JPH0441256A - Method of manufacturing ceramic-metal composite body having pores - Google Patents

Abstract

PURPOSE:To manufacture a ceramic-metal complex having pores without any sintered residue therein by forming a pore formation metal composite sintered body in such a manner that a pattern is buried in a ceramic green compact consisting of a plurality of ceramic green sheets so as to form a pattern buried composite body and burn it. CONSTITUTION:A pattern consisting of a pore formation material and a conductive part formation material is to be formed on one face of a ceramic green sheet consisting of a ceramic material and an organic binder. The pattern constituted of the pore formation material and the conductive material is buried in the ceramic green compact constituted of a plurality of ceramic green sheets so as to form a pattern lay complex. The pattern lay complex is burnt so as to form a pore formation metal composite sintered body. In the burning, for example, the pattern lay complex is supplied to a heater so as to degrease and burnt to form the pore formation metal composite sintered body. Here, the hole is formed due to diffusion of the pore formation material in the process of burning.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for manufacturing a ceramic-metal composite having pores, and more specifically, a ceramic-metal composite having pores in which no sintering residue remains. The present invention relates to a method for manufacturing a ceramic-metal composite.

(Prior Art) As for a method for producing a ceramic-metal composite having pores, there is, for example, a method described in Japanese Patent Application Laid-Open No. 63-99955. This manufacturing method involves forming a pattern with a photopolymerizable photosensitive resin, sandwiching this pattern between ceramic green sheets, forming a conductive part on another ceramic green sheet, and then laminating these together. Then, this laminate is fired to eliminate the resin pattern by thermal decomposition, thereby obtaining a ceramic-metal composite having pores. Furthermore, Japanese Patent Application Laid-Open No. 63-4959 discloses a ceramic inkjet head in which an ink flow path is formed using a photoreceptive resin sheet in the same manner as described above.

When producing a ceramic-metal composite having pores by the above method, the thermal decomposition temperature of the cured photopolymerizable photosensitive resin pattern is higher than the thermal decomposition temperature of the organic binder in the ceramic green sheet. During firing, the organic binder in the ceramic green sheet is thermally decomposed first. In this way, if the organic binder in the ceramic green sheet is thermally decomposed first, the ceramic material in the ceramic green sheet has not yet started sintering when the photosensitive resin pattern shrinks due to thermal decomposition. Since it is in a very brittle state, the ceramic material around the pattern will be peeled off as the pattern shrinks. Therefore, after firing, there is a problem that a residue having the same composition as the ceramic material remains inside the pores.For example, in the case of the above-mentioned ceramic inkjet head, this sintering residue tends to cause ink to become clogged. was there. In addition, since the ceramic green sheets in which the conductive part and the pore-forming base material are formed independently are laminated, misalignment occurs between the two during lamination, and the pores that are finally obtained are There was a drawback that the positional accuracy between the conductive part and the hole in the ceramic-metal composite deteriorated.

(Problems to be Solved by the Invention) The present invention has been made in view of the above problems, and provides a method for manufacturing a ceramic-metal composite having pores in which no sintering residue remains. With the goal.

(Means for Solving the Problems) Known ceramic green sheets can be used as the ceramic green sheet used in the present invention. For example, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, After adding an organic solvent such as toluene and kneading with a mixer such as a ball mill or a vibration mill, a product formed by a molding method such as casting with a doctor blade or extrusion can be used.

The above ceramic materials are not particularly limited, and include, for example, powders of alumina, zirconia, magnesia, sialon, spinel, mullite, crystallized glass, silicon carbide, silicon nitride, aluminum nitride, boron nitride, and MgO-3iOz. -CaO system, Bz(h-5
iOz system, PbO-B2O, -3iO, system, Ca0si
o, -Mgo-sto, system, CaO-3iOz-BaO
-BzO+ system, pbo -3iO□-BzO3-CaO
Examples include glass lift powders such as 2-type glass lift powders, which can be used alone or in combination of two or more types.

The above organic binder is not particularly limited,
Examples include polymeric materials such as polyvinyl alcohol, polyvinylbraral, polymethyl methacrylate, polybutyl methacrylate, cellulose, dextrin, polyethylene wax, starch, and casein, which may be used alone or in combination of two or more. Furthermore, a plasticizer such as dioctyl phthalate, dibutyl phthalate, polyethylene glycol, etc. may be added as necessary.

The pore-forming material used in the present invention includes an organic material that thermally decomposes at a temperature lower than the thermal decomposition initiation temperature of the organic binder, a sublimable material that sublimes at a temperature lower than the thermal decomposition initiation temperature of the organic binder, and the organic material. It is one or more materials selected from the group consisting of volatile materials that decompose at a temperature higher than the thermal decomposition initiation temperature of the binder.

The above-mentioned organic material is not particularly limited as long as it is thermally decomposed at a temperature lower than the thermal decomposition start temperature of the organic binder, and examples thereof include paraffin wax, microcrystalline wax, polymethylstyrene, polybutylene, polystyrene, etc. can be given. Particularly when the organic binder is polyvinyl butyral, paraffin wax, microcrystalline wax, etc. are suitable.

The above-mentioned sublimable material is not particularly limited as long as it is a solid that sublimes at a temperature lower than the thermal decomposition initiation temperature of the organic binder, and examples thereof include naphthalene, benzoic acid, anthraquinone, anthranilic acid, isophthalonitrile, 2. 3
-dichloro-1,4-naphthoquinone, α-naphthol,
Examples include p-phenylphenol and p-nitrophenol.

The vaporizable material is not particularly limited as long as it is thermally decomposed at a temperature higher than the thermal decomposition end temperature of the organic binder, but it is preferably one that decomposes and vaporizes without melting, such as graphite, Carbon black,
Examples include carbon powder such as glassy carbon, powder of melamine, polyimide, isophthalic acid, terephthalic acid, and tetrafluoroethylene resin.

The conductive part forming material used in the present invention is not particularly limited, and examples thereof include gold, silver, copper, palladium,
Examples include metals such as nickel and alloys thereof.

The first step in the present invention is to coat one side of a ceramic green sheet made of a ceramic material and an organic binder.
This is a step of forming a pattern made of the hole-forming material and the conductive part-forming material.

The method for forming the pattern on one surface of the ceramic green sheet is not particularly limited. For example, a pore-forming material is cast on a release film in which a large number of grooves are formed, and then this surface is coated. A method in which a pattern made of a pore-forming material formed by squeegeeing is transferred onto a ceramic green sheet, and then a pattern made of a conductive part-forming material is formed by a screen printing method is formed on a release film by a screen printing method. A method in which a pattern made of a pore-forming material is transferred onto a ceramic green sheet, and then a pattern made of a conductive part-forming material is formed by a screen printing method, and a pattern made of a conductive part-forming material is formed on a support by a plating method. A method of forming a pattern made of a pore-forming material by a screen printing method after transferring the pattern onto a ceramic green sheet;
Examples include a method in which a pattern made of a hole-forming material is formed on a ceramic green sheet by a screen printing method, and then a pattern made of a conductive part forming material is formed by a screen printing method.

Note that when forming the pattern by screen printing,
In order to form a fine pattern and improve the adhesion between the ceramic green sheet and the pattern, a small amount of polymer binder and solvent are added to the above-mentioned pore-forming material and conductive part-forming material, and the mixture is processed using a ball mill, vibration mill, etc. It is desirable to knead it in a mixer to make a paste and use that as a screen printing ink.

The polymer binder is not particularly limited as long as it decomposes at a lower temperature than the thermal decomposition start temperature of the organic binder, and examples thereof include polymethyl methacrylate, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, starch, etc. The amount added may be appropriately determined depending on the types of the above-mentioned pore-forming material and the conductive part-forming material. Since it becomes difficult to decompose and vaporize, the amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the above-mentioned pore-forming material or conductive part-forming material.

The above-mentioned solvent is not particularly limited, and examples thereof include water, methyl alcohol, ethyl alcohol, butyl alcohol, isopropyl alcohol, cyclohexanol, terpineol, methyl ethyl ketone, acetone, ethyl acetate, toluene, xylene, benzene, hexane, Examples include carbon chloride.

The second step in the present invention is to form a pattern-embedded composite by embedding the pattern made of the above-mentioned pore-forming material and conductive material in a ceramic green molded body formed of a plurality of ceramic green sheets. This is the process of The method of embedding the pattern in the ceramic green molded body is not particularly limited, and for example,
One example is a method of sandwiching an 8-pattern pattern between a plurality of ceramic green sheets and bonding them under heat.

The third step in the present invention is a step of forming a pore-forming metal composite sintered body by firing the pattern-embedded composite.

Firing consists of a degreasing process and a firing process, and any known method can be used. For example, the pattern-embedded composite is fed into a heating furnace, degreased, and then fired to form a pore-forming metal composite sintered body. One example is how to form a . Note that the pores are formed by scattering the pore-forming material during the firing process.

The above-mentioned degreasing conditions and scattering conditions for the pore-forming material are appropriately determined depending on the type of organic binder in the ceramic green molded body. After holding at the thermal decomposition temperature or sublimation temperature of the pore-forming material for 5 to 30 hours to scatter the pore-forming material, the temperature can be raised to 1 to b and held at that temperature for 1 to 5 hours to degrease. Desirably, when the pore-forming material is the vaporizable material,
280-700° at a heating rate of 1-100°C/hr
After degreasing by holding at that temperature for 1 to 10 hours, the temperature is increased to the decomposition vaporization temperature of the pore-forming material, e.g. 900°C.
It is desirable to raise the temperature to C and hold at that temperature for 5 to 30 hours. Note that this degreasing step may be performed under reduced pressure.

The above firing conditions are appropriately determined depending on the type of the ceramic material, but the temperature is raised to 600 to 1850°C at a heating rate of 10 to 300°C/hr, and at that temperature
It is desirable to hold it for 5 hours.

(Example) Hereinafter, an example of the method for manufacturing a ceramic-metal composite having pores according to the present invention will be described.

Note that "parts" means "parts by weight."

夾五■ Yualumina powder (average particle size 3μm) 96 parts Pb
PbO-5to'Ca0-BzOs glass lift 4 parts (average particle size 5 μm, yield point 684°C) Polymethyl methacrylate 17 parts (Mw
; I 30,000) Dibutyl phthalate 5 parts Methyl ethyl ketone 23 parts Toluene
18 parts isopropyl alcohol
18 parts of the above ceramic composition was kneaded in an alumina ball mill for 24 hours to obtain a ceramic slurry.

Next, the surface of the polyethylene terephthalate sheet, on which many parallel grooves of 1 mm width, 5 mm spacing, and 500 μm depth were formed on the surface by hot pressing, was treated with a silicone mold release agent, and then the sheet was heated to 80 ° C. Melted paraffin wax (melting point 68°C) is applied to the surface of the sheet, and by moving a squeegee under pressure of 2 kg/-, the paraffin wax on the surface of the sheet is removed and paraffin wax is applied to the grooves. After filling, the paraffin wax was solidified by cooling to room temperature. Next, the slurry is supplied to the surface of the sheet, applied and dried to form a ceramic green sheet with a thickness of 1 mm, and then the polyethylene terephthalate sheet is peeled off and the surface is coated with a line width of 1 mm, a line spacing of 5 mm, and a height of 1 mm. 500
A ceramic green sheet on which a μm paraffin wax pattern was formed was obtained.

The resulting ceramic green sheet with the paraffin wax pattern formed thereon is fed to a screen printing machine.
Silver/
After printing a conductive paste (manufactured by Nichi-Chinese Massey Co., Ltd.) consisting of palladium = 80/20, it is dried, and a line width of 1 mm is printed on the surface.
A ceramic green sheet was obtained in which a rose fin wax pattern with a height of 500 μm and a conductive part forming material pattern with a line width of 500 μm and a height of 20 μm were alternately formed at a line spacing of 2.25 mm.

The obtained ceramic green sheet was 50×50II
After supplying it to a mold of IR1 size, stacking 20 sheets, and pressing at room temperature under a pressure of 65 kg/clll for 3 minutes,
5 having the above pattern by slicing perpendicular to the laminated surface
A ceramic green molded body of 0x22x3 mm was obtained. In the pattern embedded in this ceramic green molded body, the distance between the paraffin wax pattern and the conductive part forming material pattern is 2.3 m.
It was m.

Next, the ceramic green molded body having the above pattern was fed into a heating furnace and held at 80°C for 10 hours, and then heated to 175°C at a rate of 2.5°C/hr to form a paraffin wax pattern. Decomposed zero order, 2,5
After raising the temperature to 500°C at a heating rate of °C/hr, hold at that temperature for 2 hours to degrease, and then increase the temperature to 100"C/hr.
After heating up to 900℃ at a heating rate of r, at that temperature 2
Firing was performed while holding for a certain period of time to obtain a ceramic-metal composite having pores. The distance between the pores in the obtained ceramic-metal composite and the part parallel to the laminated surface of the conductive part is 1.
It was 9mm. The distance between the hole and the conductive part was 1.9 mm at any part of the cross section of the ceramic-metal composite. In addition, the obtained ceramic-metal composite has a cross-sectional size of 800 x 400 μm.
pores were formed, and no sintering residue remained in these pores.

1 Application 1 A composition similar to the ceramic slurry used in Example 1 was applied onto a polyethylene terephthalate film and dried to obtain a ceramic green sheet with a thickness of 1 mm.

Next, the naphthalene was crushed and supplied to an alumina ball mill, and further, to the alumina ball mill, 20 parts of benzene, 10 parts of ethyl alcohol, and 100 parts of naphthalene were added to the alumina ball mill.
10 parts of terpineol, polymethyl methacrylate (
0.01 part of Mw; 80,000) was added and kneaded for 48 hours,
A naphthalene paste was obtained by increasing the viscosity to 2600 cps while splattering the solvent at 40°C. Next, the above-mentioned ceramic green sheet is fed to a screen printing machine, and first, a conductive paste (manufactured by Nichi-Chinese Massey Co., Ltd.) consisting of silver/palladium-80/20 is printed and then dried to give a line width on the surface of the ceramic green sheet. 150μm, height 2
A parallel line conductive part forming material pattern with a line spacing of 0 μm and a line spacing of 600 μm is formed, and the naphthalene paste is printed in the center between the lines of the conductive part forming material pattern and dried,
A ceramic green sheet was obtained in which a conductive part pattern with a line width of 150 μm and a height of 20 μm and a naphthalene pattern with a line width of 150 μm and a height of 20 μm were alternately formed on the surface with a line spacing of 225 μm.

The obtained ceramic green sheet is 50×50+w
20 sheets were stacked in a mold with a size of
A ceramic gellin molded body of 22×3 mm was obtained. In the pattern embedded in this ceramic green molded body, the distance between the conductive part forming material pattern and the naphthalene pattern in a portion parallel to the laminated surface was 230 μm.

Next, the ceramic green molded body having the above pattern was supplied to a heating furnace and heated at 20°C and 10.5 Torr for 2 hours.
After holding for 0 hours, holding at 20°C 10.1 Torr for 10 hours, further holding at 20°C 210-''Torr for 5 hours, and then heating at a heating rate of 10°C/hr to 60°C.
The naphthalene pattern was sublimed by increasing the temperature to °C. Next, the temperature was increased to 500°C in the atmosphere at a heating rate of 2.5°C/hr.
After raising the temperature to 900°C, hold it at that temperature for 2 hours to degrease it, then raise the temperature to 900°C at a heating rate of 100°C/hr, and then hold it at that temperature for 2 hours to perform baking. A ceramic-metal composite with pores was obtained.

The distance between the holes in the obtained ceramic-metal composite and the part parallel to the laminated surface of the conductive part was 190 μm. The distance between the pores and the conductive portion was 190 μm in any part of the cross section of the ceramic-metal composite. In addition, pores with a cross-sectional size of 120×16 μm were formed in the obtained ceramic-metal composite, and no sintering residue remained in the pores.

1 application ±1 carbon paste (manufactured by Fujikura Kasei Co., Ltd., product name: XC-12
) Add 20 parts of terpineol to 100 parts and knead, then mix at 40°C with 2600 cp while scattering the solvent.
The viscosity was increased to 1.5 m to obtain a pore-forming powder.

In the same manner as in Example 2, except that the above carbon paste for forming pores was used instead of the naphthalene paste, a conductive part forming material pattern with a line width of 150 μm and a height of 20 μm was formed on the surface, and a carbon layer with a line width of 150 μm and a height of 20 μm was formed on the surface. A ceramic green sheet was obtained in which patterns were alternately formed with a line spacing of 225 μm.

The obtained ceramic green sheet is 50×50a+
20 sheets were stacked and heated at 160°C.
After pressing for 3 minutes under a pressure of 1250 kg/aa, slices were made perpendicular to the laminated surface to obtain 50 pieces with the above pattern.
A ceramic green molded body measuring 22 mm by 3 mm was obtained.

Butter embedded in this ceramic green molded body
The distance between the conductive part forming material pattern and the carbon pattern in the part parallel to the laminated surface was 230 μm.

Next, the ceramic green molded body having the above pattern was supplied to a heating furnace and heated to 650°C at a heating rate of 10°/hr, held at that temperature for 2 hours to degrease, and further heated at 50°C. 900°C at a heating rate of °C/hr
After raising the temperature to a temperature of 100.degree. C., it was kept at that temperature for 2 hours and fired to obtain a ceramic-metal composite having pores.

The distance between the holes in the obtained ceramic-metal composite and the part parallel to the laminated surface of the conductive part was 190 μm. The distance between the pores and the conductive portion was 190 μm in any part of the cross section of the ceramic metal composite. In addition, pores with a cross-sectional size of 120 x 16 μm were formed in the obtained ceramic-metal composite, and no sintering residue remained in the pores.

(Effects of the Invention) In the method for producing a ceramic-metal composite having pores according to the present invention, the scattering of the pore-forming material pattern occurs before the start of thermal decomposition of the organic binder in the ceramic green molded article or after the end of thermal decomposition. To obtain a ceramic-metal composite having pores in which the walls of the ceramic material around the pores do not collapse and, as a result, no sintered residue of the ceramic material remains within the pores. In addition, the pore-forming material pattern and the conductive part-forming material pattern are arranged accurately at regular intervals using a ceramic green sheet in which the pore-forming material pattern and the conductive part-forming material pattern are arranged accurately at regular intervals. Since it is possible to obtain a buried ceramic green molded body, it is possible to obtain a ceramic-metal composite having pores in which the pores and conductive parts are accurately embedded at regular intervals even after firing.

Claims (1)

[Claims] 1. On one side of a ceramic green sheet made of a ceramic material and an organic binder, an organic material that thermally decomposes at a temperature lower than the thermal decomposition starting temperature of the organic binder, and a sublimable material that sublimes at a lower temperature than the thermal decomposition starting temperature of the organic binder. and one or more pore-forming materials selected from the group consisting of volatile materials that decompose at a higher temperature than the thermal decomposition initiation temperature of the organic binder;
A step of forming a pattern made of a conductive part forming material made of metal, a step of embedding the pattern in a ceramic green molded body made of a plurality of ceramic green sheets to form a pattern embedding composite, and a step of embedding the pattern. A ceramic having pores, comprising the step of: forming a pore-forming metal composite sintered body by firing the composite.
Method for manufacturing metal composites.