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    • 专利摘要:
    OF THE DESCRIPTION Ceramic particles which can increase the reaction area with an eluate etc. without reducing the diameter of the particle itself and a manufacturing process therefor are provided. A ceramic particle 10 according to the present invention has an average particle diameter of 5 μm or more and 5 mm or less and a plurality of open pores formed at the outer surface, and has two pore size distributions when measured with a mercury porosimeter, in which the two pore size distributions include a first pore size distribution. peak within a range of 300 nm or more and 20 μm or less and another pore size distribution having a peak in a range of 200 nm or less.
    公开号:SE535118C2
    申请号:SE0950563
    申请日:2009-07-21
    公开日:2012-04-17
    发明作者:Hideo Uemoto；Hiroyuki Goto；Taikei Yasumoto；Tomoki Sugino
    申请人:Covalent Materials Corp；
    IPC主号:
    专利说明:

    535 'H8 average pore size as described in JP-08-32551B, a portion having a significant reactivity may be limited to only the outer surface of the ceramic particle. Consequently, the reaction area with the eluate etc. can not be increased and there is a limitation on the improvement of separation property.
    Furthermore, the technique of reducing the diameter of the particle itself to obtain a large specific surface area is a problem, for example that the pressure loss increases when particles of reduced diameter are packed in a column because the flow resistance of the eluate etc. sent to the column is increased to increase the load on the apparatus. .
    The ceramic particle of the present invention is a ceramic particle having an average particle diameter of 5 μm or more and 5 mm or less, in which a plurality of open pores are formed at the outer surface, the ceramic particle having two pore size distributions when measured with a mercury porosimeter.
    More specifically, the two pore size distributions include a first pore size distribution having a peak in a range of 300 nm or more and 20 μm or less and a second pore size distribution having a peak in a range of 200 nm or less.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of the appearance of a ceramic particle according to the present embodiment.
    Fig. 2 is a schematic view of the cross section from the surface to the inside of a ceramic particle according to the present embodiment. Fig. 3 is a schematic view of the steps for explaining the process for producing ceramic particles according to the present embodiment.
    Fig. 4 shows an SEM photograph of a ceramic particle prepared in Example 1.
    Fig. 5 shows analysis of a ceramic particle prepared in Example 1 with a mercury porosimeter.
    Fig. 6 shows an SEM photograph of a ceramic particle prepared in Comparative Examples 1-3.
    Fig. 7 shows analysis of a ceramic particle prepared in Comparative Examples 1-3 with a mercury porosimeter.
    Fig. 8 shows the result of evaluation with respect to separation property in Example 7.
    Fig. 9 shows the result of evaluation with respect to separation property in Comparative Example 4.
    Fig. 10 shows the result of evaluation with respect to separation property in Comparative Example 5.
    Fig. 11 shows the result of evaluation with respect to separation property in Comparative Example 6.
    Fig. 12 shows an SEM photograph of a ceramic particle prepared in Example 7 prior to classification into an average particle size of 80 microns.
    The following is a description of reference numerals in the drawings. 10 15 20 25 30 535 'H8 4 10 ceramic particle 10a outer surface 20 open pore (the first open pore) 20a surface open pore 20b inner open pore 20c inner open pore DETAILED DESCRIPTION OF THE INVENTION above and it intends to provide a ceramic particle which can increase the reaction area with the eluate etc. In the ceramic particle according to the embodiment of the present invention, the reaction area with the eluate etc. can be increased without reducing the size of the particle itself by the nature described above.
    In addition, the ceramic particle of the present invention is a ceramic particle in which a plurality of open pores are formed at the outer surface, the open pore having a first open pore formed at the outer surface having an average pore size of 1 μm or more and 50 μm. or smaller and a second open pore formed in communication with the inner wall surface of the first open pore having an average pore size of 1 μm or more and 50 μm or less; the pore size of the opening portion of the first open pore on the side of the outer surface and the pore size of the connecting portion between the first open pore and the second open pore is 500 nm or more and 30 μm or less; and the skeletal portion forming the open pore comprises a porous body.
    Since the eluate etc flows to the inside of the ceramic particle of the nature described above, the reaction area with the eluate etc can be further increased. The open pore is preferably formed from an outer surface which communicates with the other outer surface of the ceramic particle.
    Since the eluate etc can flow evenly to the inside of the ceramic particle due to the nature described above, the reaction area with the eluate etc can be maximized.
    The ceramic particle comprises one of inorganic oxides such as alumina, silica, mullite, zirconia and calcium phosphate, silicon carbide, boron carbide and silicon nitride.
    Depending on the nature described above, the ceramic particle of the present invention can be used generally for catalyst supports, cell culture substrates, fillers for liquid chromatography, etc.
    A process for producing a ceramic particle according to the present invention includes a step of: adding a first oil and a hydraulic surfactant to a slurry (W) containing a ceramic powder. a binder, a dispersant and pure water, and to provide shear force to the first oil to form an oil droplet particle (O) comprising the first oil, to prepare an ONV emulsion in which the oil droplet particles (O) are dispersed in the slurry (W) ; a step of adding the ONV emulsion to a second oil (0) containing an oleophilic surfactant and imparting shear to the O / W emulsion to form a fine liquid droplet (O / W) comprising a slurry in which the oil droplet particles (O ) are enclosed on the inside thereof to prepare an OIW / O emulsion in which the liquid droplets (ONV) are dispersed in the second oil (0); and a step for burning the fith drop of liquid (O / N).
    The ceramic particle of the present invention described above can be prepared by the production method described above. 10 15 20 25 30 535 'H8 A preferred embodiment of the present invention is specifically described below.
    The first embodiment Fig. 1 shows a schematic view of the appearance of the ceramic particle according to the present embodiment and Fig. 2 shows a schematic view of the cross section from the surface to the inside of the ceramic particle according to the present embodiment.
    As shown in Fig. 1, the ceramic particle 10 of the present embodiment has a plurality of first open pores 20 at the outer surface 10a and further has a plurality of second open pores (not illustrated) having a pore size smaller than that of the first open pore 20. at the outer surface 10a and the surface of the skeletal part 30 which constitutes the first open pore 20.
    The first open pore is formed by a spherical pore. The skeletal part constituting the spherical open pore, i.e. the other open pore, is formed by a non-spherical porous body. The spherical shape referred to herein is not limited to a purely spherical shape but also includes, for example, a shape that is slightly flattened or deformed from the pure spherical shape. The non-spherical shape refers to those other than the spherical shape described above.
    As shown in Fig. 2, the first open pore 20 has a first open pore 20a formed at the outer surface 10a, an inner open pore 20b formed in communication with the inner wall surface 20a1 of the surface-open pore 20a, and an inner open pore 20c, formed in communication with the inner wall surface 20b1 of the inner open pore 20b.
    More specifically, in the ceramic particle 10 according to the present embodiment, the peak in the pore size distribution which depends on the pore size 0, for the opening on the side of the outer surface 10a of the surface-open pore 20a, is the pore size Ru for the connecting portion communicating with the surface-open pore 10 Vi-B 20a and the inner open pore 20b, and the pore size RQ of the connecting portion connecting between the inner open pores (between 20b and 20c in Fig. 2) (hereinafter referred to as a peak in the open pore distribution which is dependent on the first open pore) 300 nm or more and 20 μm or less. Furthermore, the peak in the pore size distribution is the pore size of the opening portion of the outer surface 10a constituting the second open pore (not illustrated), the pore size of the opening portion of the first open pore 20 (not illustrated), and the pore size of the connecting portion connecting the second open pores. (not illustrated) (hereinafter referred to as the peak in the pore size distribution which is dependent on the second open pore) 200 nm or less.
    Since the ceramic particle 10 according to the present embodiment, as described above, has a number of the open pores as described above and consequently can react with an eluate etc. not only at the outer surface but also at the surface of the skeletal part constituting the open pore by the flow of the eluate etc into the open pore, the reaction area with the eluate etc can be increased without reducing the diameter of the particle itself. In a case where the peak in the pore size distribution depending on the first open pore is less than 300 nm, it is difficult because the pore size 0 for the opening portion on the side of the outer surface 10a is reduced and the eluate etc. flows less into the open pore 20. , to increase the reaction area with the eluate, etc. In a case where the peak in the pore size distribution depending on the first open pore exceeds 20 μm, it is because the pore size Rp, RQ of the opening part is increased and the strength of the ceramic particle 10 itself is also not reduced. preferred. In addition, since lowering the strength of the ceramic particle 10 itself causes fracture of the ceramic particle 10, which causes a decrease in the diameter of the ceramic particle, a problem of increasing pressure loss is caused as a result. In a case where the peak in the pore size distribution depending on the second open pore exceeds 200 nm, it is not preferred because the reactivity with the eluate etc. is lowered by reducing the specific surface area.
    The first open pore 20 is preferably formed through the ceramic particle 10 from an outer surface to the second outer surface.
    Since the eluate etc can flow evenly to the inside of the ceramic particle, with such a nature the reaction area with the eluate etc can be maximized.
    The peak in the pore size distribution is a value measured with a mercury penetration method using a mercury porosimeter.
    The particle diameter of the ceramic particle 10 according to the present embodiment is not particularly limited as long as the open pore is formed in fl number and has such a size that the strength can be maintained as the ceramic particle 10. The particle diameter (average particle diameter) of the ceramic particle 10 according to the present embodiment is, for example, 5 μm or more and 5 mm or less.
    The ceramic particle 10 of the present embodiment described above preferably comprises any of inorganic oxides such as alumina, silica, mulite, zirconia, calcium phosphate, and titanium oxide, silicon carbide, boron carbide and silicon nitride.
    With such a nature, the ceramic particle of the present invention can be used generally, for example as a catalyst support, a cell culture medium, a liquid chromatographic filler, etc.
    Among these, calcium phosphate is suitably used as the filler for liquid chromatography such as HPLC (High Performance Liquid Chromatography) 1035 20 25 30 535 'HB because it has high adsorption capacity to proteins etc. and a higher effect as a filler can be obtained by using the ceramic particle 10 of the nature described above. As the calcium phosphate referred to herein, any calcium phosphate at a CalP ratio of 1.5 to 1.8 can be used and includes, for example, tricalcium phosphate, hydroxyapatite and oro-uroapatite. In addition, in a case constituting the ceramic particle 10 of the present invention with calcium phosphate and using the particle as the filler, the ceramic particle 10 preferably has a specific surface area of 10 m 2 / g or more. For this purpose, calcium phosphate used as the raw material preferably has a specific surface area of 50 m 2 / g or more, also taking into account the increase in strength after calcination in the manufacturing process which will be described later.
    As described above, it is necessary that the skeletal portion 30 constituting the first open pore 20 be formed by the porous body. The specific surface area of the material constituting the skeletal part 30 is, for example, 5 mzg / g or more and 60 mzlg or less.
    Next, a manufacturing method for the ceramic particle 10 according to the present embodiment will be described with reference to the drawings. Fig. 3 is a schematic view of the steps for explaining the manufacturing process of the ceramic particle according to the present embodiment.
    First, a slurry (W) 50 is prepared which contains a ceramic powder, a binder, a dispersant and pure water (Fig. 3 (a)).
    The ceramic powder used herein is a powder of any of inorganic oxides such as alumina, silica, mulite, zirconia, calcium phosphate and titanium oxide, silicon carbide, boron carbide and silicon nitride. In addition, for the binder used herein, agar may be preferably used. For the dispersant used herein, ammonium polyacylate can be used in 535 'P1-B10 examples. Pure water referred to herein is pure water commonly used in the field of semiconductor production generally formed by industrial water, tap water, etc. such as raw water by separating contaminants contained therein for purification by using, for example, a very pure ion exchange resin, a high performance membrane, a deaerator. etc. For example, the pure water refers to those that are purified to, for example, a specific resistivity of 1 MQ-cm or greater compared to domestic tap water of 0.01 to 0.05 MQ-cm.
    Then, a first oil 51 and a hydrophobic surfactant (not illustrated) are added to the slurry (VV) 50 to provide the first oil 51 with a shear force 52 (Fig. 3 (b)). - As the first oil 51 used herein, , isoparafene, hexadecane, etc. are preferably used. Furthermore, for the hydro surfactant, polyoxyethylene sorbitan monooleate can be preferably used.
    Furthermore, the shear force 52 can be provided by a mixer.
    As described above, by giving the shear force 52 to the first oil 51, oil droplets (O) 53 are formed which comprise the first oil 51 to prepare an ONV emulsion 54 in which the oil droplets (O) 53 are dispersed in the slurry (W) 50 (Fig. 3 (c)).
    Then a second oil (O) 55 is prepared which contains an oleo surfactant.
    The O / N emulsion 54 prepared as described above is added to the second oil (O) 55 and a shear force 56 is given to the ONV emulsion 54 (Fig. 3 (d)).
    For the second oil 55 used herein can normally be paraffin, isoparaffin. hexadecane etc. should be suitably used. Furthermore, for the oleophilic surfactant 535 'HB 11 sorbitan sesquioleate can be suitably used. Furthermore, the shear force 56 can be provided by a mixer.
    By providing the O drops (O / W) 57 which are dispersed in the second oil (O) 55 are prepared (Fig. 3 (e)). Finally, when the liquid droplets (ONV) 57 are recovered from the O / N / O emulsion 58 and the liquid droplets (O / N) 57 are calcined, the slurry (W) 50 is calcined in the liquid droplets (ONV). 57 and the oil droplet particles (O) 53 are gasified, by which the ceramic particle 10 according to the invention having the open pore 20 formed by the part of the oil droplet particle (O) 53 can be produced.
    The pore sizes 0 ,, R ", Ra can be regulated according to the amount of use of the first oil 51, the stroke and the amount of use of the hydraulic surfactant, the intensity of the shear force 52, etc.
    Furthermore, the porosity of the porous body in the skeletal part 30 can be controlled by the particle diameter, the calcination temperature of the raw material used as the ceramic powder, etc. The step of producing the ceramic particle 10 is further carried out in a case using agar (for example at 40 ° C or higher) from the preparation of the slurry (W) 50 to form the liquid droplets (ONV) 57. This can effectively form the fine liquid droplets (0 / 1N) 57 without solidifying agar.
    Furthermore, it is preferable to provide a step for cooling the O / W / O emulsion 58 after formation of the liquid droplets (O / W) 57 and before recovering the liquid droplets (ONV). 57 from the (O / N / O) emulsion 58. Since the agar contained in the fi hub liquid droplet (ONV) 57 is solidified after formation of the fi na liquid droplet (ONV) 57 and all the fi na liquid droplets (ONV) 57 are gelled through this step creating this an effect to stabilize the shape.
    Furthermore, the gelled liquid droplets (ONV) 57 are preferably washed using a solvent such as ethanol after recovery and before calcination. It removes the surfactant component contained in the fi liquid drops (ONV) 57 and water contained in the fi liquid drops (O / W) 57 is replaced with the solvent. Since this can gasify the substitution solvent component at an early stage during calcination, the gelled liquid droplet (ONV) 57 can be calcined keeping its shape stable as it is.
    Furthermore, a drying treatment can also be applied after washing with the solvent and before calcination. The drying treatment is carried out, for example, by vacuum drying under a reduced pressure. Since it removes the solvent component before calcination, calcination can be performed while keeping the shape of the fi n liquid drop (ONV) 57 stable as it is.
    Furthermore, an adhesive coating treatment for coating an oily component on the gelled liquid droplets (ONV) 57 can also be performed after washing with the solvent and before the drying treatment. With the coating treatment as described above, calcination can be further carried out while keeping the shape of the liquid drop (O / N) 57 stable as it is. For the oily component, paraffin, isoparaffin, hexadecane, etc. can normally be suitably used.
    The ceramic particle 10 of the present embodiment can also be prepared by preparing the O / N emulsion 54 by the method described above and granulating the O / N emulsion 54 by spray drying to form a granular powder , followed by calcination of the granulated powder.
    The second embodiment Fig. 1 shows a schematic view of the appearance of a ceramic particle according to the present embodiment, and Fig. 2 shows a schematic view of a cross section from the surface to the inside of a ceramic particle according to the present embodiment. The ceramic particle 10 according to the present embodiment has a sufficient number of open pores 20 at an outer surface 10a as shown in Fig. 1.
    As shown in Fig. 2, the open pore 20 corresponding to the first open pore in the second embodiment has a surface open pore 20a formed at the outer surface 10a and having an outer pore size of 500 nm or more and 50 μm or less in which the pore size 01 of the opening portion of the surface-open pore 20a on the side of the outer surface 10a is 300 nm or more and 20 μm or less.
    Since the eluate etc. flows to the inside of the surface-open pore 20a of the ceramic particle 10 due to the nature described above, the reaction area with the eluate etc. can be increased without reducing the size of the particle itself in the ceramic particle according to this embodiment. In a case where the average pore size is less than 500 nm it is, because the pore size of the orifice part is sometimes less than 300 nm and the eluate etc flows less into the surface open pore, it is difficult to increase the reaction area with the eluate etc and there is a limitation on the improvement. of the separation property. furthermore, in a case where the average pore size is over 50 μm, the pore size of the opening part is sometimes over 20 μm and the strength of the ceramic particle 10 itself may optionally be lowered, which is not preferred.
    Decreasing the strength of the ceramic particle 10 itself leads to a problem in the decomposition of the ceramic particle 10 being induced. In addition, since this reduces the size of the ceramic particles, the pressure loss is increased as a result.
    The open pore 20 (first open pore), as shown in Fig. 2, has at least one surface open pore 20a formed at the outer surface 10a and having an average pore size of 500 nm or more and 50 μm or less and an inner open pore 20b formed in communication with the inner wall surface 20a1 of the surface-open pore 20a and having an average pore size of 500 nm or more and 50 μm or less.
    It is preferred that the pore size O. of the opening portion of the surface open pore 20a on the side of the outer surface 10a and the pore size Ru of the connecting portion between the surface open pore 20a and the inner open pore 20b be 300 nm or more and 20 μm or less.
    Since the eluate etc. flows into the inside of the ceramic particle 10 (the inner open pore 20b) due to the structure described above, the reaction area with the eluate etc. can be further increased.
    It is more preferred that the open pore 20 is formed from an outer surface in communication with the second outer surface of the ceramic particle 10. In other words, it is preferred that a plurality of surface open pores 20a and inner open pores 20b, 20c are formed from an outer surface in communication with the second outer surface of the ceramic particle 10 as shown by the second inner open pore 20c formed in connection with the inner wall surface 20b1 of the inner open pore 20b and having an average pore size of 500 nm or more and 50 μm or less as shown in Fig. 2. Also in this case, the pore size Ru of the connecting portion between the inner open pores 20b and 20c is preferably from 300 nm or more and 20 μm or less in the same manner as above. Since the eluate etc can flow evenly to the inside of the ceramic particle depending on the structure described above, the reaction area with the eluate etc can be maximized.
    The surface-open pore and the inner open pore are formed of spherical pores.
    The skeletal portion constituting the spherical open pore (corresponding to the second open pore in the first embodiment) is formed by a non-spherical porous body. The spherical shape is not limited to a purely spherical shape and also includes, for example, a shape which is slightly flattened or deformed from the purely spherical shape. The non-spherical shape refers to those other than the spherical shape described above.
    The average pore size is a value obtained by electron microscopic observation and image diffraction for a resin-embedded ceramic particle that is polished at the surface. Furthermore, the pore sizes 0, Ru and RQ are measured by a mercury penetration method using a mercury porosimeter.
    The particle size of the ceramic particle 10 according to the present embodiment described above is not particularly limited as long as a sufficient number of the open pores 20 are formed and the particle has such a size that the strength can be maintained as the ceramic particle 10. The particle size of the ceramic particle 10 according to this embodiment is, for example, 10 μm or more and 200 μm or less.
    The ceramic particle 10 according to the embodiment described above preferably comprises one of inorganic oxides such as alumina, silica, mullite, zirconium, and calcium phosphate, silicon carbide, boron carbide and silicon nitride. 10 15 20 25 30 535 'HB 16 Depending on the nature as described above, the ceramic particle of the present invention can be used generally, for example, for catalyst supports, cell culture substrates, fillers for liquid chromatography, etc.
    Among these, calcium phosphate is most suitably used as the liquid chromatographic filler such as HPLC (High Performance Liquid Chromatography) due to its good adsorption property to proteins etc. A high effect such as the filler can be obtained by using the ceramic particle 10 having the structure described above. As the calcium phosphate referred to herein, any calcium phosphate having a Ca / P ratio of from 1.5 to 1.8 can be used and includes tricalcium phosphate, hydroxylapatite and oro-uroapatite. In a case where the ceramic particle 10 of the present invention comprises calcium phosphate and is used as the filler, the ceramic particle 10 preferably has a specific surface area of 10 m 2 / g or more. For this purpose, the calcium phosphate used as the raw material preferably has a specific surface area of 50 mzlg or more also to improve the strength after firing in the production process which will be described later.
    It is necessary that the skeletal part 30 forming the open pore 20 comprises a porous body. The specific surface area of the material forming the skeletal part 30 is, for example, 5 mz / g or more and 60 mz / g or less.
    Next, a method of making a ceramic particle 10 according to the present embodiment is described with reference to the drawings. Fig. 3 is a schematic view of the steps for explaining the method of manufacturing the ceramic particle according to the present embodiment.
    First, a slurry (W) 50 is prepared which contains a ceramic powder, a binder, a dispersant and pure water (Fig. 3 (a)). 10 15 20 25 30 535 'H8 17 For the ceramic powder used herein, a powder of one of inorganic oxides such as alumina, silica, mullite, zirconia, and calcium phosphate, silicon carbide, boron carbide, or silicon nitride is used. As the binder used herein, agar may be suitably used. Furthermore, as the dispersant used herein, ammonium polyacylate, etc. can be used. Pure water referred to herein is water generally used in the field of semiconductor production, which is prepared from industrial water, tap water, etc. such as raw water and by purifying and separating contaminants contained therein by using a very pure ion exchange resin, a high performance film, a deaerator and so on. refers to water that has been purified to a degree of, for example, 1 MQ-cm or greater, such as the specific resistivity compared with 0.01 to 0.05 MQ-cm of tap water for home use.
    Then a first oil 51 and a hydro surfactant (not illustrated) are added to the slurry (VV) 50 and shear force 52 is given to the first oil 51 (Fig. 3 (b)).
    As the first oil 51 used herein, paraffin, isoparaffin, hexadecane, etc. can normally be suitably used. In addition, as the hydrophilic surfactant, polyoxyethylene sorbitan monooleate can be suitably used. Furthermore, the shear force 52 can be provided by a mixer.
    As described above, by giving the shear force 52 to the first oil 51, oil droplets (O) 53 are formed which comprise the first oil 51 to prepare an ONV emulsion 54 in which the oil droplets (O) 53 are dispersed in the slurry (W) 50 (Fig. 3 (c)).
    Then a second oil (O) 55 is prepared which contains a hydraulic surfactant.
    The O / N emulsion 54 prepared as described above is added to the second oil (O) 55 and a shear force 56 is given to the O / N emulsion 54 (Fig. 3 (d)). Like the other oil 55 used herein, paraffin, isoparaffin, hexadecane, etc. can normally be suitably used. As the oleo surfactant, sorbitan sesquioleate can be suitably used. Furthermore, the shear force 56 can be provided by a mixer.
    By applying the shear force 56 to the ONV emulsion 54, a liquid droplet (OAN) 57 is formed which comprises a slurry 50 in which the oil droplet particle (O) 53 is enclosed, followed by preparation of an O / W / O emulsion 58 in which they The droplets (OAN) 57 are dispersed in the second oil (O) 55 (Fig. 3 (e)).
    Finally, by extracting the liquid droplets (ONV) 57 from the O / N / O emulsion 58 and burning the liquid droplets (ONV) 57, the slurry (W) 50 is burned in the liquid droplets (ONV) 57, and the oil droplet particle (O 53 is gasified, by which the ceramic particle 10 according to the present invention, in which the open pore 20 is formed by the part of the oil droplet particle (0) 53, can be produced.
    The average pore size and aperture sizes O., Ru, and RQ of the open pore 20 can be controlled, for example, depending on the amount of the first oil 51 to be used, the type and amount of use of the hydraulic surfactant, the intensity of the shear force 52, etc.
    In addition, the porosity of the porous body in the skeletal part 30 can be controlled, for example, by the particle size and the firing temperature of the raw material used as the ceramic powder.
    Furthermore, in the step of producing the ceramic particle 10, in a case using agar as a binder, it is preferably prepared under a heated state (for example at 40 ° C or higher) from the production of the slurry (VV) 50 to form of the liquid droplets (O / W) 57. This can effectively form the liquid droplets (ONV) 57 without solidification of agar. Furthermore, it is preferable to provide a step for cooling the O The O) emulsion 58. Since the agar contained in the fine liquid droplet (O / N) 57 solidifies after formation of the fine liquid droplet (ONV) 57 and all the fine liquid droplets (ONV) 57 are gelled, giving an effect of stabilizing the form.
    Furthermore, it is preferable to wash the gelled liquid drop (ONV) 57 using a solvent such as ethanol after recovery and before firing. It removes the surfactant component contained in the fine liquid drop (ONV) 57 and replaces the water content contained in the fi n liquid drop (ONV) 57 with the solvent. Since this can gasify the substitution solvent component at an early stage during firing, the gelled liquid droplet (ONV) 57 can be fired where its shape is kept stable.
    Furthermore, a drying treatment can also be applied after washing with the solvent before firing. The drying treatment is carried out, for example, by vacuum drying under a reduced pressure. Since it removes the solvent component before firing, firing can be performed while keeping the shape of the fi n liquid drop (ONV) 57 stable.
    Furthermore, an adhesive coating treatment for coating an oily component on the gelled liquid drop (ONV) 57 can also be performed after washing with the solvent and before the drying treatment. With the film coating treatment described above, firing can be performed while keeping the shape of the liquid droplet (ONV) 57 further stable as it is.
    For the oily component, paraffin, isoparaffin, hexadecane, etc. can normally be suitably used. The ceramic particle 10 of the present embodiment can also be prepared by preparing the O / 1N emulsion 54 by the method described above, and then granulating the ONV emulsion 54 by spray drying to form a granular powder. followed by firing of the pelleted powder.
    The present invention provides a ceramic particle which can increase the reaction area with an eluate etc without reducing the size of the particle itself, and a production process therefor.
    Examples Although the following will describe the present invention in detail with reference to the examples, the present invention is not limited thereto.
    An example according to the first embodiment is specifically described.
    Example 1 To an agar solution in water formed by adding agar to pure water at a weight ratio of 0.5% was mixed a hydroxyapatite powder at a weight ratio of 30% based on the agar solution in water, and ammonium polyacylate was added as a dispersant at a weight ratio of 5%. % based on the hydroxyapatite powder. They were mixed in a ball mill for 10 hours or more to prepare a slurry containing hydroxyapatite.
    Then, polyoxyethylene sorbitan monooleate at 1% based on pure water and isoparaffin were added at 30% based on pure water to the resulting slurry, and they were stirred using a mixer. The isoparaffin was emulsified in the slurry by stirring to form oil droplet particles, and an apatite slurry in which the oil droplet particles were dispersed was prepared. Next, the isoparaffin and a surfactant (sorbian sesquioleate: at a weight ratio of 4% based on the isoparaffin) were added to a beaker; was stirred using a mixer while heating; and the apatite slurry prepared as described above containing the oil droplet particles dispersed therein was added over and over again in the stirred state of the beaker. By stirring, liquid droplets were formed comprising a slurry enclosing the oil droplet particles on the inside of the beaker.
    The treatments so far have been carried out under a state while maintaining the temperature at 40 ° C or higher so that agar such as the binder did not harden.
    Thereafter, the beaker was cooled to effect gelation of the fine liquid droplets formed as described above. Then the gelled liquid droplets were recovered and, after solvent washing with ethanol, vacuum dried under reduced pressure, followed by a calcination treatment at 700 ° C.
    The obtained ceramic particles were classified into an average particle diameter of 80 μm as a sample according to Example 1.
    Comparative Examples 1 to 3 To an agar solution in water formed by adding agar to pure water at a weight ratio of 0.5% was mixed a hydroxyapatite powder at a weight ratio of 30% based on the agar solution in water, and ammonium polyacylate was added as a dispersant at a weight ratio of 5% based on the hydroxyapatite powder. They were mixed in a ball mill for 10 hours or more to prepare a slurry containing hydroxyapatite.
    Then, without forming the oil droplet particle as shown in Example 1, isoparaffin and a surfactant (sorbitan sesquioleate: at a weight ratio of 4% to isoparaffin) were added to a beaker and stirred while heating using a 535 'HB 22 mixer. In the stirred state, the slurry prepared as described above was added to the beaker over and over again. By stirring, liquid droplets formed in the beaker comprising a slurry which does not enclose the oil droplet particle to the inside.
    The treatments so far have been carried out under a state while maintaining the temperature at 40 ° C or higher so that agar such as the binder did not harden.
    Thereafter, the beaker was cooled to effect gelation of the liquid droplets formed as described above. The gelled drops were recovered and, after solvent washing with ethanol, vacuum dried under reduced pressure, followed by a calcination treatment at 700 ° C.
    The obtained ceramic particles were classified into the average particle diameters of 80 μm, 60 μm, and 40 μm, which are respectively used as samples of Comparative Examples 1, 2 and 3.
    Then, for the samples prepared in Example 1 and Comparative Examples 1 to 3, a protein separation function test was performed.
    Protein Separation Function Test The protein separation function test was performed using a high resolution liquid chromatograph (Lachorm L-7000, manufactured by Hitachi Ltd.).
    An eluate, a protein sample, an empty column, a filler slurry, test conditions, etc. were as described below.
    For the eluate, 1 mM sodium phosphate buffer and 400 mM sodium phosphate buffer were used.
    Each of the eluates was adjusted to pH 6.8. As the protein sample, albumin, ribosome and cytochrome C were used, and protein sample solutions each containing protein at 0.03 mM were used. For the solvent for the 535 'WB 23 protein sample solution, 1 mM sodium phosphate buffer was used. For the empty column, a stainless steel column of 2 mm ø> <150 mm was used.
    As the filler slurry, 0.3 g of each of different kinds of fillers diluted with 400 mM sodium phosphate buffer was used to be a particle concentration of 10% by weight. When packing in a column, an empty column was arranged with a packer attached to a high-resolution liquid chromatograph, to which the filler slurry was charged and filled by flowing 1 mM sodium phosphate buffer at a flow rate of 2 mM / min.
    For the evaluation of the protein separation function, the eluate was allowed to flow at a flow rate of 1 ml / min. After digestion of the 1 mM sodium phosphate buffer as the eluate for 5 minutes, it changed linearly from 1 mM to 200.5 mM (1 mM (50%) + 400 mM (50%)) for 15 minutes.
    Considering the result of the separation function in Comparative Example 1 to Comparative Example 3, it was confirmed that the protein separation function improved more as the particle diameter was smaller. It was found that peaks for albumin and ribosome separated more as the particle diameter was smaller. This is considered to be due to the fact that the specific surface area was increased due to the decrease in the particle diameter and the contact surface with the eluate was increased. It was confirmed that albumin and lysozyme were not separated in Comparative Example 1 where the average particle diameter was 80 μm.
    On the contrary, it was confirmed in Example 1 that peaks of the albumin and lysozyme were very much separated even though the average particle diameter was identical to that of Comparative Example 1.
    Fig. 4 shows an SEM photograph of ceramic particles prepared in Example 1 and Fig. 5 shows the result of analysis of the ceramic particles prepared in Example 1 with a mercury porosimeter. Furthermore, Fig. 6 shows an SEM photograph fi of 10 15 20 25 30 535 ”HB 24 ceramic particles prepared in Comparative Examples 1 to 3. and Fig. 7 shows the result of analysis for the ceramic particles manufactured in Comparative Example 1 to Comparative Example 3. through a mercury porosity.
    It can be confirmed as shown in Fig. 4 and Fig. 5 that the ceramic particles prepared in Example 1 have two types of peaks which are a peak in the pore size distribution of 300 nm or more and 20 μm or less and a peak in the pore size distribution in 200 nm or less. The top right end of Fig. 5 detects a free space between particles through the mercury porosimeter, which is different from the top of the ceramic particles of the present invention. On the contrary, as shown in Fig. 6 and Fig. 7, in the ceramic particles made in Comparative Examples 1 to 3, there was no peak in the pore size distribution of 300 nm or more and 20 μm or less, and a result was confirmed that only the peak in the pore size distribution of 200 nm or less occurred.
    When the specific surface area was measured for skeletal part of the ceramic particles in Example 1 and Comparative Examples 1 to 3, the specific surface area was 30 mg / l for each of them.
    Example 2 Ceramic particles were produced by the same procedure as in Example 1 except using an alumina powder instead of the hydroxyapatite powder.
    As a result, in the same manner as in Example 1, ceramic particles could be obtained in which two pore size distributions occurred when measured with a mercury porosimeter, within a range of 300 nm or more and 20 μm or less and within a range of 200 nm or less. . Example 3 Ceramic particles were produced by the same procedure as in Example 1 except using a silica powder instead of hydroxyapatite powder in Example 1.
    As a result, in the same manner as in Example 1, ceramic particles could be obtained in which two pore size distributions occurred when measured with a mercury porosimeter, within a range of 300 nm or more and 20 μm or less and within a range of 200 nm or less. .
    Example 4 Ceramic particles were produced by the same procedure as in Example 1 except using a mulite powder instead of the hydroxyapatite powder.
    As a result, in the same manner as in Example 1, ceramic particles could be obtained in which two pore size distributions occurred when measured with a mercury porosimeter, within a range of 300 nm or more and 20 μm or less and within a range of 200 nm or less. .
    Example 5 Ceramic particles were produced by the same procedure as in Example 1 except using a zirconia powder instead of the hydroxyapatite powder.
    As a result, in the same manner as in Example 1, ceramic particles could be obtained in which two pore size distributions occurred when measured with a mercury porosimeter, within a range of 300 nm or more and 20 μm or less and within a range of 200 nm or less. . Example 15 Ceramic particles were produced by the same procedure as in Example 1 except for using a silicon carbide powder instead of the hydroxyapatite powder.
    As a result, in the same manner as in Example 1, ceramic particles could be obtained in which two pore size distributions occurred when measured with a mercury porosimeter, within a range of 300 nm or more and 20 μm or less and within a range of 200 nm or less. .
    An example according to the second embodiment is specifically described.
    Example 7 To an agar solution in water formed by adding agar to pure water at a weight ratio of 0.5%, a hydroxyapatite powder was mixed at a weight ratio of 30% based on the agar solution in water, and ammonium polyacylate was added as a dispersant at a weight ratio of 5% based on the hydroxyapatile powder. They were mixed in a ball mill for 10 hours or more to prepare a slurry containing hydroxyapatite.
    Then 1% polyoxyethylene sorbitan monooleate based on pure water and 30% isoparaffin based on pure water were added to the resulting slurry, and then they were stirred using a mixer. the isoparaffin was emulsified in the slurry by stirring to form an oil droplet particle, and an apatite slurry in which the oil droplet particles were dispersed was prepared.
    Then the isoparaf fi n and a surfactant (sorbitan sesquioleate: at 4% by weight ratio based on the isoparaf fi n) were charged into a beaker and stirred using a mixer while heating. The apatite slurry, in which the oil droplet particles thus prepared were dispersed, was added alternately in the stirred state in the beaker. By stirring, liquid droplets were formed comprising a slurry enclosing the oil droplet particles on the inside of the beaker.
    The treatments so far have been carried out under a state in which the temperature is maintained at 40 ° C or higher so that agar such as the binder is not solidified.
    Thereafter, the beaker was cooled and gelling liquid droplets formed as described above. Then the gelled drops were recovered and, after solvent washing with ethanol, vacuum dried under reduced pressure and subjected to a firing treatment at 700 ° C.
    The obtained ceramic particles were classified into an average particle size of 80 μm as a sample according to Example 7.
    Comparative Examples 4 to 6 To an agar solution in water formed by adding agar to pure water at a weight ratio of 0.5% was mixed a hydroxyapatite powder at a weight ratio of 30% based on the agar solution in water, and ammonium polyacylate was added as a dispersant at a weight ratio of 5% based on the hydroxyapatite powder. They were mixed in a ball mill for 10 hours or more to prepare a slurry containing hydroxyapatite.
    Then, without forming the oil droplet particles as shown in Example 7, the isoparafene and a surfactant (sorbitan sesquioleate: at a weight ratio of 4% to the isoparaffin) were charged into a beaker and stirred while heating using a mixer. In the stirred state, the slurry prepared as described above was added to the beaker over and over again. By stirring, liquid droplets were formed in the beaker comprising a slurry in which the oil droplet particles were not trapped. 10 15 20 25 30 535 'HB 28 The treatments so far have been carried out under a state while maintaining the temperature at 40 ° C or higher so that agar such as the binder was not solidified.
    Thereafter, the beaker was cooled and gelling liquid droplets formed as described above. Then the gelled drops were recovered and, after solvent washing with ethanol, vacuum dried under reduced pressure and subjected to a firing treatment at 700 ° C.
    The obtained ceramic particles were classified in the average particle size of 80 μm, 60 μm and 40 μm as samples of Comparative Examples 4, 5 and 6.
    Then, for the samples prepared in Example 7 and Comparative Examples 4 to 6, a protein separation property test was performed.
    Protein Separation Property Test The protein separation property test was performed using a high resolution liquid chromatograph (Lachorrn L-7000, manufactured by Hitachi Ltd.). an eluate, a protein sample, an empty column, a filler slurry, and test conditions are as described below.
    For the eluate, 1 mM sodium phosphate buffer and 400 mM sodium phosphate buffer were used. Each of the eluates was adjusted to pH 6.8. For the protein sample, albumin ribosome, cytochrome C were used and protein sample solutions each containing 0.03 mM protein were used. As the solvent for the protein sample solution, 1 mM sodium phosphate buffer was used. As the empty column, a 2 mm ø> <150 mm column made of stainless steel was used. For the filler slurry, those prepared were used by diluting 0.3 g of each of different fillers with 400 mM sodium phosphate buffer at a particle concentration of 10% by weight. The filler slurry was filled into the column by arranging an empty column with a packer at a high resolution liquid chromatograph and a filler slurry was loaded therein. At a flow rate of 2 ml / min to pack the column, 1 mM sodium phosphate buffer was brought to flow.
    For the evaluation of the protein separation property, the eluate was caused to fl at a flow rate of 1 ml / min. After digestion of 1 mM sodium phosphate buffer as an eluate for 5 minutes, it changed linearly from 1 mM to 200.5 mM (1 mM (50%) + 400 mM (50%)) for 15 minutes.
    Fig. 8 shows the result of evaluation with respect to the separation property in Example 7, while Figs. 9 to Fig. 11 show the result of the evaluation with respect to the separation property in each of the respective Comparative Examples.
    Looking at the results from Comparative Example 4 to Comparative Example 6 (Fig. 9 to Fig. 11), it appears that the protein separation property is more excellent as the particle size is smaller. In other words, it can be seen that peaks for albumin 21 and ribosome 22 separate more as the particle size is smaller. This is considered to increase the specific surface area due to the decrease in particle size and the contact area with the eluate was increased. In Comparative Example 4 for the average particle size of 80 μm (Fig. 9), it can be confirmed that albumin 21 and lisotime 22 were not separated.
    On the contrary, it can be confirmed in Example 7 (Fig. 8) that peaks for albumin 21 and lisotime 22 are conspicuously separated although the average particle size is identical to that in Comparative Example 4. Fig. 12 shows a SEM photography of ceramic particles prepared in Example 7 prior to classification into an average particle size of 80 μm.
    As shown in Fig. 12, it can be confirmed in the ceramic particles prepared in Example 7 that a plurality of open pores having an average pore size of 1 μm or more and 30 μm or less and having the pore diameter of the aperture portion and the connecting portion of 500 nm or more and 20 μm or less are formed by the outer surface to the inside thereof. In other words, it is estimated that the result of the test for the protein separation property depends on a simple number of open pores formed in the ceramic particle. In the ceramic particles of Comparative Examples 4 to 6, a sufficient number of open pores as confirmed for Example 1 was not confirmed. / g.
    Comparative Example 7 Ceramic particles were produced in the same procedure as in Example 7 except that the formation of smaller oil droplet particles than those of Example 7 was formed by controlling the amount of isoparaffin used and the intensity of the mixer in forming the oil droplet particles.
    When the protein separation property test was performed in the same manner as in Example 7 for the sample made by Comparative Example 7, the protein separation property was confirmed at a degree identical to that of Comparative Example 5. When the open pore of the ceramic particle was evaluated in this case, the pore size was the opening portion and the connecting portion, respectively, of the open pores 200 nm or less, and ceramic particles having the pore size of the opening portion and the connecting portion exceeding 300 nm were not confirmed. 10 8 20 25 30 535 'HB 31 Example 8 Ceramic particles were made by the same procedure as in Example 7 except for the formation of larger oil droplet particles than those in Example 7 by controlling the amount of isoparaffin used and the intensity of the mixer in forming the oil droplet particles and controlling the intensity of the mixer in forming the liquid droplets to obtain the larger particle size of the ceramic particles than that of Example 7. Thereafter, the obtained ceramic particles were classified into an average particle size of 200 .mu.m as a sample for Example 8.
    When the protein separation property test was performed on the sample prepared in Example 8 by the same procedure as in Example 7, the protein separation property was confirmed to a degree identical to that of Example 1.
    When the open pore of the ceramic particles was evaluated in this case, a plurality of open pores having an average pore size of 25 μm or more and 50 μm or less and with the pore size of the opening portion and the connecting portion of 10 μm or more and 20 μm or less were confirmed.
    Comparative Example 8 Ceramic particles were produced in the same procedure as in Example 8 except that the formation of further larger oil droplet particles than those of Example 8 was formed by controlling the amount of isoparaffin used and the intensity of the mixer in forming the oil droplet particles.
    When the obtained ceramic particles were confirmed by SEM photography, the particle size of the obtained ceramic particles was extremely small compared to those of Example 8. The ceramic particle was tipped or cracked in some places, and many particles that were broken in themselves were confirmed. When the open pores of the broken ceramic particles were evaluated, many particles with the pore size of the opening portion and the connecting portion of the open pores were confirmed to be more than 20 microns.
    Example 9 Ceramic particles were produced by the same procedure as in Example 7 except for using an alumina powder instead of the hydroxylapatite powder.
    As a result, in the same manner as in Example 7, ceramic particles having a sufficient number of open pores having an average pore size of 500 nm or more and 40 μm or less and a pore size of the opening portion and the connecting portion of 300 nm or more and 10 μm could or less from the outer surface to the inside thereof as shown in Fig. 12 is obtained.
    Example 10 Ceramic particles were produced by the same procedure as in Example 7 except for using a silica powder instead of the hydroxylapatite powder.
    As a result, as in Example 7, ceramic particles having a plurality of open pores having an average pore size of 500 nm or more and 40 μm or less and a pore size for the aperture portion and the connecting portion of 300 nm or more and 10 μm or less from the outer surface of the inside thereof as shown in Fig. 12 is obtained.
    Example 1 1 Ceramic particles were produced by the same procedure as in Example 7 except using a mullite powder instead of the hydroxylapatite powder. As a result, in the same manner as in Example 7, ceramic particles having a plurality of open pores having an average pore size of 500 nm or more and 40 μm or less and a pore size for the opening portion and the connecting portion of 300 nm or more and 10 μm or less from the outer surface to the inside thereof as shown in Fig. 12 are obtained.
    Example 1 Ceramic particles were manufactured by the same procedure as in Example 7 except for using a zirconia powder instead of the hydroxylapatite powder.
    As a result, in the same manner as in Example 7, ceramic particles having a simple number of open pores having an average pore size of 500 nm or more and 40 μm or less and a pore size for the opening portion and the connecting portion of 300 nm or more and 10 μm could or less from the outer surface to the inside thereof as shown in Fig. 12 is obtained.
    Example 13 Ceramic particles were produced by the same procedure as in Example 7 except for using a silicon carbide powder instead of the hydroxylapatite powder.
    As a result, as in Example 7, ceramic particles having a plurality of open pores having an average pore size of 500 nm or more and 40 μm or less and a pore size of the aperture and connecting portion of 300 nm or more and 10 μm or less from the outer surface to the inside thereof as shown in Fig. 12 is obtained. 10 14 20 25 30 535 'HB 34 Example 14 Ceramic particles were produced by the same procedure as in Example 7 except for using an alumina powder, a silica powder, a mullite powder, a zirconia powder, and a silicon carbide powder, respectively, which formed larger oil droplet particles through them in Example 7. to control the amount of use of the isoparaffin and the intensity of the mixer in forming the oil droplet particles and to control the intensity of the mixer in forming the liquid droplet to obtain a larger particle size of the ceramic particles than that of Example 7. Then the respective obtained particles were classified average particle size of 200 μm as a sample for Example 14.
    When the open pores of the obtained ceramic particles for each of the powders were evaluated, a sufficient number of open pores having the average pore size of 25 μm or more and 50 μm or less and the pore size of the opening portion and the connecting portion of 10 μm or more and 20 were confirmed. pm or less from the outer surface to the inside thereof for all the ceramic particles.
    The ceramic particles of Example 1 to Example 14 prepared as described above can be suitably used, for example, for catalyst supports.
    The present invention is not limited to the embodiments described above and may be practiced with various modifications within a range which is included within the scope of the present invention.
    This patent application is based on Japanese Patent Application No. 2008- 188675 filed July 22, 2008, Japanese Patent Application No. 2008-251238 filed September 29, 2008, Japanese Patent Application No. 2008-275836 535 'HB 35 filed October 27, 2008 and the Japanese Patent Application No. 2009-144502 filed June 17, 2009 and the contents thereof are incorporated herein by reference.
    权利要求:
    Claims (13)
    [1] 1. A ceramic particle: having an average particle diameter of 5 um or moreand 5 mm or less and a plurality of open pores formed atthe outer surface; and having two pore size distributions in the measurement by a mercury porosimeter.
    [2] 2. The ceramic particle according to claim 1, whereinthe two pore size distributions include a first pore sizedistribution having a peak within a range from 300 nm ormore and 20 um or less and a second pore size distribution having a peak within a range of 200 nm or less.
    [3] 3. A ceramic particle in which a plural number ofopen pores are formed at the outer surface, wherein the average pore size of the open pores is 500 nm ormore and 50 um or less; the pore size for the opening part of the open poreon the side of the outer surface is 300 nm or more and 20um or less; and a skeleton part which forms the open pores comprises a porous body.
    [4] 4. A ceramic particle in which a plural number of open pores are formed at the outer surface, wherein the open pore has a surface open pore formed at theouter surface with an average pore size of 500 nm or moreand 50 um or less and a internal open pore formed incommunication with the inner wall surface of the surfaceopen pore with an average pore size of 500 nm or more and50 um or less; the pore size for the opening part of the surfaceopen pore on the side of the outer surface and the poresize for the communication part between the surface openpore and the internal open pore is 300 nm or more and 20 umor less; and the skeleton part which forms the open pores comprises a porous body.
    [5] 5. The ceramic particle according to claim 3, whereinthe open. pore is formed. in communication fronl one outer surface to the other outer surface of the ceramic particle.
    [6] 6. The ceramic particle according to claim 4, whereinthe open. pore is formed, in communication fronx one outer surface to the other outer surface of the ceramic particle.
    [7] 7. A ceramic particle according to clain1 l, whichcomprises any one of inorganic oxides, silicon carbides, boron carbides, and silicon nitrides. 46
    [8] 8. A ceramic particle according to claim. 2, whichcomprises any one of inorganic oxides, silicon carbides, boron carbides, and silicon nitrides.
    [9] 9. A ceramic particle according to claim. 3, whichcomprises any one of inorganic oxides, silicon carbides, boron carbides, and Silicon nitrides.
    [10] 10. lå ceramic particle according tu) claim 4, whichcomprises any one of inorganic oxides, silicon carbides, boron carbides, and silicon nitrides.
    [11] 11. ll. A ceramic particle according to claim 5, whichcomprises any one of inorganic oxides, silicon carbides, boron carbides, and silicon nitrides.
    [12] 12. ZX ceramic particle according txn clainx 6, whichcomprises any one of inorganic oxides, Silicon carbides, boron carbides, and silicon nitrides.
    [13] 13. A method for producing a ceramic particleincluding a step of: adding a first oil and a hydrophilic surfactant to aslurry (W) containing a ceramic powder, a binder, a dispersant, and pure water and 47 providing shear stress to the first oil to form anoil droplet particle (O) comprising the first oil in orderto prepare an O/W emulsion in which the oil dropletparticles (O) are dispersed in the slurry (W); a step of: adding the O/W emulsion to a second oil (O)containing an oleophilic surfactant and providing shear stress to the O/W emulsion to form afine liquid droplet (O/W) comprising a slurry in which theoil droplet particles (O) are confined in the insidethereof in order to prepare an O/W/O emulsion in which thefine liquid droplets (O/W) are dispersed in the second oil(O); and a step of baking the fine liquid droplet (O/W). 48
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    同族专利:
    公开号 | 公开日
    SE0950563A|2010-01-23|
    SE0950563L|2010-01-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2014-03-04| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2008188675|2008-07-22|
    JP2008251238|2008-09-29|
    JP2008275836A|JP2010100502A|2008-10-27|2008-10-27|Ceramic particle|
    JP2009144502A|JP2010100514A|2008-07-22|2009-06-17|Ceramic particle and method of manufacturing the same|
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