JPH0885175A - Method for manufacturing honeycomb-shaped ceramic structure - Google Patents

Abstract

PURPOSE: To permit the manufacture of fine cell structure easily by a method wherein a plurality of layers of ceramics material sheets, each comprising a sheet type substrate printed with a slurry based on a ceramic material, are superposed to define cells by the combination of the ceramic material sheets superposed on the printed pattern. CONSTITUTION: For manufacturing the honeycomb structural body 9 of ceramic, a thick printing of slurry 2, having a thickness of 5μm-2mm, is applied on a sheet 1 at first to obtain a ceramics material sheet 3, into and/or onto which ceramics material is laminated and/or impregnated. Next, a screen 4, having a predetermined pattern, is put on the sheet 1 and the slurry 2 is applied to flow on the surface of the screen 4, then, a predetermined pattern, padded thick with the slurry 2, is printed in a stage 8 to form a pattern sheet 5. Subsequently, the ceramic material sheet 3 and the pattern sheet 5 are piled up to form the honeycomb structural body 9 of ceramic, with open cells 10 whose upper surface is constituted of the ceramics material sheet 3 and whose lower surface is constituted of the specific surface of non-printing part 7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a honeycomb-shaped ceramic structure, and more particularly to a method for manufacturing a honeycomb structure which can be freely designed by laminating printing sheets using screen printing of a ceramic slurry.

[0002]

2. Description of the Related Art Extrusion molding is a typical method for manufacturing a honeycomb-shaped ceramic structure.
In Japanese Patent Application Laid-Open No. 48-66112, a flat ceramic material sheet is processed to have an uneven shape, and the uneven sheet is laminated or rolled in the circumferential direction (direction parallel to the surface forming the honeycomb) of a cell (uneven portion) and baked. It was a honeycomb-shaped ceramic structure provided with open cells.

Further, in Japanese Patent Application Laid-Open No. 48-66112, a plurality of long tubular pipes forming open cells are wound around a flat ceramic material sheet and fired in a direction parallel to a plane forming a honeycomb. It was a honeycomb-shaped ceramic structure provided with open cells.

Japanese Patent Laid-Open No. 179060/1982 discloses a ceramic structure having a three-dimensional mesh structure, in which the structure has plasticity, and rods are provided from both ends of the structure so as not to penetrate the structure alone or mutually. Then, a ceramic structure having open cells communicating with the holes by a three-dimensional mesh structure was manufactured.

In Japanese Patent Laid-Open No. 2-261652, a photosensitive pore forming material such as an organic material which is melted or decomposed by heat at a lower temperature than the organic binder in the green sheet is used to form a green sheet on the surface of the green sheet by a photoresist technique. A fine wire pattern is formed, and then a ceramic material is filled between the patterns, and a plurality of green sheets are laminated, pressure-bonded and fired, and pores are formed after the fine wire pattern is burned off during firing, A formed ceramic sintered body was obtained.

Japanese Patent Laid-Open No. 2-296779 differs from the previous publication only in that the fine line pattern is removed with an organic solvent before firing.

[0007]

However, in extrusion molding, there is a limit to the honeycomb shape that can be obtained. For example, in order to form a fine cell diameter, the cylindrical part of the die corresponding to the cell must have a fine diameter, but it must be thick enough to withstand the flow pressure of the molding material, and the cell of the micrometer order It was not possible to produce a ceramic structure with a diameter.

Furthermore, the axially thick structure of the open cells is difficult to extrude because the fluidity of the molding material is lowered, and the mold must be made large in order to obtain a large structure.

Further, during the manufacturing process, in the honeycomb structure forming process in a state of having a predetermined plasticity, cracks, cracks or breakage easily occur due to the limit of the self-holding force and the forming pressure, and particularly complicated cell shapes and cell patterns are formed. It was difficult to manufacture a honeycomb-shaped ceramic structure having a small cell diameter.

Further, in a method in which a ceramic sheet is processed by a corrugated method or the like to form a hollow tubular body and the hollow tubular bodies are aggregated to form a honeycomb structure, a fine cell form with little dimensional accuracy error is produced. It was difficult to do so, and the step of forming a tubular body was essential.

Also, in the method of making a hole in a ceramic having a plasticity with a rod and using this hole as a cell, a fine-shaped cell cannot be obtained as in extrusion molding, and the communicating shape of the cell is linear. However, the decisive drawback is that the cell walls cannot be made strong enough. On the other hand, a ceramic material having no plasticity cannot be extruded, and an expensive binder is required for extrusion molding.

Further, after forming a fine line pattern by a photoresist and filling the void space between the patterns with the ceramic raw material, the fine line pattern is removed and a ceramic having fine pores in which fine line pattern traces are formed as cells (cells). The method of manufacturing a structure requires a multi-step process of laminating a photosensitive resin, forming a photomask, exposing and developing, and has a drawback that the process is complicated.

Further, it is difficult to form a fine line pattern having a small width and a high height (thickness) by a photoresist technique, and the pattern after etching is inevitably deformed by over-etching or the like. It was not suitable for forming a cell having a size of.

The basic object of the present invention is that the cell structure and cell pattern forming the honeycomb can be freely designed including the cell shape, cell diameter, cell wall thickness, etc., and it is possible to easily accommodate design changes. There is a simple method for manufacturing a honeycomb-shaped ceramic structure.

Furthermore, it is an object of the present invention to provide a method for manufacturing a honeycomb-shaped ceramic structure having a cell structure having a particularly fine shape.

Another object of the present invention is to provide a method for manufacturing a honeycomb-shaped ceramic structure which is simple and suitable for mass production.

Still another object of the present invention is to provide a method for manufacturing a honeycomb-shaped ceramic structure having a very wide range of applicability to raw materials.

The present invention achieves at least one of the above objects and problems.

[0019]

According to the present invention, a pattern sheet forming step of forming a ceramic material sheet having a predetermined printing pattern by printing a slurry containing a ceramic raw material as a main component on a sheet-shaped substrate, A honeycomb including at least one pattern sheet, a plurality of ceramic material sheets being superposed on each other, and forming a cell by a combination of the printed pattern and the superposed ceramic material sheets. A method for manufacturing a ceramic structure is provided. The sheet-shaped substrate may be any one capable of printing the slurry, and the ceramic material sheet is not only the pattern sheet on which the slurry is printed but also the ceramic material adhered or impregnated on a part or all of the sheet-shaped body. It also includes ceramic paper, etc.

[0020]

Preferably, the printing of the slurry is a screen printing in which a screen formed in a predetermined pattern is arranged on the sheet and the slurry is printed on the sheet-shaped substrate through the screen. .

Further, the ceramic material sheets and the pattern sheets are alternately laminated.

Further, the above-mentioned pattern sheets are laminated in a plurality of layers.

Further, the cell is characterized in that it is a cell communicating at least in a direction parallel to the pattern printing surface.

Further, the pattern sheets having through holes perpendicular to the printing surface of a predetermined pattern are laminated to form cells in which the through holes communicate with each other in a direction perpendicular to the pattern printing surface.

Further, it is characterized in that the print patterns of at least one set of the pattern sheets are laminated so as to intersect with each other with or without the ceramic material sheet interposed therebetween.

Further, it is characterized in that the printing patterns intersect at a right angle.

Further, the printing pattern is printed in line symmetry.

Further, the method is characterized by including the step of printing the slurry on the entire surface of the sheet-shaped substrate to form a ceramic layer to form the ceramic material sheet.

Furthermore, at least one of the pattern sheet and the ceramic material sheet is made of a raw material containing ceramics and organic fibers as main components.

Further, the non-printed portion of the pattern sheet is burned off during the firing of the structure, so that the cells communicate with each other in the stacking direction.

Further, the thickness of the layer of the printing pattern is 5
It is characterized in that it is μm to 2 mm.

Further, the short diameter of the cells of the honeycomb-shaped ceramic structure in the cross-sectional direction is 0.01 to 2 mm.

Further, it is characterized in that the print patterns on the same print pattern sheet are different in shape and / or material.

It is characterized in that the sheet-like substrate is made of paper or cloth whose main component is organic matter.

It is characterized in that the slurry contains a metal component.

[0036]

The term "ceramic" is also used as an abbreviation for ceramic raw material or ceramic material.

According to the method for manufacturing a honeycomb-shaped ceramic structure of the present invention, it will be outlined. A slurry containing a ceramic raw material as a main component is printed on a sheet to form a three-dimensional pattern consisting of a predetermined pattern of ceramic material and a non-printed portion. And, a ceramic printing (material) pattern sheet having planar unevenness is manufactured, and a ceramic material sheet including at least one layer of the ceramic printing sheet having the unevenness of the predetermined pattern is overlaid in a plurality of layers, and the printed pattern and the ceramic material sheet are combined. A predetermined honeycomb shape having cells surrounded by a wall is formed.

By printing a ceramic-based slurry instead of ink by a printing technique,
Only 5 patterns made of ceramic instead of printing
Three-dimensional thick printing can be performed on a sheet with an error of about μm or less. Since this pattern is a printing technique, an arbitrary pattern can be freely designed and manufactured simply by changing the screen in screen printing.

It is also possible to pattern non-extrudable, non-plastic ceramic materials by the printing technique of the invention.

Printing techniques include offset printing and screen printing.

Offset printing is a method in which the ink is first transferred to a flat or roll-shaped transfer plate and then the ink is transferred from the transfer plate to the printing medium. Of course, in the present invention, a slurry containing ceramic as a main component is used instead of the ink. This method is suitable for forming a printing pattern made of a relatively thin ceramic.

On the other hand, in the screen printing, a mold (frame) formed in a predetermined depth (three-dimensional form) and a predetermined pattern (planar form) is set on a material to be printed (sheet-like body), The slurry is printed from above, and the ceramic is adhered to the patterned part on the sheet-shaped part corresponding to the unpatterned part of the mold at a height corresponding to the depth of the mold. Therefore, a two-dimensional and three-dimensional ceramic printing pattern is formed.

In the screen printing technique using a screen formed in a predetermined pattern, the pattern is formed by attaching a pattern or a photosensitive resin pattern of a predetermined pattern to a mesh frame made of silk or stainless steel, and placing it on a sheet-like body. ,
The slurry can be printed on the sheet-like body under the net frame. Since the photosensitive resin is expensive, it is suitable as a raw material for manufacturing a product having a particularly high unit price.

The screen formed in a predetermined pattern may be formed by cutting or the like, but in order to produce a screen having a high dimensional accuracy and a fine pattern on the order of micrometer or a complicated shape, photoengraving is used. Suitable for screen production. Similar to a circuit pattern of a semiconductor or the like, it has high accuracy, and a fine and complicated pattern can be easily created.

The screen can also be formed by masking with tape.

As the method for adhering the slurry to the sheet-like body, the slurry is pressure-bonded with a roller, a stage, etc., the excess slurry is peeled off by a doctor blade after the slurry flows, and the sheet-like body with the screen attached is immersed in the slurry. There is a method, a method of spraying or applying a slurry.

Further, it is easy to form each pattern by using slurries having different materials (properties) so that multi-color inks are printed. For example, by printing a slurry containing ceramic that becomes a dense layer after firing on the outer peripheral portion to improve sealing property, and printing a slurry containing ceramic that becomes porous after firing on the inner peripheral portion on a catalyst carrier or a sensor. Any suitable structure can be formed.

By the way, the sheet-like substrate on which such a slurry is printed is a burnable material as long as it is a material to which a ceramic material adheres and does not cause defects due to a difference in heat shrinkage strain with the ceramic during firing. It is not limited but arbitrary. For example, a ceramic green sheet, silicon, metal or the like can be used.

Here, if the sheet-shaped substrate is paper or cloth, the printability of the slurry is good, the cost is low, and further, the organic fibers, which are components of the paper or cloth, are burnt out during firing, resulting in the structure. The material of the wall portion is porous, and the porous wall of the cell can be effectively used for various purposes, and the structure is lightweight and has high structural strength. Further, since the non-printed portion of the slurry of the sheet-like body is burnt out by firing, it is possible to form through holes in the stacking direction (direction perpendicular to the stacking surface) and to form cells communicating in a grid pattern.

By the way, the slurry to be printed has a ceramic material as a main component, has a predetermined degree of fluidity at the time of printing, and has a viscosity so as not to lose its shape from the time of printing to the time of stacking and drying, thereby generating a binding force. It is necessary.

The slurry may contain a metal component (metal powder, fiber, etc.). After firing, a sintered body composed of a composite of ceramic and metal is obtained, so that the mechanical strength is increased, and various functions can be exhibited depending on the characteristics of the added metal. For example, if stainless steel or a lithium alloy is added, the corrosion resistance is particularly high. In addition, commonly used metals (including alloys) such as iron and aluminum alloys can be added.

The ceramic raw material means a material which produces a ceramic sintered body by firing, and includes metal oxides, other heat-resistant compounds or their composite compounds (oxynitride,
Carbonitride, etc.) The ceramic raw material may further include a precursor (which may be a metal salt or an organic compound, or a sol or gel thereof) that produces a ceramic material by heating or firing, or a part thereof. As the ceramic raw material, typically, a powdery substance which is crushed can be used. The following is a description centering on particles and powders.

The solvent in which the ceramic raw material (particles, powder) is dispersed is usually water, but organic solvents such as methanol, ethanol, other higher alcohols, methyl ethyl ketone, acetone, ethyl acetate, toluene, etc. can also disperse the ceramic. Is selected in consideration of the above.

The weight ratio of the binder dissolved in the solvent or the solvent alone (that is, the liquid component) to the ceramic powder is 5 to 35:95 to 65 of the liquid component. The weight ratio of the liquid component to the ceramic powder is also appropriately selected depending on the properties of the ceramic, the properties of the binder and the solvent, or the shape and height of the print pattern.

Further, as a binder, a polymer material such as polyvinyl alcohol, polyvinyl butyral, poly (meth) acrylate, cellulose, dextrin, polyethylene wax, starch, casein, dioctyl phthalate, dibutyl phthalate, polyethylene glycol and various polysaccharides are used. A plasticizer such as the above is appropriately selected and added to adjust the viscosity and the curability.

As the material of the screen, in addition to the synthetic resin film used for ordinary pattern / pattern printing of ceramics, ink printing, liquid crystal color filter printing, etc., paper or cloth containing organic fibers as a main component is also used. be able to.

The screen may be detachable after the slurry printing step, but if the screen is made of a material whose main component is organic matter that is burned down by firing, such as paper or cloth, the detaching step becomes unnecessary and the number of steps can be reduced. It is preferable that the printed slurry does not lose its shape when the screen is removed.

Although the field is different from that of the present invention, in the ceramics field, printing techniques are used for dyeing or overpainting of ceramics, but these are for printing flat patterns using pigments. The production of a honeycomb structure is completely different in dimension.

Although the printing technique is applied to the formation of the ceramic resistance thin film of the electric resistor, the printed thin film is not used as a three-dimensional structure. These techniques may be partially applicable as a printing method.

An unfired raw honeycomb molded body (elemental structure) is obtained by laminating a plurality of ceramic material sheets including at least one ceramic printed pattern sheet having a predetermined pattern of irregularities formed in this way.

The laminating method is arbitrary such as pressure bonding, adhesion, welding and fitting.

As the sheets to be laminated, for example, only sheets having a print pattern can be laminated in a direction perpendicular to the printing surface. Then, the thickened print pattern becomes a side wall, and the two sheets having the print pattern become an upper bottom wall to form a cell wall. In this example, if the lamination is performed in an undried or semi-dried state in which the printed slurry has plasticity, the printed pattern itself serves as a bonding agent, and a new adhesive is unnecessary.

Further, for example, a sheet having a printing pattern and a flat ceramic sheet can be laminated in a direction perpendicular to the printing surface. Then, the thick printed pattern serves as a side wall, the sheet having the printed pattern serves as an intermediate layer, and the flat ceramic sheet serves as an upper bottom wall to form a cell wall.

This flat ceramic sheet can be manufactured by solid-printing the slurry on the entire surface by screen printing. In this case, the honeycomb-shaped element structure can be easily manufactured, and the honeycomb-shaped element structure can be manufactured by a consistent printing process, which is suitable for mass production.

A honeycomb-shaped ceramic structure can be manufactured by firing the element structure manufactured by the manufacturing method as described above.

The firing conditions are appropriately selected mainly depending on the ceramic component or the additive component (organic fiber, inorganic / organic binder, etc.). For example, in the case of cordierite, the firing temperature is preferably 1000 to 1250 ° C. When the organic matter is contained, it is indispensable to burn it off, but an oxidizing atmosphere is usually preferable for that purpose. In the case of a reducing atmosphere or an inert gas atmosphere, there are cases where an organic matter removing and burning step, a so-called degreasing step is included. If the ceramic raw material is a nitride or a special fine ceramic material such as silicon nitride, it may be fired in a vacuum furnace or an inert gas atmosphere.

[0067]

【Example】

<Example 1> With reference to FIGS. 1A to 1D, a process for producing a honeycomb-shaped ceramic structure by a screen printing method according to Example 1 of the present invention will be described with reference to schematic process diagrams.

In FIG. 1A, the slurry 2 is spread over the entire surface of the sheet 1.
FIG. 6 is a top perspective plan view of the paper sheet 1 and the ceramic material sheet 3, showing a solid printing step for solid printing. The slurry 2 is overprinted on the sheet 1 to a thickness of 5 μm to 2 mm, and the ceramic material is laminated or / and penetrates into the sheet 1 and / or into the sheet 1, so that the sheet 1 becomes the ceramic material sheet 3. In addition, in order to increase the thickness, it is possible to perform printing by stacking a plurality of times, or it is possible to further increase the thickness by repeating stacking.

The thickness of the above-mentioned print pattern is preferable for forming cells and has good printability, but the print thickness may be thinner or thicker than this.

In FIG. 1B, a screen 4 formed in a predetermined pattern is placed on the sheet 1, the slurry 2 is flown on the surface, and a predetermined pattern in which the slurry is thickened is imprinted on the stage 8. A pattern printing sheet forming step of forming the pattern sheet 5 will be described.

The sheet 1 is composed mainly of an organic fiber such as paper or cloth or an organic sheet such as methacrylic acid resin, paper or cloth coated with or impregnated with a ceramic material, and mainly composed of ceramics. A green sheet as a component or a component containing ceramic fiber as a main component is preferably used, but the material is not particularly limited as long as the slurry can be printed, and a metal material or the like can also be used.

FIG. 1 (c) shows a honeycomb-shaped ceramic element in which the ceramic material sheet 3 and the pattern sheet 5 manufactured in the above two steps are laminated in the normal direction of the upper and lower surfaces of each sheet (perpendicular to the pattern printing surface). A structure formation process is shown.
A honeycomb-shaped ceramic element structure having open cells in which the pattern printing portion 5 is a side surface and the predetermined surfaces of the ceramic material sheet 3 and the non-printing portion 7 are upper and lower surfaces is formed.

FIG. 2 shows a honeycomb-shaped ceramic element structure 9 having a large number of open cells 10. When this is fired, a ceramic structure having a honeycomb structure is completed.

As described above, a large number of ceramic material sheets 3
When the predetermined pattern printed sheets 5 are stacked in the normal direction of the ceramic printing surface of each sheet and fired, a honeycomb shape having a large number of open cells that communicate with each other in parallel to the printing surface (perpendicular to the stacking direction) Ceramic structures can be manufactured.

By such a method, a honeycomb ceramic structure having a fine diameter such that the short diameter of the cells of the honeycomb ceramic structure in the cross sectional direction is 0.2 to 1 mm, which has been difficult in the past, can be obtained. It is easy to manufacture with high precision. The minor axis of the cell in the cross-sectional direction can be selected according to the intended purpose, but it can be, for example, about 0.1 to 0.3 μm to about 1 mm, or a smaller diameter. It has the advantage of high flexibility.

The sheet 1 may be made of any material as long as it can print the slurry containing ceramic as a main component. For example, ordinary paper and cloth, polyester, polyethylene, etc., which is a raw material for green sheets manufactured by the doctor blade method, are used.

Further, if a ceramic sheet is used, the above solid printing step can be omitted. The ceramic sheet can be manufactured by a conventional wet papermaking method containing ceramics and fibers (organic or inorganic, and a mixture thereof) as main components (not shown).

FIG. 3 is a schematic process diagram showing a method of manufacturing the ceramic material sheet 3 by the calendar method (roll method). In this roll method, the ceramic / binder mixture 20 and the organic sheet 21 are compressed by a pressure roll 25 to form a sheet impregnated with ceramic, and further dry-molded by a heating roll 26 to form a ceramic material sheet 3. Can be manufactured.

By the way, the pressure roll 25 may be used as a rotary press to continuously print a predetermined pattern. Especially suitable for mass production.

It is also possible to obtain a honeycomb structure having open cells by subjecting the mixture of the organic fiber and the ceramic raw material to a bulk by a wet or dry press and performing press die cutting as a thick sheet-like body (block-like body) ( Illustration is omitted).

As a preferable example of the composition of the slurry 2 as the printing ink, the ceramic 70 is used in a weight ratio.
%, Fiber quality, other additives (binder or plasticizer 3
0%), the liquid component is toluene, and the weight ratio of the powder (solid content) containing ceramic as a main component to the liquid component is 7: 3. With such a composition, printability (quick-drying property, spreading property, no bleeding, etc.) is excellent.

Further, Table 1 shows examples of ceramic, organic and inorganic fibers which are raw materials of the slurry 2 and the ceramic material sheet 3. Materials other than those listed in Table 1 can also be used as raw materials. The new ceramic materials are subsequently shown in Table 2.

[0083]

[Table 1]

[0084]

[Table 2]

Further, an additive (plasticizer, curing agent, deflocculant) may be added to the main component of ceramic or ceramic and fiber. For example, it is possible to use a slurry of 36% water by adding about 0.3% of a peptizer and 3% of cellulose powder to a slurry made of ceramics. Examples of the components of the peptizer include phosphoric acid type, polycarboxylic ammonium type, polyacrylic acid type and the like.

A mixture of these ceramics or fibers or additives is dissolved in a solvent. Water is generally used as the solvent, and an alcoholic organic solvent can also be used. The weight ratio of the powder (solid content) whose main component is ceramic and the liquid component is usually powder 60 to 80: liquid component 40 to
Twenty.

In FIG. 1, the predetermined pattern printed on the sheet 1 is linear, but since this pattern is a pattern formation by printing, there is a high degree of freedom in design, and a preferable pattern can be selected on the sheet according to the purpose and application. Can be printed on to obtain a suitable open cell morphology.

<Embodiment 2> FIGS. 4 to 8 show a print pattern sheet 5 on which various patterns of ceramic patterns are printed by utilizing the degree of freedom of pattern formation by printing.

FIG. 4 shows a pattern-printed sheet 5 in which a pattern is printed on the sheet 1 in an uneven shape on a plane, (a) is an upper plan view showing a pattern-printed surface, and (b) is a cross-sectional view of the open cell. It is a side view.

By stacking the pattern printing sheet 5 and the ceramic material sheet on each other in the normal direction of the printing surface, the zigzag open cells 10 can be formed in the axial direction of the open cells. This zigzag passage is preferable because the contact area between the fluid and the wall per unit volume passing through the cell is widened.

FIG. 4 is a pattern print sheet 5 on which a pattern is printed in a curved line, (a) is an upper plan view which is a pattern print surface, and (b) is a side view in the cross section direction of the open cells. A pattern is printed on the sheet 1 and the print pattern 6 is attached in a sheet shape, and the non-printed portion is a space.

By laminating the pattern printing sheet 5 and the flat ceramic material sheet 3 on each other, the curved open cell 10 can be formed in the axial direction of the open cell. The curved passage preferably has a large contact area between the fluid and the wall per unit volume passing through the cell.

FIG. 5 shows a pattern print sheet 5 in which the cross section of the open cell is printed in a curved shape in a plane (parallel to the printing surface) and in an arc shape in a three-dimensional shape (perpendicular to the printing surface).
(A) is a top plan view of a pattern printing surface, (b) is
It is a side view of the cross section direction of an open cell. A pattern is printed on the sheet 1 and the print pattern 6 is attached in a sheet shape, and the non-printed portion is a space.

As described above, the cross-sectional shape of the open cell is not limited to the linear shape, but the three-dimensional pattern (cross-sectional shape) of the screen is formed in an arc shape, so that the cross section is substantially circular and the axial direction of the open cell is increased. A meandering pattern can be formed.

FIG. 6 is a top plan view of the pattern-printed sheet 5 on which island-shaped patterns are printed.

By stacking the pattern print sheet 5 and the ceramic sheet on each other in the normal direction of the print surface, the open cells 10 communicating with the longitudinal direction of the pattern 6 in FIG. 6 can be formed. This passage has the advantages that the contact area between the fluid and the wall per unit volume passing through the cell is expanded, and the pressure loss of the passing fluid is small.

FIG. 7 is a top plan view of the pattern printing sheet 5 on which patterns having two kinds of shapes, that is, a triangular protrusion shape and a rectangular shape in plan view, are printed.

As described above, a plurality of patterns can be provided on one plane, and a composite function can be exerted. Not only the shape but also the material can be changed for each pattern. For example, in a filtration device, it is possible to print a porous and dense ceramic pattern to achieve both fine particle adsorption rate and mechanical strength. .

FIG. 8 shows a top plan view of the pattern printing sheet 5 on which various patterns are printed. An arbitrary pattern such as a polygon such as a square, a pentagon, and a hexagon, a substantially circular shape such as a circle, a semicircle, and an ellipse, or an irregular shape is printed according to the use and purpose.

It is also possible to form a substantially spiral pattern by pattern formation by printing. For example, by printing a zigzag meandering pattern, a very long open cell passage can be formed. When the fluid passes through the open cell, the contact area with the open cell wall becomes large, which is preferable.

<Embodiment 3> In Embodiments 1 and 2, the open cells (cell axial direction) were formed parallel to the surface on which the pattern was printed. Can be formed in the normal direction).

FIG. 9 is an exploded view showing a process of forming open cells in the direction perpendicular to the pattern printing sheet 5. The above steps will be described below with reference to FIG.

As shown in FIG. 9 (a), first, the slurry is printed and thickened on the sheet 1 made of the burnable organic fiber excluding the portions to be the open cells 10 to make a large number of thin layers. A pattern printed sheet 5 having a cylindrical space portion (non-printed portion) is formed, and then this pattern printed sheet is
The cylindrical space portions (non-printing portions 7) are laminated in the direction perpendicular to the pattern printing surface so that the sheets 1 serving as the substrates overlap each other.

When this laminate is fired, the portion of the sheet 1 which is a partition between the cylindrical spaces is burned down, the cylindrical space penetrates, and the direction perpendicular to the pattern printing surface is taken as the axial direction. The honeycomb-shaped ceramic element structure 9 having the open cells 10 can be manufactured.

FIG. 9B shows a honeycomb-shaped ceramic element structure 9 having open cells 10 whose axial direction is perpendicular to the pattern printing surface.

If the sheet 1 is a non-burnout ceramic sheet or a solid-printed ceramic sheet is sandwiched between pattern printing sheets, it has open holes or cells that are not in complete communication, and is lightweight and structurally strong. A high honeycomb structure can be easily manufactured.

FIG. 10 is an exploded view of the honeycomb-shaped ceramic element structure 9 showing a step of forming prismatic open cells in the direction perpendicular to the pattern printing sheet 5. The above steps will be described below with reference to FIG.

As shown in FIG. 10, first, the slurry is printed and thickened on the sheet 1 made of the burnable organic fiber except for the portions to be the open cells 10 to form a large number of thin cylinders. A pattern printing sheet 5 having a space portion (non-printing portion) is formed, and then the pattern printing sheet is formed on the pattern printing surface so that the cylindrical space portion (non-printing portion 7) communicates with the pattern printing sheet. Stack in the vertical direction.

When this laminated body is fired, the sheet 1 portion which is the partition wall between the prismatic space portions is burned down, the prismatic space penetrates, and the direction perpendicular to the pattern printing surface is defined as the axial direction. A honeycomb-shaped ceramic structure having the open cells 10 can be manufactured.

Further, since the ceramic pattern is printed in a symmetrical pattern as shown in FIG. 10, cracks, cracks, and the like due to shrinkage of the ceramic material that normally occurs during drying and firing.
Warpage or chipping is less likely to occur, which is preferable.

Furthermore, it is also possible to form open cells that are in communication with each other in two directions parallel and perpendicular to the printing surface.

FIG. 11 shows the decomposition of the honeycomb-shaped ceramic element structure 9 in which the open cells 10 are formed so as to communicate with each other in the direction parallel to the printing surface and the direction perpendicular to the printing surface by stacking several pattern sheets 5 again. The figure is shown.

On the ceramic material sheet 3 having prismatic holes, the slurry is printed to form the ceramic pattern portion 6 to form the pattern sheet 5, and a plurality of the pattern sheets 5 are formed in the direction perpendicular to the printing surface. By stacking the prismatic pores so that they communicate with each other, it is possible to manufacture the honeycomb-shaped ceramic element structure 9 in which the open cells 10 are formed so as to communicate with each other in the direction parallel to the printing surface and the direction perpendicular to the printing surface. Such a cell structure is suitable for fluid mixing and heat exchangers. The ceramic material sheet 3 may be the burnable sheet 1 as shown in FIG.

<Embodiment 4> FIG. 12 is an exploded view of the honeycomb-shaped ceramic element structure 9 in which the pattern sheets 5 are laminated so that the print patterns of the pair of pattern sheets 5 intersect with each other through the ceramic material sheets. Indicates.

The slurry is printed on the ceramic material sheet 3 to form island-shaped pattern portions in stripes, and the print pattern portions 6 of the two pattern sheets 5 of the same shape are formed so as to intersect each other at right angles. 90 pattern sheet 5
The pattern sheets are superposed on each other by rotating ゜, and the lower surface of one ceramic material sheet 3 (pattern sheet 5) is the upper wall, the pattern portion 6 is the side wall, and the upper surface of the other ceramic material sheet 3 (pattern sheet 5) is the bottom. It is possible to manufacture the honeycomb-shaped ceramic element structure 9 in which the open cells which are walls and communicate with each other in parallel to the printing surface are independently formed in two directions.

As described above, in the honeycomb-shaped ceramic element structure having the open cells communicating independently in two directions, cracks, cracks, warps, chips, etc. occur due to shrinkage of the ceramic material that usually occurs during drying and firing. It is difficult because it is preferable,
Furthermore, it is resistant to stress from both directions and is suitable for structural materials. Further, it is suitable for a heat exchanger that allows two kinds of fluids having different properties to be conducted.

<Embodiment 5> In FIGS. 13A to 13C, various pattern sheets 5 or perpendicular to the print pattern portion 6 of the honeycomb-shaped ceramic element structure by laminating the pattern sheet 5 and the ceramic material sheet 3 are stacked. FIG. 3 is an exploded cross-sectional view taken along a different direction.

In (a), the print pattern portions 6 are in contact with each other on their printing surfaces, in (b) they are in contact with each other via the ceramic material sheet 3, and in (c), the print pattern portion 6 is the non-print portion of the other pattern sheet. And a cell having a relatively small cell diameter can be obtained.

Example 6 The honeycomb-shaped ceramic structure having various patterns produced by the production method of the present invention is suitable for a chemical reaction device, particularly a catalyst carrier, a bioreactor, a water purifier, a waste water purification device. ing. In these cases, it is preferable to reduce the cell diameter (honeycomb diameter) in order to increase the surface area. Since it is a printing technique, the dimensional accuracy such as the cell diameter can be made very high and is about 5 μm, so that it is suitable for precision parts such as an inkjet head. In addition, the relatively large cell diameter reduces weight while maintaining strength, so building materials (walls, ceilings,
Suitable for partition materials, etc.)

[0120]

As described above, according to the present invention,
First, a pattern sheet forming step of printing a slurry containing a ceramic raw material as a main component on a sheet-like body to form a predetermined print pattern on which ceramic is thickly formed, and a plurality of pattern sheet containing at least one pattern sheet. A cell for forming a honeycomb by a method for manufacturing a honeycomb-shaped ceramic structure, which includes a step of stacking sheets in a layered manner to define cells by the thickened predetermined pattern and the stacked sheets. It is possible to provide a method for manufacturing a honeycomb-shaped ceramic structure, which has a fine structure, a highly precise structure, a simple and suitable for mass production, in which the structure and cell pattern can be freely designed.

Secondly, the printing of the slurry is a screen printing in which a screen formed in a predetermined pattern is arranged on the sheet, and the slurry is printed on the sheet-shaped substrate through the screen. It is possible to more easily print the pattern slurry.

Thirdly, by alternately laminating the ceramic material sheets and the pattern sheets, it is possible to easily manufacture a honeycomb-shaped ceramic structure by firing from an element structure having a stable structure.

Fourthly, the honeycomb-shaped ceramic structure can be easily manufactured by stacking only the pattern sheets in a plurality of layers.

Fifth, since the cells communicate with each other at least in the direction parallel to the pattern-printed surface, the fluid can pass through the cells and can be used particularly as a catalyst carrier for a chemical reaction apparatus or the like. it can.

Sixth, by stacking the pattern sheets having through holes perpendicular to the printing surface of a predetermined pattern and forming cells in which the through holes communicate with each other in the direction perpendicular to the pattern printing surface, It is possible to manufacture a honeycomb-shaped ceramic structure having communicating cells by a simple method without making holes after forming the body.

Seventh, since the printed patterns of at least one set of the pattern sheets are laminated so as to intersect with each other with or without the ceramic material sheet, it is resistant to stress from multiple directions.

Eighth, since the printing patterns intersect each other at right angles, it is resistant to stress from multiple directions, and further, defects such as cracks and cracks are less likely to occur during the drying step after printing or during firing. .

Ninth, since the printed pattern is printed in line symmetry, defects such as cracks and cracks are unlikely to occur during the drying step after printing or during firing.

Tenth, by including the step of printing the slurry on the entire surface of the sheet-like substrate to form a ceramic layer to form the ceramic material sheet, the honeycomb-like ceramic structure is formed in a continuous process using a printing method. The body can be manufactured, and it is particularly excellent in mass productivity.

Eleventh, since at least one of the pattern sheet and the ceramic material sheet is made of a raw material containing ceramics and organic fibers as main components, the printability of the slurry is good and the fibers after firing are Since the component is burned off and the structure becomes porous and has a large surface area, the honeycomb ceramic structure made of such a raw material is particularly suitable for a chemical reaction device such as a catalyst carrier.

Twelfth, since the non-printed portion of the pattern sheet is burnt down during the firing of the structure and the cells are communicated in the stacking direction, the cells can be easily formed even if a normal flat sheet without holes is used. Can form a structure.

Thirteenth, the thickness of the layer of the printing pattern is variable in a wide range of 5 μm to 2 mm and can be freely selected according to the purpose of use. Further, since the thickness can be made extremely thin, a large number of cells can be formed in one honeycomb-shaped ceramic structure, in which case the cell surface area is increased, which is particularly suitable for a catalyst carrier and the like.

Fourteenth, it is possible to manufacture a fine cell having a short diameter of 0.01 to 2 mm in the cross-sectional direction of the cell of the honeycomb-shaped ceramic structure with high dimensional accuracy and a simple method. In this way, the cross-sectional diameter of the cells can be varied over a wide range, can be freely selected according to the purpose of use, and can be extremely small, so that many cells can be formed in one honeycomb-shaped ceramic structure. In that case, the cell surface area is increased, and it is particularly suitable for a catalyst carrier and the like.

Fifteenth, on the same print pattern sheet,
Due to the different shapes and / or materials of the printing patterns, individual functions can be given to the cells, and the applicability to raw materials and applications is extremely high.

Sixteenth, since the sheet-like substrate is made of paper or cloth containing an organic substance as a main component, the slurry has good printability, is inexpensive, and is a component of paper or cloth at the time of firing. The organic fibers are burned down, and the material of the wall of the structure becomes porous, so that the porous wall of the cell can be effectively utilized for various purposes, and the structure becomes lightweight and has high structural strength. In addition, since the unprinted portion of the slurry of the sheet-like body is burned by firing, the stacking direction (direction perpendicular to the stacking surface)
Through holes can be provided, and cells that communicate in a grid can be formed.

Seventeenth, since the slurry contains a metal component composed of metal powder or metal fibers (or both of them), a sintered body composed of a composite of ceramic and metal can be obtained after firing. The mechanical strength is increased, and various functions can be exhibited depending on the characteristics of the added metal component. For example, corrosion resistance can be made particularly high by adding stainless steel or a lithium alloy. Other than that,
Commonly used metals (including alloys) such as iron and aluminum alloys can also be added.

Finally, on the basis of the variety of manufacturing methods described above, it is also a great advantage that a honeycomb-shaped ceramic structure having a structure and dimensions that cannot be manufactured or is difficult to obtain by other methods can be obtained.

[Brief description of drawings]

FIG. 1 is a process schematic diagram that is an upper perspective plan view illustrating a manufacturing process of a honeycomb-shaped ceramic structure by a screen printing method that is an embodiment of the present invention, and in FIG. The solid printing process for solid printing
A predetermined pattern print sheet forming step of forming a predetermined pattern sheet 5 by imprinting the predetermined pattern 6 on the sheet 1 through the screen 4 in (b), and the ceramic material sheet 3 and the predetermined pattern print sheet 5 in (c). Shows the honeycomb structure forming step of stacking the sheets in the normal direction of the upper and lower surfaces of each sheet.

FIG. 2 is a perspective view showing a honeycomb-shaped ceramic structure 9 having a large number of open cells.

FIG. 3 is a schematic process diagram showing a method for manufacturing a ceramic material sheet 3 by a calendar method (roll method).

4A and 4B show a pattern-printed sheet 5 on which pattern printing is performed in a concavo-convex pattern, in which FIG. 4A is a top plan view of a pattern-printed surface, and FIG.

FIG. 5 is a pattern print sheet 5 in which a cross section of an open cell is curved (arcuate), (a) is an upper plan view showing a pattern printed surface, and (b) is a cross section direction of the open cell. FIG.

FIG. 6 is a top plan view of a pattern printing sheet 5 on which an island pattern is printed.

FIG. 7 is a top plan view of the pattern printing sheet 5 on which patterns having two types of shapes, triangular protrusions and rectangles, are printed.

FIG. 8 is a top plan view of the pattern printing sheet 5 on which various patterns are printed. Pattern cross section is square, pentagon,
An arbitrary pattern such as a polygon such as a hexagon, a circle such as a circle, a semicircle, an ellipse, or an irregular shape is printed according to the use and purpose.

FIG. 9 is a process schematic diagram showing a process of forming apertured cells in a direction perpendicular to the pattern print sheet 5.

FIG. 10 is an exploded view of the honeycomb-shaped ceramic element structure 9 showing the step of forming prismatic open cells in the direction perpendicular to the pattern printed sheet 5.

FIG. 11 is an exploded view of the honeycomb-shaped ceramic element structure 9 in which the open cells 10 are formed so as to communicate with each other in a direction parallel to the printing surface and a direction perpendicular to the printing surface by stacking several pattern sheets in FIG. The figure is shown.

FIG. 12 is an exploded view of the honeycomb-shaped ceramic element structure 9 in which the pattern sheets 5 are laminated so that the printed patterns of the set of pattern sheets 5 intersect with each other with the ceramic material sheets interposed therebetween.

FIG. 13 is an exploded cross-sectional view taken in a direction perpendicular to the print pattern portion 6 of the honeycomb-shaped ceramic element structure formed by laminating various pattern sheets 5 or the pattern sheet 5 and the ceramic material sheet 3, (a) In (), the print pattern portions 6 are in contact with each other on the print surfaces, in (b) they are in contact with each other via the ceramic material sheet 3, and in (c), the print pattern portions 6 are bonded to the non-print portions of the other pattern sheet.

[Explanation of symbols]

 1 Sheet 2 Slurry 3 Ceramic Material Sheet 4 Screen 5 Pattern Sheet (Printing Pattern Sheet) 6 Pattern Part (Printing Pattern Part) 7 No Printing Part 8 Stage 9 Honeycomb Ceramic Element Structure 10 Cell (Open Cell)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Yamamoto 4-1 Daimon, Inuyama, Aichi Prefecture

Claims (17)

[Claims] 1. A pattern sheet forming step of forming a ceramic material sheet having a predetermined print pattern by printing a slurry containing a ceramic raw material as a main component on a sheet-shaped substrate, and a ceramic containing at least one pattern sheet. A method for manufacturing a honeycomb-shaped ceramic structure, comprising a step of stacking material sheets in a plurality of layers and defining cells by a combination of the printed pattern and the stacked ceramic material sheets. 2. The printing of the slurry is a screen printing in which a screen formed in a predetermined pattern is arranged on the sheet, and the slurry is printed on the sheet-shaped substrate through the screen. 1. The method for manufacturing a honeycomb-shaped ceramic structure according to 1. 3. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the ceramic material sheets and the pattern sheets are alternately laminated. 4. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the pattern sheets are laminated in a plurality of layers. 5. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the cells are cells communicating with each other at least in a direction parallel to a pattern printing surface. 6. A pattern sheet having a through hole perpendicular to a printing surface of a predetermined pattern is laminated to form a cell in which the through hole communicates in a direction perpendicular to the pattern printing surface. The method for manufacturing a honeycomb-shaped ceramic structure according to any one of 1 to 5. 7. The print pattern of at least one set of the pattern sheets is laminated so as to intersect with each other with or without the ceramic material sheet interposed therebetween. A method for manufacturing a honeycomb-shaped ceramic structure according to claim 1. 8. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 7, wherein the printed patterns intersect each other at a right angle. 9. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the print pattern is printed line-symmetrically. 10. The method according to claim 1, further comprising the step of printing the slurry on the entire surface of the sheet-shaped substrate to form a ceramic layer to form the ceramic material sheet.
10. The method for manufacturing a honeycomb-shaped ceramic structure according to any one of 9 to 10. 11. The honeycomb according to any one of claims 1 to 10, wherein at least one of the pattern sheet and the ceramic material sheet is made of a raw material containing a ceramic and an organic fiber as a main component. Of manufacturing a ceramic structure. 12. The honeycomb-shaped ceramic structure according to claim 1, wherein the non-printed portion of the pattern sheet is burned off during firing of the structure, and the cells are communicated in the stacking direction. Body manufacturing method. 13. The layer of the printed pattern has a thickness of 5 μm.
The method for manufacturing a honeycomb-shaped ceramic structure according to any one of claims 1 to 12, wherein the honeycomb-shaped ceramic structure has a diameter of 2 mm. 14. The honeycomb ceramic structure according to claim 1, wherein the cells of the honeycomb ceramic structure have a minor axis in the transverse direction of 0.01 to 2 mm. Body manufacturing method. 15. The manufacture of a honeycomb-shaped ceramic structure according to claim 1, wherein the print patterns on the same print pattern sheet have different shapes and / or materials. Method. 16. The sheet-shaped substrate is made of paper or cloth containing an organic substance as a main component.
2. The method for manufacturing a honeycomb-shaped ceramic structure according to any one of 1. 17. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the slurry contains a metal component.