JPS5832061A - Manufacture of ceramic formed body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a ceramic molded body for manufacturing a ceramic molded body before firing.

Generally, ceramics are non-metallic inorganic solid materials manufactured by heat treatment, and have excellent heat resistance and surface durability.
Due to its high mechanical strength, it has been used as molded objects in ceramics, refractories, glass, etc. for a long time. In addition, in recent years, it has become clear that ceramics have superior properties such as electrical, magnetic, optical, and biochemical functions in addition to the above properties, and new uses for ceramics are emerging one after another. Developed and called new ceramics or fine ceramics, military components with elaborate forms and shapes, magnetic materials,
A large number of products such as optical devices, artificial bones, and artificial tooth roots have come to be provided.

Along with the development of this new use, various methods for manufacturing ceramic molded bodies have been proposed and put into practical use. However, integrated circuits (IC) and large-scale integrated circuits (LS)
Advances in science and technology, including electronics (centered on I), and the development of industry have inevitably led to significantly more advanced requirements for various materials used, and in the field of ceramics, too, it is necessary to meet these demands. This problem is exceeding the limits that can be handled by conventional technology. Therefore, in order to meet the expectations for ceramics, which have a variety of possibilities, it is essential to develop new manufacturing technologies, and their early realization is awaited.

Conventional manufacturing methods for ceramic molded bodies, except for some manufacturing methods such as glass products that are molded in a high-temperature molten state, use an inorganic non-solid material as a starting material and mechanically crush, classify, mix, etc. A preparation process in which a raw material powder is prepared by performing operations, and a preparation process in which this raw material powder is processed into a powder form or mixed with water, an organic binder, etc. as appropriate to the powder depending on various molding methods such as pressure molding, extrusion molding, tape molding, and casting molding. This process does not include a molding step in which the TiJ' VyJ-like material or slurry-like material is formed by adding it and performing operations such as granulation, sizing, kneading, and stirring, and then processing it into a molded object of a certain shape (Z). Following this molding process, the molded body is subjected to processing operations such as cutting, barrel polishing, and drying if necessary, and then undergoes a firing process in which it is heated and fired at a high temperature to obtain a ceramic product.

However, in order to obtain the desired properties such as mechanical strength and durability, the conventional manufacturing method for ceramic molded bodies uses inorganic powders such as # as a starting material, and also differs in chemical composition or constituent mineral phase. After mixing powders to match the target chemical composition, this mixed powder is molded according to the manufacturing method described above. However, the problem with the conventional manufacturing method is that the reaction during the next firing process of the molded product is Because the process proceeds through the contact interface of Composition is extremely difficult, and the characteristics of ceramics cannot be fully exhibited.

Therefore, as a means to solve this problem, the starting raw material powder is pulverized into as fine particles as possible and thoroughly mixed, and then this mixed powder is calcined at a temperature lower than the final firing temperature, and then this calcined product is Conventionally, the method of homogenizing the composition by repeating the operation of pulverizing, mixing, and then calcining again several times, and then molding and firing this calcined powder has been exclusively praised. Even with complicated processing methods, the final ceramic product may not have sufficient compositional or structural homogeneity, and the presence of local heterogeneity and defects is inevitable.
Due to variations in the functions and properties of ceramics,
This results in a decrease in product yield, a decrease in reliability of quality-H, etc., and the economic loss is extremely large.

Another disadvantage of the conventional method is that the starting material is a powdered solid material, so a large amount of grinding power is required to obtain this fine powder, and there is also the risk of contamination by foreign matter due to wear of balls, liners, etc. during grinding. It is impossible to avoid this and it is difficult to produce high-purity raw materials, and it is difficult and complicated to handle the dust and powder generated during crushing. Complete continuity of the manufacturing process is essentially impossible, which hinders process rationalization and automation.

The present invention solves the problems and drawbacks of the conventional methods described above. (3) Ultra-high purity ceramic products can be easily manufactured. (4) Ceramic molded bodies with a smooth and homogeneous surface can be produced, especially in the form of a film, (5) An object of the present invention is to provide a method for manufacturing a ceramic molded body, which can be manufactured into a fiber-shaped or hollow molded body, and which can realize a continuous ceramic manufacturing process.

As a result of intensive research to achieve the above object, the present inventors have discovered that metal oxides such as Sl, A], Mg, Ti, etc.
It has been discovered that a highly pure and dense molded product can be obtained by injecting a colloid containing hydroxide, hydroxide, or its hydrous compound as a dispersed phase into a mold, and then volatilizing the dispersion medium of this colloid. However, since the dispersion medium content of colloids is generally high, when the dispersion medium is volatilized, the shrinkage rate of the molded product is large, causing cracks and deformation in the molded product. Therefore, we decided to develop a new molding drying method. As a result of further research, we have completed the present invention.

In addition, in this book, colloid melting rate is 10 to 10.0.
0n angstrom (A) (1 to 1000 nm
) is a system in which solid particles with a size of ) are dispersed in a liquid phase.

In the present invention, the starting material is a colloid containing one or more kinds of inorganic substances as a dispersed phase, and the upper liquid is a liquid having a density lower than that of the colloid and dissolving the dispersion medium of the colloid, and having a density higher than that of the colloid. The liquid is the lower liquid, and the colloid is around the interface of the two-layer liquid formed by the upper liquid and the lower liquid (hereinafter, this [around the interface of the two-layer liquid] is abbreviated as the "two-liquid interface part"). ) of the colloid dispersion medium at this two-liquid interface.
Part or all of the colloid is eliminated, and the dispersed phase remaining in the colloid is formed into a molded body.

Although it is preferable that the colloid is continuously supplied to the interface between the two liquids, it is still preferable that the upper liquid contains one or more organic compounds.

It is ingenious that this organic compound contains at least one or more kinds of alcohols, ketones, and aldehydes.

It is preferable that the alcohol has 6 or less carbon atoms.

Preferably, the ketones are ketones having 6 or less carbon atoms.

Moreover, it is preferable that the aldehyde is an aldehyde having 5 or less carbon atoms.

Further, it is preferable that the lower liquid contains one or a mixture of two or more selected from organic halogen compounds.

Moreover, it is preferable that the lower layer liquid consists of mercury or a fusible metal.

It is preferable that the melting point of the fusible metal is 90°C or lower.

Further, it is preferable to use a colloid obtained by hydrolyzing one or more types of alkoxides as the starting material.

Furthermore, it is preferable to use a mixture of two or three or more types of colloids produced by hydrolyzing one or more types of alkoxides as the starting material layer. The dispersion medium of the supplied colloid is absorbed by the soil liquid and it moves from a sol state to a gel state at a negative speed, and as a result, the colloid retains its shape at the time of supply [7, but the lower layer liquid has a high density. The colloid moves through the two-liquid interface, and the dispersion medium is subsequently absorbed and removed from the colloid, resulting in a molded article whose main component is an open-cell dispersed phase. When the dispersion medium is desorbed from this colloid, the molded body shrinks considerably, but since the molded body is located at the interface between the two liquids and the shrinkage is not restrained, cracks and cracks do not occur in the molded body. Furthermore, by continuously supplying the colloid, it is possible to obtain a continuous molded product in the shape of a film, fiber, or other shape.

The temperature l't of the two-liquid interface to which the colloid is supplied is set higher than the freezing point of the dispersion medium of the colloid and the two-layer liquid, and lower than the boiling point thereof.

Although the above-mentioned two-liquid interface may be at normal pressure, it is thought that it can also be carried out under increased pressure or reduced pressure.

Furthermore, after the dispersion medium is removed until the colloid gels and deforms, the molded body is rolled up in the liquid according to its shape, and (b) -! , or the soil is poured into the space above the liquid, f9
Alternatively, a liquid container is provided with an outlet and the liquid is discharged from the outlet and then taken out from the liquid container.

The molded body is then dried to remove the dispersion medium remaining in the molded body and the bilayer liquid that has penetrated by 7 cm.

In this drying method, the material is left to dry in the air at room temperature and pressure, or if necessary, it is dried in an atmosphere with appropriate temperature or pressure conditions.

The dispersed phase of the colloid used in the present invention is not particularly limited and is determined solely by the intended use and properties of the product, but includes, for example, A1, ?, (g, XS1, Tj, Ba.

Examples include oxides and hydroxides of metals such as Pb, Zn, Zr, and rare earth metals, and hydrated compounds thereof, and mixtures thereof may also be used.

Furthermore, colloids are obtained by hydrolyzing alkoxides with a size of -200m or more! f is so clever.

Here, the alkoxides, metal elements, silica, phosphorus, arsenic, selenium, tellurium, borosilicate, carbon, and silica refer to compounds obtained by hydrolyzing alcohols in which hydrogen is replaced with sulfur.

For example, aluminum isoprobogicide (Al(1
-,051hO')s] Add 100 parts of water to 1 part and hydrolyze at about 80°C for 30 minutes.
By generating [Aloo1+], adding a small amount of (-) hydrochloric acid and decomposing it, a stable boehmite sol or pseudo-boehmite sol is produced.This sol is supplied to the two-liquid interface. A desired molded body is obtained.

The advantage of molding a sol obtained by hydrolyzing an alkoxide as a starting material becomes even more pronounced when producing a ceramic molded body made of a composite oxide. In other words, a composite oxide is produced by hydrolyzing a mixture of alkoxides made of a plurality of metal elements constituting this oxide.
It is easily synthesized at low temperatures below -1M and can form a sol, in other words, a colloid, by appropriate peptization treatment as in the case of boehmite5, and is widely used, for example, as a high dielectric constant material. In the case of barium titanate (Ba T, 1.05), barium isopropoxide and titanium isopropoxide are weighed out so that the molar ratio is 1=1, and they are thoroughly mixed in a benzene solution. After mixing and reacting sufficiently at 61 to 80°C, water is added and hydrolyzed to produce white BaTi.
C) Obtain a precipitate. This white precipitate, as in the case of other compounds obtained by hydropurification of alkoxides, consists of fine particles and can be easily obtained into a multistable colloid by peptization. , 4fu provides a suitable starting material for the molding process of the present invention.

On the other hand, the synthesis of 13a Ti 03 by the conventional method requires barium carbonate (Bad!05) and titanium dioxide (T102).
The starting material is powder of
It occurs only when heated above ℃, and at least 1
This reaction will not be completed unless the material is heated to about 100°C, and furthermore, high temperature treatment of 1350°C or higher is required to ensure sufficient sintering. In this method, significant expansion and contraction occur and mechanical stress is applied to the product, resulting in adverse effects such as distortion and cracking.

On the other hand, if the alkoxide is used as the starting material in the production method of the present invention, BaTiO2 is produced at a temperature of 100°C or lower, and the firing temperature of the molded body is set to a low temperature of around 1200°C.
Ceramic products with a higher degree of sintering than conventional methods can be obtained even if the temperature is lowered by the conventional method, and there is no phase change during the firing process. can.

Even when producing ceramic products with more complex compositions, homogeneous properties can be obtained by homogeneously mixing two or more colloids obtained by hydrolyzing -fUj or a mixture of two or more alkoxides. Excellent products can be produced stably and in high yields. The above method is
For example, positive temperature characteristics that require strict control and homogenization of composition (
It is extremely effective when applied to the production of PTO) thermistors.

Furthermore, using an alkoxide as a starting material means that each component is mixed in an organic solvent, making homogenization extremely easy. An automatic continuous system has the advantage of being able to create a starting material (colloid), and it is possible to form a continuous production line for ceramics from the subsequent molding process to the firing process.

Note that the starting materials for the production method of the present invention are not limited to those obtained by hydrolysis and peptization of the alkoxides, but include, for example, those obtained by adding aqueous ammonia to metal salts to produce metal hydroxides. Various methods can be used, such as making a hydroxide into a colloid using a higher alcohol or a dispersion medium such as esters. Furthermore, a homogeneous mixed colloid can be easily produced from a plurality of colloids that are produced using different colloidalization techniques, and this mixed colloid can also be used as a starting material in the present invention.

In addition, if a highly flexible molded product is required in the next process of removing the dispersion medium, molding step 1, or the subsequent firing process, organic binders with porous colloids may be used. The purpose can be achieved by mixing them in advance and then molding them. Examples of the organic binder include polyvinyl alcohol, polyhinyl petral, methyl cellulose, polyacrylic acid, polymethacrylic acid, and the like.

Furthermore, prior to molding the colloid, various thickeners may be added and mixed in order to adjust the viscosity of the colloid to a range suitable for molding.

The colloid is continuously supplied (J() as the liquid constituting the layer of the two-layer liquid supplied with alcohol, aldehyde,
Examples include organic compounds such as ketones.

This upper layer liquid must absorb the continuously supplied colloidal dispersion medium, cause solidification and hardening by gelation of the molded body, and subsequently remove the dispersion medium from the molded body. When the dispersion medium is composed of water and benzene, etc., an organic compound with a small number of carbon atoms is preferable, and the density of the colloid is generally about 1.1 to 1.3. Therefore, it is preferable that the density is 1.0 g'crd or less.

The alcohols are preferably compounds having 6 or less carbon atoms, such as methyl alcohol, ethyl alcohol,
Includes furfuryl alcohol, propyl alcohol, methyl alcohol, hexyl alcohol, and isomers of these compounds.

The aldehydes are preferably compounds having 5 or less carbon atoms, such as acetaldehyde, propionaldehyde, butyraldehyde, acrolein, furfural, and isomers of these compounds.

The ketones are preferably compounds having 6 or less carbon atoms, such as acetone, ethyl methyl ketone, propyl methyl ketone, methyl vinyl ketone, cyclohexanone, and isomers of these compounds.

The compound F11 constituting the upper layer liquid and the various compounds described above may be used alone, or a mixed liquid may be used in which a number of the compounds are mixed. The selection of this organic compound takes into account various conditions such as the type and content of the dispersion medium constituting the colloid, the colloid supply rate, the cross-sectional area and shape of the compact, the speed of removal of the dispersion medium, and the type of lower liquid. be exposed.

In addition, the liquid constituting the lower layer of the two-layer liquid (like the colloid) must also have a high density.As mentioned above, the density of the colloid is generally about 1.1 to 1.3 g/-, so .4 g/c4 or more is preferable; for example, if it is necessary to increase the smoothness of a sheet-like molded product, the shape of the molded product and the application method may be selected, such as selecting a liquid with as high a density as possible. An appropriate compound may be selected from the compounds described below in consideration of the desired characteristics and the like.

Examples of the lower liquid include organic halogen compounds (eg, methylene iodide, tribromobenzene, shortbenzene, bromoform, etc.). In particular, when the organic halogen compound is employed as the lower layer liquid, it is preferable to select an alcohol having low mutual solubility with the organic halogen compound as the upper layer liquid. Furthermore, as the lower layer liquid, for example, mercury or various types of fusible metals (for example, solid Sn such as Wood alloy and Plant alloy) can be used.

1?1) A fusible alloy with a melting point of 90° C. or less consisting of XCdXBi, Zn % XHp;

This mercury or various fusible metals has a higher density than an organic halogen compound, so it has a high surface tension and can support the colloid more stably on the surface. Note that the use of fusible alloys with melting points exceeding 90°C, except in special cases, may cause undesirable effects such as excessively high de-dispersion medium speed and drying speed of the molded product, or the generation of air bubbles within the molded product. Therefore, it is better to avoid adopting it.

Furthermore, as a method for supplying the colloid to the two-liquid interface, for example, a method of extruding the colloid to the two-liquid interface from a mouthpiece or nozzle having a predetermined cross-sectional shape while pressurizing the colloid at low pressure is adopted.

The continuously supplied colloid is formed into a molded body while maintaining its extruded shape at the mouthpiece through gelation and condensation, and is supported by the lower liquid, which has a higher density than the molded body, and forms a two-liquid product. It moves in the upper layer liquid at the interface, receives the de-dispersion medium, and is continuously transported out of the system by a winding device, guide rollers, etc. placed outside the two-layer liquid. Next, by firing this carried out molded body using a tunnel kiln or the like, a desired ceramic product is obtained.
If necessary, cutting is performed prior to the firing process to continuously and efficiently manufacture high-performance ceramic products.

The cross-sectional shape of this molded body can be defined by the shape of the mouthpiece □ as described above, and molded bodies of various shapes such as sheet, rond, tube, honeycomb, and fiber shapes are continuously produced. In addition to the above-mentioned molded body to which a flexible binder is added, it is also possible to obtain ceramic products with various cross-sectional shapes by pressing the sheet-like molded body.

As mentioned above, according to the present invention, (1) since solid powder is not used, there is no need for a pulverization process or a calcination process prior to molding, and there is almost no contamination of foreign matter, resulting in a homogeneous product. (2) Even for ceramic molded bodies with complex compositions such as composite oxides, ultra-high purity molded bodies can be manufactured by mixing the components to form a raw material colloid and removing the dispersion medium. (3) By supplying the raw material colloid to the two-liquid interface from a mouthpiece or nozzle with various cross-sectional shapes, a homogeneous molded body can be easily produced. (4) Since molding is performed continuously in a liquid, there is an excellent effect that a continuous production line for ceramics can be formed up to the firing process.

In order to fully clarify the aspects of the present invention, a more specific explanation will be given below by showing Examples and Comparative Examples, but the examples shown here are merely examples and are not intended to limit the scope of the present invention. do not have.

[Example 1] Commercially available alumina sol and silica sol were mixed with water as a dispersion medium and had a mullite composition (molar ratio of Al2O3:5io2=3:
2) to prepare a raw material colloid.

Next, butanol is used as the upper liquid and methylene iodide is used as the lower liquid.The raw material colloid having the above-mentioned mullite composition is continuously extruded from the nozzle into the 92-liquid interface at a temperature of 20°C and dispersed in a thickness of 100 μm and a width of 30 cm. After removing the medium water with the upper layer liquid butanol until it becomes almost deformed and completely gelling the raw material colloid, it was pulled out of the two-layer liquid and heated at 40°C.
The molded sheet was dried by leaving it in atmospheric air to obtain a molded sheet.

This formed sheet was fired at 1300°C to obtain a mullite ceramic sheet having a thickness of 26 μm after firing.

This mullite ceramic sheet is homogeneous and has a surface roughness of 0.
The diameter was 311 m or less, there were no through holes at all, and the surface roughness was sufficient for use without polishing.

It was also confirmed using an X-ray diffraction device that the mineral composition consisted only of ultra-high purity mullite.

[Comparative Example 1] A raw material colloid having the same mullite composition as in Example 1 is once powdered and calcined at 1000°C, and then a whole calcined powder is prepared.

This calcined powder was then molded using a tape molding method to obtain a mullite ceramic sheet with a thickness of 30 μm after firing, but the mullite ceramic sheet had the same degree of sintering and the same mineral composition as the mullite ceramic sheet of Example 1. It was necessary to perform firing at a high temperature of 1450°C, which is 150°C higher than the firing temperature of Example 1.

Furthermore, the obtained mullite ceramic sheet has many through-holes, and the surface roughness is 1.0 to 2.0 μm, which means that it takes a long time to obtain a smooth surface of 0.3 μm or less. It required time-consuming polishing, and the mechanical strength was significantly weaker than the sheet made according to Example 1, making it difficult to handle.

[Example 2] The alumina sol used in Example 1 is prepared into a raw material colloid using water as a dispersion medium.

Next, the above raw material colloid is continuously extruded from a nozzle at a thickness of 50/jm and a width of 30 wI& (-1 dispersion The water-metal upper layer liquid isobutyraldehyde, which is the medium, is used to remove the material in a groove that does not deform, and after gelling the raw material colloid, it is pulled out of the two-layer liquid and left in the air at room temperature and pressure to dry, forming a formed sheet. Obtained.

This formed sheet was fired at 1400°C to obtain an alumina ceramic sheet having a thickness of 12 μm after firing.

This alumina ceramic sheet is homogeneous and has a surface roughness [1
, 3 μm or less, and there were quite a few through holes.

It was also confirmed using an X-ray diffraction device that the mineral composition consisted only of ultra-high purity alumina. Moreover, although the thickness was about half that of the ceramic sheet of Example 1, it had practically sufficient strength without causing any trouble in handling.

[Comparative Example 2] The same alumina sol as in Example 2 was once powdered and then molded using a tape molding method to have the same thickness and width as in Example 2, but the molded product was thin and had low strength. Therefore, the molded product could not be peeled off from the casting tape, and a ceramic sheet with the same thickness as in Example 2 could not be obtained.

[Example 3] Aluminum isopropoxide obtained by reacting gold-layer aluminum with inglobil alcohol had a pH of 2 to 4.
Boehmite sol was obtained by adding water adjusted to the above and hydrolyzing it.

On the other hand, magnesium methoxide obtained by reacting metallic magnesium with methanol was hydrolyzed by adding water to obtain blue side sil.

Both of these are combined into a spinel composition ν (in molar ratio Al2O3:Mg
0=l: Mix 1) to make W and 4 raw material colloids.

Next, cyclohexanone is used as the upper liquid, and the plant alloy (
Bl 48%, pb 23%, 8n 23%, H(<
The raw material colloid having the above spinel composition was continuously extruded from a nozzle into a two-liquid interface maintained at 60°C with a lower liquid of water and a lower liquid of 40 μm and a width of 50 mm, and then extruded with cyclohexanone, a dispersion medium of water and gold, an upper liquid. After the colloid was removed until it no longer deformed and the raw material colloid was gelled, it was pulled out of the two-layer liquid and left to dry in air at room temperature and pressure to obtain a molded sheet.

This formed sheet was fired at 1200°C to obtain a spinel ceramic sheet 'Jk having a thickness of 8 μm after firing.

This spinel ceramic sheet is homogeneous and has a surface roughness of 0.
3 μm or less, and there are no through holes.1. There wasn't.

The mineral composition was confirmed using an X-ray diffractometer to consist only of ultra-high purity spinel. Moreover, although the thickness was thinner than that of the ceramic sheets of Examples 1 and 2, it had sufficient strength for practical use without any trouble in handling, as in Examples 1 and 2.

[Comparative Example 3] A raw material colloid with the same spinel composition as in Example 3 was once powdered and then molded using a tape molding method to have the same thickness and width as in Example 3, but in the same manner as in Comparative Example 2. For this reason, it was not possible to obtain a spinel ceramic sheet.

Note that the temperature at which a spinel ceramic molded body is generally fired by the tape molding method is 1400°C, so in Example 3, a spinel ceramic sheet could be obtained at a firing temperature of 7 Jt, which is 200°C lower than this temperature.

[Example 4] The silica sol obtained by adding water to ethyl orthosilicate and hydrolyzing it, the boehmite sol used in Example 3, and blueside sil were mixed into cordierite composition (MgO in molar ratio).
: k120s : 5i02 = 2 : 2 : 5
) to prepare the raw material colloid.

Next, methanol is used as the -E layer liquid, and mercury is used as the lower layer liquid.The raw material colloid with the cordierite composition shown in "-" is placed on the W surface area maintained at 5℃, with a diameter of 10 mm and a thickness of 500 mm.
It is extruded into a tube shape with a diameter of μm, and the water in the dispersion medium is removed by the methanol in the upper layer liquid until it no longer deforms. After the raw material colloid is gelled, it is pulled out from the two-layer liquid, and the water is removed from the two-layer liquid. It was dried in air at 1 atm at °C to obtain a molded tube.

This formed tube was fired at 1300° C. to obtain a cordierite ceramic tube having a thickness of 100 μm after firing.

A nitrogen compound (carbon tetrachloride) dissolved in methanol as the upper layer liquid was added to the raw material colloid, and the specific gravity of the upper layer liquid was adjusted to 1.2 C in advance to prevent deformation of the tube.

[Comparative Example 4] An attempt was made to powder a raw material colloid having the same cordierite composition as in Example 4, and then to mold it by extrusion molding to the same diameter and thickness as in Example 4. However, the deformation was severe and it was not possible to make it into a tube shape.

[Example 5] Water is added to 100 parts by weight of the boehmite sol used in Example 2 and 15 parts by weight of the polyacrylic acid-based hydrophilic binder to prepare a raw material colloid.

Next, the above raw material colloid was extruded through a nozzle with a diameter of 50 pm into the two-liquid interface maintained at 20°C, with butanol as the upper liquid and methylene iodide as the lower liquid, and water as the dispersion medium was transferred to 1 ethanol as the upper liquid. After the raw colloid was gelatinized, it was pulled out of the two-layer liquid and allowed to stand in the air at room temperature and pressure to dry, yielding shaped fibers.

This shaped fiber was wound up and fired at 700°C to obtain boehmite fiber.

Patent applicant: Mitsubishi Mining and Cement Co., Ltd. Agent Patent attorney: ``■ Filial procedure amendment Showa,! Manufacture of ceramic molded bodies 3i!i method 3, relationship with the case of the person making the amendment Patent applicant representative Hisaaki Kobayashi 4 Name of agent Patent attorney (7823) Nao Ide i
′□ ′, :, 5'j5 Date of amendment order (voluntary amendment) 6. Number of inventions increased by amendment No. 1) Line 7 of page 5 of the detailed description [...preparation i! l"j manufacturing process" is corrected to "... raw material preparation process."

(2) In Meishin 1, page 8, line 12, [...Metals such as Mg, 'L1, etc.] is corrected to [...Nonmetals or metals such as J, Ti, etc.].

(3) In the specification, page 12, line 5 to line 6 of the same page, "after gelling, deformation...desorption" is replaced with "gelation and subsequent desorption of the dispersion medium." Even if an external stress such as potash is applied to the molded body, it will deform (after hardening has progressed to the extent that 7 disappears).

'(4) On page 13, line 6 of the specification, ``...metals such as rare earths'' is corrected to [...nonmetallic metals such as rare earths or metals-1].

(5) Specification page 16, line 9 1" [Boron, carbon, also "total 1 boron, 1" is corrected.

(6) Specification No. 136, line 10 to page 11, line [・
It refers to a metal compound obtained by hydrolyzing a substituted compound. " refers to a compound in which [... is substituted.

Correct it to 1.

(7) Statement Annex 13, line 14, “100 copies for 1 part” is “100 moles for 1 mole”
I am corrected.

(8) Specification No. 15 Tei No. 9 line I” ~ Dou Yoshi No. 11 line [1 “
··is necessary. This method...the result of joining...''
! i17 [... is necessary. Furthermore, in the conventional method, as seen in the firing process of ferroelectric composite oxides such as BaTiO3 and Pb (Zr, Ti) Os,
Volumetric expansion accompanying the formation of the mineral phase and subsequent firing contraction occur, and the compact undergoes mechanical stress due to the significant volume change during this firing process.

(9) "Add a thickener" on page 17, line 19 of the specification is corrected to "add a thickener or dispersant, etc."

00 Specification page 20, line 16 to page 20, line 17 []
``Because the density is large, the surface tension is large, so -1 is corrected to [-1 because the density is large and the surface tension is large.

0◇ Akira

(] → Specification page 22, line 15 - page 22, line 16 “
In particular, a homogeneous molded body can be made at room temperature +1
"A molded body that can form compatible oxides in close proximity and is homogeneous both compositionally and structurally."

(1:) Specification page 23, line 17 to page 18, “
Detach it with butanol until it no longer deforms, and correct 1.1 to "detach it with butanol."

(1 → Revised ``After 1 calcination'' in line 11 of 2411 to ``After 1 calcination.'')

0 → Specification 1, page 25, line 12, "Detach with isobutyraldehyde until no longer deformed," is amended to "detach with isobutyraldehyde."

0O Specification No. 27 @ line 9 to line 10 of the same page, ``Demorate the rice cake with cyclohexanone until it no longer deforms,'' is corrected to ``Desorb with cyclohexanone.''

αη "Cordierite composition" on page 28, line 18 to page 19 of the specification
ite, 2 Mg0 ・2 , A1.203 ・58
102).

0 → Specification, page 29, line 5 to page 6, line ``Methanol deforms and removes with a strong sweetness'' is corrected to ``methanol desorbs, J''.

(lI In the specification, page 30, line 10 to line 11 of Dosei, "detach with butanol until the deformation collapses," is corrected to "desorb with butanol.")

(1) Specification No. 30 @ line 15 Correct "boehmite fiber" to "alumina fiber".

Claims (9)

[Claims] (1) -! Alternatively, a colloid in which two or more types of inorganic substances are dispersed is used as a starting material (-1 A liquid having a lower density than the colloid and dissolving the dispersion medium of the colloid is used as an upper liquid, and a liquid having a higher density than the colloid is used as a lower liquid. and supplying the colloid around the interface of the two-layer liquid formed by the upper liquid and the lower liquid, and desorbing part or all of the dispersion medium of the colloid around the interface of the two-layer liquid. . A method for producing a ceramic molded body, which comprises forming a dispersed phase remaining in the colloid as a molded body. (2) -1. A method for producing a ramix molded body according to claim (1), wherein the colloid is continuously supplied around the interface of the two-layer liquid. (3) The method for producing a ceramic molded body according to claim (1) or (2), wherein the upper layer liquid contains one or more organic compounds. (4) The method for producing a ceramic molded body according to claim (3), wherein the organic compound contains one or more selected from alcohols, ketones, and aldehydes. (5) The method for producing a ceramic molded body according to claim (4), wherein the alcohol is an alcohol having 6 or less carbon atoms. (6) The method for producing a ceramic molded body according to claim (4), wherein the ketones are ketones having 6 or less carbon atoms. (7) The method for producing a ceramic molded body according to claim (4), wherein the aldehyde is an aldehyde having 5 or less carbon atoms. (8) The ceramic molded article according to any one of claims (1) to (7), wherein the lower liquid contains one f1M selected from organic halogen compounds or a mixture of two or more thereof. manufacturing method. (9) The method for producing a ceramic molded body according to any one of claims (1) to (7), wherein the lower liquid is made of mercury or a fusible metal. (11) A method for producing a ceramic molded body according to claim (9), wherein the melting point of the fusible alloy is 90°C or less. A method for producing a ceramic molded body according to any one of claims 1 to 01, using as a starting material a colloid obtained by hydrolyzing one alkoxide and two or more alkoxides. The method for producing a ceramic molded body according to any one of claims 1 to 00, using a mixture of 2 to 341 as a starting material.