degreasing are formed. No formation processing is required.

The degreasing condition of the laminated body 4 may be appropriately determined in consideration of the material of the hole pattern 3a and the organic binder in the green sheet 1, but the hole pattern 3a is formed of the above-mentioned organic material or sublimable material. In the case of the laminated body, it is appropriate to raise the temperature at a temperature rising rate of 1 to 100 ° C./hr and hold it at 280 to 600 ° C. for 1 to 5 hours to degrease it. In the case of a laminate formed of the material, the temperature is raised at a heating rate of 1 to 100 ° C / hr,
It is suitable to hold at 280 to 700 ° C for 1 to 5 hours for degreasing.

The firing conditions after degreasing may be appropriately determined in consideration of the type of ceramic powder of the green sheet 1, but generally, the temperature is raised at a heating rate of 10 to 300 ° C / hr to 760 to 1650 ° C.
It is suitable to hold at 1 to 5 hours for firing.

In the void-forming ceramics sintered body obtained as described above, since the ceramic powder around the void pattern does not collapse in the void forming stage, the sintering residue is not contained in the voids.

(Operation) As described above, the method for producing the pore-forming ceramics sintered body according to the present invention is an organic material which is thermally melted or decomposed at a lower temperature than the organic binder in the green sheet, and the thermal decomposition of the organic binder is started. Using a pore-forming material made of one or more of a sublimable material that sublimes at a temperature lower than the temperature and a powder material that thermally decomposes at a temperature higher than the thermal decomposition end temperature of the organic binder, a pore pattern is formed on the surface of the green sheet. When the hole pattern is made of the above organic material or sublimable material, the holes are formed at the initial stage of firing (the stage before degreasing), because the layers are formed, and a plurality of these layers are stacked and pressure-bonded and fired. The pattern material is decomposed or vaporized to form vacancies. At this vacancies formation stage, the organic binder on the green sheet is not thermally decomposed, and the ceramic powder is firmly bound by the organic binder. Was done Because the state is not to enter into the pores ceramic powder around the holes pattern collapses. Further, when the pore pattern is formed of the above powder material, the powder material is decomposed to form pores in the latter stage of firing (the stage after degreasing). At the forming stage, since the ceramic powder starts sintering shrinkage and is firmly bonded, the ceramic powder around the hole pattern does not collapse and enter the holes. Therefore, in any case, it is possible to obtain a ceramics sintered body in which the sintering residue of the ceramics powder is not contained in the pores.

(Examples) The present invention will be described below with reference to Examples. The term "part" means "part by weight".

Example 1 In an alumina ball mill, 96 parts of alumina powder having an average particle size of 3 μm, 4 parts of PbO—SiO ₂ —B ₂ O ₃ —CaO glass frit having an average particle size of 5 μm, and polymethacrylate (Mw: 130,000) were used. 1
7 parts, dibutyl phthalate 5 parts, methyl ethyl ketone 24 parts, toluene 18 parts, isopropyl alcohol 18 parts
0.5 parts of Solvent Black 7 was kneaded and kneaded for 3 hours to obtain a slurry. This slurry was supplied to a doctor blade type green sheet making machine, coated on a polyethylene terephthalate film and dried to produce a green sheet (100 mm × 100 mm) having a thickness of 60 μm.

On the other hand, methyl methacrylate-n-butyl methacrylate-
Acrylic acid copolymer (6/2/2, Mw: 150,000) 60 parts, 2,2 'bis (4-methacryloxydiethoxyphenyl) propane
15 parts, 15 parts of hexamethylene diacrylate, 2 parts of 2,4-dimethylthioxanthone, 2 parts of ethyl p-dimethylaminobenzoate, 0.05 parts of malachite green, 0.1 parts of paramethoxyphenol and 200 parts of methyl ethyl ketone are uniformly dissolved and exposed. A liquid is obtained, and this photosensitive liquid is applied on a polyethylene terephthalate film having a thickness of 20 μm and dried,
A dry film photoresist having a thickness of 25 μm was produced.

This dry film photoresist is heat-laminated on the green sheet at 100 ° C. at 3 kg / cm ² , and the polyethylene terephthalate film that is the support of the dry film photoresist is brought into close contact with a negative photomask having a fine line pattern, from a 3 kW high pressure mercury lamp. 3 UV rays at a distance of 50 cm
It was exposed to 5 mJ / cm ² . Then remove the polyethylene terephthalate film, spray a 1% by weight aqueous solution of sodium carbonate at 30 ° C at 1 kg / cm ² and develop in 30 seconds, line width 25μ
m, a fine line pattern having a line interval of 30 μm was formed on the surface of the green sheet.

The green sheet on which this fine line pattern was formed was heated to 80 ° C, and the paraffin wax (mp68
C) was applied and the squeegee pressed with a pressure of ² kg / cm ² was moved to fill the paraffin wax between the fine line patterns and then cooled to room temperature to solidify the paraffin wax. Then, spray a 3% by weight aqueous solution of sodium hydroxide at 30 ° C. at 1 kg / cm ² and treat for 3 minutes. Peel off the fine line pattern of the dry film photoresist to obtain a line width of 30 μm.
A hole pattern of paraffin wax having a thickness of 20 μm was formed on the surface of the green sheet.

The polyethylene terephthalate film, which is the support, was peeled from this green sheet, and the green sheet was
Laminate the sheets and press at room temperature under pressure of 35 kg / cm ² for 3 minutes,
A laminate of 100 × 100 × 48 mm was obtained. This laminated body is sliced perpendicularly to the laminating plane to form a sliced body having a thickness of 3 mm, and the sliced body is supplied to a heating furnace and held at 80 ° C. for 10 hours, and then 175 at a heating rate of 2.5 ° C./hr. The temperature was raised to ℃ and kept for 10 hours to decompose the paraffin wax. Next 2.5 ° C / hr
At a heating rate of 500 ℃, hold for 2 hours to degrease,
Further, the temperature was raised to 1650 ° C. at a heating rate of 100 ° C./hr, and firing was performed for 2 hours to obtain a ceramics sintered body having a thickness of 2.5 mm. This ceramic sintered body had a large number of holes communicating from one surface to the other surface facing each other, and no sintering residue was contained in the holes.

Example 2 Similar to Example 1, a line width of 25 μm was formed on the green sheet,
A fine line pattern made of a dry film photoresist with a line interval of 30 μm was formed.

Next, crush the naphthalene and add benzene to this powder.
Parts, 10 parts of ethanol and 10 parts of terpineol were added and kneaded, and the viscosity was increased to 2600 ps while scattering the solvent at 40 ° C. to obtain a naphthalene paste.

This naphthalene paste was applied between the fine line patterns of the green sheet, a squeegee pressed with a pressure of ² kg / cm ² was moved, the naphthalene paste was filled between the fine line patterns, and then dried at room temperature for 30 minutes. Then, a 1% by weight aqueous solution of sodium carbonate at 30 ° C. is sprayed at 1 kg / cm ² and treated for 2 minutes, the fine line pattern of the dry film photoresist is peeled off, and the line width is 30 μm, the line interval is 25 μm, and the thickness is 12 μm. And a hole pattern was formed on the surface of the green sheet.

This green sheet was 40 kg / cm ^{2 at} room temperature as in Example 1.
Pressure bonding under the conditions of, and sliced to form a sliced body with a thickness of 3 mm, this sliced body is supplied to a decompression furnace, and 20 ° C,
After holding at 0.5 Torr for 10 hours, hold at 0.1 Torr for 10 hours,
The temperature was further maintained at 10 ⁻³ Torr for 5 hours, and the temperature was raised to 60 ° C. at a temperature rising rate of 10 ° C./hr. And 2.5 ℃ / hr at atmospheric pressure
The temperature is raised to 400 ° C at a heating rate of 2 hours, held for 2 hours to degrease, then raised to 1650 ° C at a heating rate of 100 ° C / hr and fired for 2 hours. I got a union. This ceramic sintered body had a large number of holes communicating from one surface to the other surface facing each other, and no sintering residue was contained in the holes.

Example 3 Benzoic acid was used in place of the naphthalene of Example 2, 20 parts of benzene, 10 parts of ethanol and 10 parts of terpineol were added to the powder and kneaded, and the solvent was scattered at 40 ° C.
The viscosity was increased to 2600 ps to obtain a benzoic acid paste. Then, a sliced body having a thickness of 3 mm was obtained in the same manner as in Example 2, the sliced body was supplied to a decompression furnace, held at 60 ° C. and 0.1 Torr for 10 hours, and further heated to 100 ° C. at 10 ° C./hr. Then 5 × 10 ^-2 To
Hold at rr for 10 hours. Then 40 at atmospheric pressure 2.5 ℃ / hr
The temperature was raised to 0 ° C., and thereafter, in the same manner as in Example 2, a pore-forming ceramics sintered body having no sintering residue in the pores was obtained.

Example 4 In an alumina ball mill, 40 parts of alumina powder having an average particle size of 3 μm, 60 parts of PbO—SiO ₂ —B ₂ O ₃ —CaO glass frit having an average particle size of 5 μm, 12 parts of polyvinyl butyral and dibutyl phthalate were used. 5 parts, methyl ethyl ketone 24 parts, toluene 18 parts, isopropyl alcohol 18 parts, Solven
0.5 parts of t Black 7 was supplied, and a green sheet was obtained in the same manner as in Example 1.

Then, in the same manner as in Example 1, the line width is 25 μm and the line spacing is 30 μm.
A thin line pattern of m is formed on a green sheet, 20 parts of terpineol is mixed with carbon paste (Fujikura Kasei Co., Ltd., XC-12), the solvent is dispersed at 40 ° C and the viscosity is increased to 2600ps. The squeegee pressed on the surface of the sheet and pressed with a pressure of ² kg / cm ² was moved to fill the thickened carbon paste between the fine line patterns, and dried at room temperature for 30 minutes. Then, the fine line pattern of the dry film photoresist was peeled off in the same manner as in Example 2 and then held at 80 ° C. for 30 minutes to solidify the carbon paste to obtain a line width of 30 μm and a line interval of 25 μm.
A hole pattern made of carbon paste having a thickness of 12 m and a thickness of 12 m was formed on the surface of the green sheet.

The polyethylene terephthalate film that is the support is peeled from this green sheet, and 600 sheets are laminated to form 120 sheets.
Pressed for 3 minutes under the condition of ℃ and 60kg / cm ² , 100 × 100 × 40mm
A laminated body of was obtained. Then, this laminated body was sliced perpendicularly to the laminated surface to form a sliced body having a thickness of 3 mm, which was supplied to a heating furnace and heated to 650 ° C. at 10 ° C./hr for 4 hours and then further heated to 100 ° C. The temperature was raised at a rate of / hr and firing was carried out at 950 ° C. for 2 hours to obtain a pore-forming ceramics sintered body having a thickness of 2.5 mm and no sintering residue in the pores.

Example 5 In the same manner as in Example 1, a line width of 25 μm was formed on the green sheet,
A fine line pattern of dry film photoresist with a line spacing of 30 μm was formed. On the other hand, 30 parts of terpineol and 10 parts of isopropanol were added to the isophthalic acid powder and kneaded to obtain 40 parts.
While isolating the solvent at ℃, the viscosity was increased to 2600 ps to obtain an isophthalic acid paste. Then, this paste is used in Example 2.
In the same manner as above, fill the space between the thin line patterns on the green sheet, dry at 60 ° C for 30 minutes, then spray a 3% by weight aqueous solution of sodium hydroxide at 30 ° C at 1 kg / cm ² for 3 minutes and dry. After peeling off the thin line pattern of film photoresist, it is dried at 120 ° C for 30 minutes, line width 30μm, line interval 25μ
A hole pattern made of isophthalic acid having a thickness of m and a thickness of 12 μm was formed on the surface of the green sheet.

This green sheet was laminated, pressure-bonded and sliced in the same manner as in Example 1 to obtain a sliced body having a thickness of 3 mm. Then, put this sliced body in a heating furnace and 2.5 ℃ / hr
After heating to 300 ° C. for 2 hours to degrease the green sheet, the temperature was raised to 330 ° C. at 2.5 ° C./hr and maintained for 24 hours to vaporize isophthalic acid. Then, the temperature is raised to 500 ° C at 5 ° C / hr, further raised to 1650 ° C at 100 ° C / hr, and fired for 2 hours to form a 2.5 mm-thick pore-forming ceramic with no sintering residue in the pores. A sintered body was obtained.

(Effect of the Invention) In the method for producing a void-forming ceramics sintered body of the present invention, since the ceramic powder around the void pattern does not collapse and enter the voids in the void forming stage, A remarkable effect is obtained in that a pore-forming ceramic sintered body can be obtained in which the sintering residue of the ceramic powder is not contained in the pores.

[Brief description of drawings]

FIGS. 1 (a) to 1 (e) are explanatory views for explaining step by step a method for producing a void-forming ceramics sintered body of the present invention. 1 ... Green sheet, 2 ... Fine line pattern, 3 ... Hole forming material, 3a ... Hole pattern, 4 ... Laminated body, 5
…… Void, A …… Void-forming ceramic sintered body.

Claims (1)

[Claims] 1. An organic substance which is formed by forming a fine line pattern made of a photosensitive resin composition on the surface of a green sheet containing an insulating ceramic material as a main component, and which is melted or decomposed by heat at a lower temperature than the organic binder in the green sheet. A material, a sublimable material that sublimes at a temperature lower than the thermal decomposition starting temperature of the organic binder,
A pore-forming material comprising any one or more of powder materials that are pyrolyzed at a temperature higher than the thermal decomposition end temperature of the organic binder,
After filling between the fine line patterns described above, the fine line patterns are eliminated to form a hole pattern made of a hole forming material, and a plurality of green sheets having the hole patterns are laminated, pressure-bonded and fired. A method of manufacturing a pore-forming ceramic sintered body, comprising: