JP3357200B2 - Method for manufacturing honeycomb-shaped ceramic structure - Google Patents

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 printed sheets using a ceramic slurry screen printing method.

[0002]

2. Description of the Related Art As a method of manufacturing a honeycomb-shaped ceramic structure, extrusion molding is a typical method.
In JP-A-48-66112, a flat ceramic material sheet is subjected to uneven processing, and the uneven sheet is laminated or rolled up in the circumferential direction of the cells (irregular portions) (a direction parallel to the surface forming the honeycomb) and fired. The honeycomb-shaped ceramic structure provided with open cells was used.

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 the plane of the honeycomb. The honeycomb-shaped ceramic structure provided with open cells was used.

Japanese Patent Application Laid-Open No. 57-179060 discloses that in a ceramic structure having a three-dimensional network structure, holes which do not penetrate the structure independently or mutually are formed by rods from both ends of the structure in a plastic state. Thus, a ceramic structure having an open cell communicating with the hole by a three-dimensional network structure has been manufactured.

[0005] Japanese Patent Application Laid-Open No. 2-261652 discloses that a photosensitive hole forming material such as an organic material which is heat-melted or thermally decomposed at a lower temperature than an organic binder in a green sheet is applied to the surface of the green sheet by a photoresist technique. A fine line pattern is formed, and then a ceramic material is filled between the patterns, a plurality of the green sheets are stacked, pressed and fired, and holes are formed after the thin line pattern is burned out during firing. A formed ceramic sintered body was obtained.

Japanese Patent Application Laid-Open No. 2-296779 is different from the previous one only in that a thin line pattern is removed with an organic solvent before firing.

[0007]

However, in extrusion molding, there is a limit to the obtained honeycomb shape. 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 a cell of micrometer order A ceramic structure having a diameter could not be produced.

[0008] Furthermore, the thick structure in the axial direction of the open cell is difficult to extrude because the flowability of the molding material is reduced, and in order to obtain a large structure, the mold must be large.

Also, in the honeycomb structure forming step in a state having a predetermined plasticity during the manufacturing process, cracks, cracks or breakage are liable to 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 has been difficult to manufacture a honeycomb-shaped ceramic structure having a fine cell diameter.

In a method of forming a hollow tubular body by processing a ceramic sheet by a corrugation method or the like and assembling the hollow tubular body into a honeycomb structure, a fine cell structure having a small dimensional error is also manufactured. And a step of forming a tubular body was indispensable.

Also, a method in which a hole is formed in a plastic in a plastic state with a rod and the hole is used as a cell cannot produce a cell having a fine shape as in the case of extrusion molding, and the communicating shape of the cell is also linear. A critical disadvantage is that the cell walls cannot be made sufficiently strong. On the other hand, a ceramic material having no plasticity cannot be extruded, and an expensive binder is required for extrusion molding.

In addition, after forming a fine line pattern by a photoresist and filling a ceramic material in a gap layer between the patterns, the fine line pattern is removed, and a ceramic having fine pores having pores (cells) as a trace of the fine line pattern is formed. The method of manufacturing a structure requires a multi-step process such as lamination of a photosensitive resin, formation of a photomask, exposure and development, and has a disadvantage that the process is complicated.

Further, it is difficult to form a thin line pattern having a small width and a high height (thickness) by a photoresist technique, and deformation due to over-etching or the like of the pattern due to etching after exposure is inevitable or optional. It was not suitable for forming a cell having the following dimensions.

A basic object of the present invention is to freely design a cell structure and a cell pattern for forming a honeycomb, including a cell shape, a cell diameter, a cell wall thickness, and the like, and it is possible to easily cope with a design change. An object of the present invention is to provide a simple method for manufacturing a honeycomb-shaped ceramic structure.

It is a further object of the present invention to provide a method for manufacturing a honeycomb-shaped ceramic structure having a cell structure with 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 of manufacturing a honeycomb-shaped ceramic structure having extremely wide applicability to raw materials.

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

[0019]

According to the present invention, there is provided a pattern sheet forming step of forming a ceramic material sheet having a predetermined print pattern by printing a slurry containing a ceramic material as a main component on a sheet-like substrate. A sheet laminating step of laminating ceramic material sheets including at least one of the pattern sheets and superimposing the ceramic material sheets in a plurality of layers to define cells by a combination of the printing pattern and the superposed ceramic material sheets. A method of manufacturing a ceramic ceramic structure is provided. The sheet-like substrate may be any sheet on which the slurry can be printed, and the ceramic material sheet means that, in addition to the pattern sheet on which the slurry is printed, the ceramic material adheres to or impregnates part or all of the sheet-like body. And ceramic paper.

[0020]

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

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

Further, the invention is characterized in that the pattern sheets are overlapped in a plurality of layers.

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

The present invention is characterized in that the pattern sheets having through holes perpendicular to the printing surface of the predetermined pattern are laminated to form cells in which the through holes communicate in the direction perpendicular to the pattern printing surface.

Further, at least one set of the printed patterns of the pattern sheets is laminated so as to intersect with or without a ceramic material sheet interposed therebetween.

Further, the printing patterns intersect at right angles.

Further, the printing pattern is printed symmetrically.

The method further comprises a 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.

Further, at least one of the pattern sheet and the ceramic material sheet is made of a raw material mainly composed of ceramic and organic fibers.

Further, the non-printed portion of the pattern sheet is burned off when the structure is fired, and the cells communicate with each other in the stacking direction.

The thickness of the layer of the printing pattern is 5
μm to 2 mm.

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

Further, the printing pattern on the same printing pattern sheet has a different shape and / or material.

[0034] The sheet-like substrate is made of paper or cloth mainly composed of organic matter.

[0035] The slurry is characterized in that it contains a metal component.

[0036]

In the following, 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, a slurry is formed by printing a slurry containing a ceramic material as a main component on a sheet, and a three-dimensional pattern including a predetermined pattern made of ceramic and a non-printed portion. A ceramic printing (material) pattern sheet having flat irregularities is manufactured, and the ceramic material sheet including at least one ceramic printing sheet having the irregularities of the predetermined pattern is overlapped in a plurality of layers, and the printed pattern and the ceramic material sheet are used. To form a predetermined honeycomb shape having cells surrounded by walls.

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

Further, a pattern can be formed by the printing technique of the present invention using a non-plastic plastic material which cannot be extruded.

Printing techniques include offset printing and screen printing.

Offset printing is a method in which ink is first transferred to a flat or roll-shaped transfer plate, and then the ink is transferred from the transfer plate to a printing material. Of course, in the present invention, a slurry containing a 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 screen printing, a mold (frame) formed in a predetermined depth (three-dimensional form) and a predetermined pattern (two-dimensional form) is placed on an object to be printed (sheet-like body). The slurry is printed from above, and the ceramic is deposited on the part of the sheet corresponding to the non-pattern part of the mold at a height corresponding to the depth of the mold, and the ceramic adheres to the patterned part To avoid this, a planar and three-dimensional ceramic print pattern is formed.

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

The screen formed in a predetermined pattern can be formed by cutting or the like. However, in order to produce a fine pattern of a micrometer order or a screen having a complicated shape with high dimensional accuracy, a photoengraving is required. Is suitable for screen production. Similar to a circuit pattern of a semiconductor or the like, a high-precision, fine and complicated pattern can be easily created.

The screen can be formed by masking with a tape.

The method of adhering the slurry to the sheet is as follows: pressing the slurry by a roller, a stage or the like; removing the excess slurry with a doctor blade after flowing the slurry; and dipping the sheet with the screen adhered into the slurry. And a method of spraying or applying a slurry.

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

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 from the ceramic during firing. It is optional without limitation. For example, ceramic green sheets, silicon, metal and the like can be used.

Here, if the sheet-like substrate is paper or cloth, the printability of the slurry is good and inexpensive. Further, at the time of firing, the organic fibers which are the components of the paper or cloth are burned off and the structure is formed. The wall material 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. In addition, since the unprinted portions of the sheet-shaped body without the slurry are burned out by baking, through holes can be provided in the laminating direction (perpendicular to the laminating surface), and cells communicating in a lattice can be formed.

By the way, the slurry to be printed contains a ceramic material as a main component, has a predetermined fluidity at the time of printing, and has a viscosity not to lose its shape from printing to lamination and drying, and generates a bonding force. It is necessary.

The slurry may include a metal component (metal powder, fiber, etc.). After sintering, 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, corrosion resistance is particularly high if stainless steel or a lithium alloy is added. In addition, commonly used metals (including alloys) such as iron and aluminum alloys can also be added.

The ceramic raw material refers to a material that forms a ceramic sintered body by firing, and includes metal oxides, other heat-resistant compounds or composite compounds thereof (oxynitrides,
Carbonitrides). 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 substance by heating or firing, or a part thereof. Typically, a powdery substance containing particles can be used as the ceramic raw material. The following mainly describes examples of particles and powder.

The solvent in which the ceramic raw materials (particles, powders) are dispersed is usually water, but organic solvents such as methanol, ethanol, other higher alcohols, methyl ethyl ketone, acetone, ethyl acetate, and toluene are also used for dispersing the ceramic. Is appropriately selected in consideration of

The weight ratio of the binder or the solvent alone (that is, the liquid component) dissolved in the solvent to the ceramic powder is suitably from 5 to 35:95 to 65 for 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 binders, high molecular materials such as polyvinyl alcohol, polyvinyl butyral, poly (meth) acrylate, cellulose, dextrin, polyethylene wax, starch, casein, dioctyl phthalate, dibutyl phthalate, polyethylene glycol, and various polysaccharides And the like are appropriately selected and added to adjust the viscosity and the curability.

As the material of the screen, besides a synthetic resin film used for ordinary ceramic pattern / pattern printing, ink printing, liquid crystal color filter printing, etc., paper, cloth, etc. mainly composed of organic fibers are used. be able to.

The screen may be made detachable after the slurry printing step. However, if the screen is made of a material mainly composed of an organic substance that is burned off by firing, such as paper or cloth, the detachment step becomes unnecessary and the number of steps can be reduced. It is preferable that the slurry printed when the screen is separated does not lose its shape.

Although the field of the present invention is different from that of the present invention, in the ceramic art field, printing techniques are used for dyeing or painting on ceramics, but these are used to print planar patterns using pigments. This is completely different from the production of the honeycomb structure.

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

By laminating a plurality of ceramic material sheets including at least one ceramic printed pattern sheet having a predetermined pattern of irregularities formed as described above, an unfired green honeycomb molded body (raw structure) is obtained.

The method of lamination is arbitrary, such as pressure bonding, adhesion, welding, fitting and the like.

As the sheets to be laminated, for example, only sheets having a printing pattern can be laminated in a direction perpendicular to the printing surface. Then, especially the thickly embossed print pattern becomes the side wall, and the two sheets having the print pattern become the upper bottom wall, thereby forming the cell wall. In this example, if the lamination is performed in an undried or semi-dry state in which the printed slurry has plasticity, the printed pattern itself becomes a bonding agent, and no new adhesive is required.

Further, for example, a sheet having a printing pattern and a flat ceramic sheet can be laminated on each other in a direction perpendicular to the printing surface. Then, the thick printed pattern becomes a side wall, a sheet having the printed pattern becomes an intermediate layer, and a flat ceramic sheet becomes an upper bottom wall, thereby forming a cell wall.

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

The honeycomb-shaped ceramic structure can be manufactured by firing the elementary structure manufactured by the above-described manufacturing method.

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 from 1000 to 1250 ° C. When organic matter is contained, its burning is indispensable, but an oxidizing atmosphere is usually preferred for that purpose. In the case of a reducing atmosphere or an inert gas atmosphere, a step of removing and burning off organic substances, a so-called degreasing step, may be included. If the ceramic raw material is a nitride, particularly a fine ceramic material such as silicon nitride, firing may be performed in a vacuum furnace or an inert gas atmosphere.

[0067]

【Example】

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

FIG. 1A shows that the slurry 2
FIG. 2 is a top perspective view of a paper sheet 1 and a ceramic material sheet 3 showing a solid printing step of solid printing. The slurry 2 is thickly printed on the sheet 1 to a thickness of 5 μm to 2 mm, and the ceramic material is laminated or / and penetrated into and / or into the sheet 1, so that the sheet 1 becomes a ceramic material sheet 3. It should be noted that the thick embossing can be performed by laminating a plurality of times of printing, and can be further increased by repeating lamination.

The thickness of the above-mentioned print pattern is preferable for forming cells, and the printability is good. However, the thickness of the print pattern can be thinner or thicker.

In FIG. 1 (b), a screen 4 formed in a predetermined pattern is placed on the sheet 1, the slurry 2 is caused to flow on the surface, and a predetermined pattern in which the slurry is thickly imprinted on the stage 8 is printed. And a pattern printing sheet forming step of forming the pattern sheet 5.

The sheet 1 mainly includes an organic fiber sheet such as paper or cloth or an organic sheet such as methacrylic acid resin, a paper or cloth coated or impregnated with ceramic, or a ceramic. A green sheet as a component or a material containing a 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 be used.

FIG. 1C 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). 4 shows a structure forming step.
A honeycomb-shaped ceramic element structure having an opening cell in which the pattern printing portion 5 is on the 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. By firing this, a ceramic structure having a honeycomb structure is completed.

As described above, a large number of ceramic material sheets 3
And, if the predetermined pattern printing sheet 5 is laminated and fired in the normal direction of the ceramic printing surface of each sheet, and fired, a honeycomb shape having a large number of open cells communicating with the printing surface in parallel (perpendicular to the laminating direction). A ceramic structure can be manufactured.

By such a method, a honeycomb-shaped ceramic structure having a fine diameter such that the short diameter in the cross-sectional direction of the cell of the honeycomb-shaped ceramic structure is 0.2 to 1 mm, which has been difficult in the past, can be obtained. It can be easily manufactured with high precision. The minor diameter of the cell in the cross-sectional direction can be usually selected according to the purpose of use. For example, a minor diameter of about 0.1 to 0.3 μm to about 1 mm or a smaller diameter is possible. There is an advantage that the degree of freedom is high.

As described above, the material of the sheet 1 is arbitrary as long as a slurry containing a ceramic as a main component can be printed. For example, there are polyester, polyethylene and the like, which are raw materials for ordinary paper and cloth, green sheets produced by the doctor blade method.

Further, if a ceramic sheet is used, the solid printing step can be omitted. The ceramic sheet can be manufactured by a usual wet papermaking method mainly composed of ceramics and fibers (organic or inorganic, and a mixture thereof) (not shown).

FIG. 3 is a schematic process chart showing a method of manufacturing the ceramic material sheet 3 by a calender method (roll method). In this roll method, a ceramic-binder mixture 20 and an organic sheet 21 are compressed by a pressure roll 25 to form a sheet impregnated with ceramic, and then dried and formed by a heating roll 26 to form a ceramic material sheet 3. Can be manufactured.

By the way, a predetermined pattern can be continuously printed using the pressure roll 25 as a rotary press. Particularly suitable for mass production.

Further, the mixture of the organic fibers and the ceramic raw material is made into a bulk by wet or dry pressing, and a thick sheet (block) is punched out to obtain a honeycomb structure having open cells. The illustration is omitted).

A preferred example of the composition of the slurry 2 as a printing ink is a ceramic 70% by weight.
%, Fiber, other additives (binder or plasticizer 3)
0%), the liquid component is toluene, and the weight ratio of the powder (solid content) mainly composed of ceramic to the liquid component is 7: 3. Such a composition is excellent in printability (quick drying property, spreading property, non-bleeding, etc.).

Table 1 shows examples of ceramic, organic and inorganic fibers used as raw materials for the slurry 2 and the ceramic material sheet 3. In addition, materials other than those described in Table 1 can be used as raw materials. Table 2 shows the new ceramic materials.

[0083]

[Table 1]

[0084]

[Table 2]

Further, additives (plasticizers, hardeners, deflocculants) may be added to the main component ceramic or ceramic and fiber. For example, a slurry obtained by adding about 0.3% of a deflocculant and 3% of a cellulose powder to a slurry made of ceramic to obtain a slurry having a water content of 36% can be used. Examples of the components of the deflocculant include phosphoric acid, polycarboxylic ammonium acid, and polyacrylic acid.

The mixture of these ceramics or fibers or additives is dissolved in a solvent. The solvent is generally water, and an alcohol-based organic solvent can also be used. The weight ratio between the powder (solid content) mainly composed of ceramic and the liquid component is usually 60 to 80 powder: 40 to liquid component.
20.

In FIG. 1, the predetermined pattern printed on the sheet 1 is a straight line. However, since this pattern is formed by printing, the degree of freedom in design is high, and a preferable pattern is selected on the sheet according to the purpose and application. To obtain a suitable open cell configuration.

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

FIGS. 4A and 4B show a pattern printing sheet 5 in which a pattern is printed on the sheet 1 in an uneven pattern on the plane. FIG. 4A is an upper plan view showing a pattern printing surface, and FIG. It is a side view.

By laminating such a pattern printing sheet 5 and a ceramic material sheet on each other in the normal direction of the printing surface, zigzag opening cells 10 can be formed in the opening cell axis direction. The zigzag passage preferably has a large contact area between the fluid and the wall per unit volume passing through the cell.

FIGS. 4A and 4B show a pattern printing sheet 5 on which a pattern is printed in a curved shape. FIG. 4A is an upper plan view showing a pattern printing surface, and FIG. The pattern is printed on the sheet 1 and the print pattern 6 adheres in a sheet shape, and the non-printed portion is a space.

By laminating such a pattern printing sheet 5 and a flat ceramic material sheet 3 on each other, it is possible to form an aperture cell 10 having a curved shape in the aperture cell axial direction. 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 printing sheet 5 in which the cross-section of the opening cell is printed in a curved shape in a plane (parallel to the printing surface) or in an arc in a three-dimensional shape (perpendicular to the printing surface).
(A) is a top plan view of the pattern printing surface, and (b) is
It is a side view of an opening cell cross section direction. The pattern is printed on the sheet 1 and the print pattern 6 adheres in a sheet shape, and the non-printed portion is a space.

As described above, the cross-sectional shape of the opening cell is not limited to a straight line, but by forming the three-dimensional pattern (cross-sectional shape) of the screen in an arc shape, the cross-section is substantially circular and the opening cell axial direction. A meandering pattern can be formed.

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

If such a pattern printing sheet 5 and a ceramic sheet are laminated on each other in the normal direction of the printing surface, an open cell 10 communicating with the pattern 6 in the longitudinal direction in FIG. 6 can be formed. This passage has the advantage that the contact area between the fluid and the wall per unit volume passing through the cell is increased, and the pressure loss of the passing fluid is small.

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

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

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

A substantially spiral pattern can be formed by forming a pattern by printing. For example, if a zigzag meandering pattern is formed by printing, a very long open cell passage can be formed. This is preferable because the contact area between the fluid and the opening cell wall when the fluid passes through the opening cell is large.

<Embodiment 3> In the embodiments 1 and 2, the aperture cells (cell axis direction) are formed parallel to the surface on which the pattern is printed. Normal direction).

FIG. 9 is an exploded view showing a step of forming an aperture cell in a direction perpendicular to the pattern printing sheet 5. Hereinafter, the above steps will be described with reference to FIG.

As shown in FIG. 9 (a), first, a slurry was printed on a sheet 1 made of burnable organic fibers except for a portion serving as an open cell 10, and a large number of thin layers were formed. A pattern printing sheet 5 having a cylindrical space portion (non-printing portion) is formed.
The layers are stacked in a direction perpendicular to the pattern printing surface so that the cylindrical space (unprinted portion 7) overlaps with the sheet 1 serving as a substrate interposed therebetween.

When this laminate is fired, the portion of the sheet 1 serving as a partition between the cylindrical spaces is burned out, the cylindrical space penetrates, and the direction perpendicular to the pattern printing surface is defined 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 aperture cells 10 whose axial direction is perpendicular to the pattern printing surface.

If the sheet 1 is sandwiched between a non-burnable ceramic sheet or a solid printed ceramic sheet between the pattern printing sheets, it is lightweight and has structural strength with cells that have openings or cells that are not completely connected. A honeycomb-shaped ceramic structure having a high density can be easily manufactured.

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

As shown in FIG. 10, first, a slurry is printed on a sheet 1 made of burnable organic fibers except for a portion serving as an opening cell 10, and a large number of thin cylindrical sheets are formed. A pattern printing sheet 5 having a space portion (non-printing portion) is formed, and then the pattern printing sheet is placed on the pattern printing surface so that the cylindrical space portion (no printing portion 7) communicates. Laminate vertically.

When this laminate is fired, the part of the sheet 1 serving as a partition between the prismatic space portions is burned out, the prismatic space penetrates, and the direction perpendicular to the pattern printing surface is defined as the axial direction. The honeycomb-shaped ceramic structure having the open cells 10 can be manufactured.

Further, since the ceramic pattern is printed as a symmetrical figure as shown in FIG. 10, cracks, cracks,
It is preferable because warping or chipping hardly occurs.

Further, it is also possible to form open cells which communicate with each other in two directions parallel and perpendicular to the printing surface.

FIG. 11 shows the disassembly of the honeycomb-shaped ceramic element structure 9 in which the opening cells 10 are formed so as to communicate in the direction parallel to the printing surface and in the direction perpendicular to the printing surface by laminating a plurality of the pattern sheets 5. The figure is shown.

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

<Embodiment 4> FIG. 12 is an exploded view of a honeycomb-shaped ceramic element structure 9 in which pattern sheets 5 are stacked so that the print patterns of one set of pattern sheets 5 intersect via a ceramic material sheet. Is shown.

The slurry is printed on the ceramic material sheet 3 to form an island-shaped pattern portion in a striped shape. One printed pattern portion 6 of the two pattern sheets 5 of the same shape intersects at right angles. 90 for pattern sheet 5
゜ Rotate and overlap the pattern sheets, 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 a honeycomb-shaped ceramic element structure 9 which is a wall and in which open cells communicating with the printing surface in parallel are formed independently in two directions.

As described above, in the honeycomb-shaped ceramic element having the open cells communicating independently in two directions, cracks, cracks, warpage, or chipping, etc., occur due to the shrinkage of the ceramic material normally generated during drying and firing. It is difficult because it is difficult,
Furthermore, it is strong against stress from both directions and is suitable for structural materials. Further, the present invention is suitable for a heat exchanger that conducts two kinds of fluids having different properties.

<Embodiment 5> FIGS. 13 (a) to 13 (c) show various pattern sheets 5 or a pattern perpendicular to a printed pattern portion 6 of a honeycomb-shaped ceramic structure formed by laminating pattern sheets 5 and ceramic material sheets 3. FIG. 3 is an exploded cross-sectional view cut in a different direction.

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

Example 6 A honeycomb-shaped ceramic structure having various patterns manufactured by the manufacturing method of the present invention is suitable for a chemical reaction device, particularly a catalyst carrier, a bioreactor, a water purifier, and a wastewater 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 of the cell diameter and the like can be extremely high and is about 5 μm. In addition, the relatively large cell diameter reduces weight while maintaining strength, so building materials (walls, ceilings,
It is also suitable for partition materials.

[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 in which ceramics are thickly embossed; A cell for forming a honeycomb by a method for manufacturing a honeycomb-shaped ceramic structure, comprising a sheet laminating step of superimposing a layer on the layer and defining a cell with the thickened predetermined pattern and the superimposed sheet. It is possible to provide a method for manufacturing a honeycomb-shaped ceramic structure which can be freely designed in structure and cell pattern, is fine and highly accurate, is simple and suitable for mass production.

Second, the slurry is printed by screen printing in which a screen formed in a predetermined pattern is arranged on the sheet, and the slurry is printed on the sheet-like substrate through the screen. Printing of the slurry of the pattern can be performed more easily.

Third, by alternately laminating the ceramic material sheets and the pattern sheets, a honeycomb-shaped ceramic structure can be easily manufactured by firing from an elementary structure having a stable structure.

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

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

Sixth, by stacking the pattern sheets having through holes perpendicular to the printing surface of the predetermined pattern, and forming cells in which the through holes communicate with each other in the direction perpendicular to the pattern printing surface, the element structure is formed. A honeycomb-shaped ceramic structure having communicating cells can be manufactured by a simple method without forming a hole after forming the body.

Seventh, since the printed patterns of at least one set of the pattern sheets are stacked so as to intersect with or without a ceramic material sheet interposed therebetween, they are resistant to stress from multiple directions.

Eighth, since the print patterns intersect at right angles, they are resistant to stress from multiple directions, and hardly cause defects such as cracks and cracks during a drying step after printing or during firing. .

Ninth, since the printing pattern is printed symmetrically, defects such as cracks and cracks are less likely to occur during a drying step after printing or during firing.

Tenth, the method includes a step of printing the slurry on the entire surface of a sheet-like substrate to form a ceramic layer to form the ceramic material sheet, thereby forming a honeycomb-like ceramic structure 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 ceramic and organic fibers as main components, the printability of the slurry is good, and the fiber Since the structure is porous and the surface area is widened by burning out, the honeycomb-shaped ceramic structure made of such a raw material is particularly suitable for a chemical reaction device such as a catalyst carrier.

Twelfth, the non-printed portion of the pattern sheet is burned off during the firing of the structure, and the cells communicate with each other in the stacking direction. Structure can be formed.

Thirteenth, the thickness of the layer of the print pattern can be varied as wide as 5 μm to 2 mm and can be freely selected according to the purpose of use. Further, since the thickness can be extremely small, many cells can be formed in one honeycomb-shaped ceramic structure. In this case, the cell surface area is increased, which is particularly suitable for a catalyst carrier or 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 by a simple method with high dimensional accuracy. As described above, since the cross-sectional diameter of the cell can be varied widely and can be freely selected according to the purpose of use and can be extremely small, it is possible to form many cells in one honeycomb-shaped ceramic structure. In that case, the cell surface area is increased, which is particularly suitable for a catalyst carrier and the like.

Fifteenth, on the same print pattern sheet,
Due to the difference in shape and / or material of the printed pattern, 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 mainly composed of an organic material, the printability of the slurry is good and the slurry is inexpensive. The organic fibers are burned off, and the material of the wall of the structure becomes porous, so that the porous wall of the cell can be effectively used 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 material due to firing is burned off, the laminating direction (perpendicular to the laminating surface)
Through holes can be provided, and cells communicating in a lattice can be formed.

Seventeenth, since the slurry contains a metal component composed of metal powder and / or metal fiber (or both), 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 exerted depending on the characteristics of other added metal components. For example, if stainless steel or a lithium alloy is added, the corrosion resistance can be particularly increased. In addition,
Commonly used metals (including alloys) such as iron and aluminum alloys can also be added.

Finally, it is a great advantage that a honeycomb-shaped ceramic structure having a structure and dimensions that cannot be manufactured by other methods is obtained based on the above-mentioned variety in manufacturing method.

[Brief description of the drawings]

FIG. 1 is a schematic top plan view illustrating a step of manufacturing a honeycomb-shaped ceramic structure by a screen printing method according to an embodiment of the present invention. FIG. Solid printing process,
(B) a predetermined pattern printing sheet forming step of forming a predetermined pattern sheet 5 by imprinting a predetermined pattern 6 on the sheet 1 via a screen 4; and (c) a ceramic material sheet 3 and a predetermined pattern printing sheet 5. Are respectively formed in a honeycomb-like structure forming step of laminating 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).

FIGS. 4A and 4B show a pattern printing sheet 5 on which a pattern is printed in an uneven shape, wherein FIG. 4A is an upper plan view showing a pattern printing surface, and FIG.

5A and 5B are pattern printing sheets 5 on which a pattern of an opening cell section is printed in a curved shape (arc shape), wherein FIG. 5A is an upper plan view showing a pattern printing surface, and FIG. 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 a pattern printing sheet 5 on which patterns having two types of shapes, a triangular protrusion and a rectangular shape, are printed.

FIG. 8 is a top plan view of the pattern printing sheet 5 on which various patterns are printed. If the pattern cross section is square, pentagon,
An arbitrary pattern such as a polygon such as 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.

FIG. 9 is a process schematic diagram showing a process of forming an aperture cell in a direction perpendicular to the pattern printing sheet 5.

FIG. 10 is an exploded view of the honeycomb-shaped ceramic structure 9 showing a step of forming a prismatic open cell in a direction perpendicular to the pattern printing 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 in the direction parallel to and perpendicular to the printing surface by stacking a plurality of pattern sheets in FIG. The figure is shown.

FIG. 12 is an exploded view of the honeycomb-shaped ceramic structure 9 in which the pattern sheets 5 are stacked so that the print patterns of one set of pattern sheets 5 intersect via the ceramic material sheet.

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 sheet 2 slurry 3 ceramic material sheet 4 screen 5 pattern sheet (print pattern sheet) 6 pattern section (print pattern section) 7 non-print section 8 stage 9 honeycomb-shaped ceramic element structure 10 cell (open cell)

──────────────────────────────────────────────────続 き Continuation of the front page (72) Osamu Yamamoto, Inventor: Omon 4-1, Daimon, Inuyama-shi, Aichi (56) References JP-A-2-296779 (JP, A) JP-A-63-99957 (JP, A) JP-A-62-101454 (JP, A) JP-A-58-219797 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C04B 38/00 -38/10

Claims (17)

(57) [Claims] 1. A pattern sheet forming step of printing a slurry containing a ceramic raw material as a main component on a sheet-like substrate to form a ceramic material sheet having a predetermined printing pattern, and a ceramic sheet containing at least one pattern sheet. A method for manufacturing a honeycomb-shaped ceramic structure, comprising: a sheet laminating step of laminating material sheets in a plurality of layers and defining cells by a combination of the printing pattern and the superposed 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-like substrate through the screen. 2. 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 overlapped in a plurality of layers. 5. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein said cells are cells communicating at least in a direction parallel to a pattern printing surface. 6. The cell according to claim 1, wherein said pattern sheets having through holes perpendicular to a printing surface of a predetermined pattern are laminated to form cells in which said through holes communicate in a direction perpendicular to the pattern printing surface. 6. The method for manufacturing a honeycomb-shaped ceramic structure according to any one of 1 to 5. 7. The printing method according to claim 1, wherein the printed patterns of at least one set of the pattern sheets are laminated so as to intersect with or without a ceramic material sheet interposed therebetween. Of manufacturing a honeycomb-shaped ceramic structure. 8. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 7, wherein said print patterns intersect at right angles. 9. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the printing pattern is printed symmetrically. 10. The method according to claim 1, further comprising a step of forming the ceramic material sheet by printing the slurry on the entire surface of the sheet-like substrate to form a ceramic layer.
10. The method for manufacturing a honeycomb-shaped ceramic structure according to any one of items 9 to 9. 11. The honeycomb according to claim 1, wherein at least one of the pattern sheet and the ceramic material sheet is made of a raw material containing ceramic and organic fibers as main components. Of manufacturing a ceramic body. 12. The honeycomb-shaped ceramic structure according to claim 1, wherein a non-printed portion of said pattern sheet is burned out when said structure is fired, and cells are communicated in a stacking direction. How to make the body. 13. The printing pattern layer 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 thickness is from 2 to 2 mm. 14. The honeycomb-shaped ceramic structure according to claim 1, wherein a minor axis of the cell of the honeycomb-shaped ceramic structure in a cross-sectional direction is 0.01 to 2 mm. How to make the body. 15. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the shape and / or the material of the printed pattern on the same printed pattern sheet are different. Method. 16. The sheet-like substrate according to claim 1, wherein said sheet-like substrate is made of paper or cloth mainly composed of an organic substance.
The method for manufacturing a honeycomb-shaped ceramic structure according to any one of the above. 17. The method for manufacturing a honeycomb-shaped ceramic structure according to claim 1, wherein the slurry contains a metal component.