KR101923257B1 - Method for preparing beta-tricalcium phosphate bone chip with a composition uniformity and bone chip therefrom - Google Patents
Method for preparing beta-tricalcium phosphate bone chip with a composition uniformity and bone chip therefrom Download PDFInfo
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- KR101923257B1 KR101923257B1 KR1020150060193A KR20150060193A KR101923257B1 KR 101923257 B1 KR101923257 B1 KR 101923257B1 KR 1020150060193 A KR1020150060193 A KR 1020150060193A KR 20150060193 A KR20150060193 A KR 20150060193A KR 101923257 B1 KR101923257 B1 KR 101923257B1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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Abstract
The present invention relates to a method for manufacturing a beta-phase tricalcium phosphate-based bone chip for tissue restoration, which can be improved in strength by using a double shielding technique, can be manufactured in various forms, and ultimately can be improved in productivity of a chip having a uniform composition ≪ / RTI >
Description
More particularly, the present invention relates to a method for producing a beta phase tricalcium phosphate based homogeneous phase, and more particularly, to a method for producing a triphasic triphosphate based homogeneous phase using a double shielding method during sintering, Based tricalcium phosphate-based biodegradable chip, which can be manufactured in various forms and can ultimately improve the productivity of the chip having a homogeneous composition.
Currently, bone grafting can restore bone grafts in various skeletal environments, such as bone grafts that are inherently larger in size, or they can be self- or allografted to bridge the bone loss associated with serious trauma, Or in the case of having an abnormal skeleton at the time of acquisition. The need for such bone grafts has been increasing, and research has been actively conducted on bone grafts for therapeutic purposes.
Such a bone graft implies that an osteocyte can attach well to reproduce the same tissue as that of the original bone tissue and can make an environment capable of proliferation and fragmentation. Such a bone graft is usually called a support, Or a bone chip having a size smaller than or equal to a certain size. Clinically, it is used in a way to fill the chip with the lost bone tissue.
The chip may be generally made of calcium phosphate-based compound ceramics, a bioglass-based material, or a biodegradable polymer. The chip may be in the form of a simple granule or a specific shape.
Korean Patent No. 1280891, which is a prior art example of such a chip, comprises a step of melting a polymer composition containing a biodegradable polymer; A step of raising the temperature of a metal mold having a fine pattern for manufacturing a bone structure regeneration microstructure chip; Injecting the molten polymer composition into the heated mold; Cooling the mold; And a step of separating a bone chip for bone tissue regeneration from the mold from the mold, and a chip for bone tissue regeneration produced by the method. However, this chip according to the prior art has low strength and has difficulty to be manufactured in various forms.
The present inventors have conducted intensive researches on a method for improving the strength of a bone chip for bone repair, improving the uniformity of the composition, and manufacturing a chip for tissue repair in various forms. It came.
Therefore, it is an object of the present invention to provide a method of manufacturing a chip having a uniform color and uniform composition at the time of sintering, Beta-tri-calcium phosphate-based chip.
In order to achieve the above object, a first aspect of the present invention provides a method for producing a triacetoxy phosphate powder, comprising the steps of: calcining a beta phase tricalcium phosphate powder; Mixing the beta-tricalcium phosphate powder and sodium; Molding the mixture to produce a molded body; And sintering the molded body, wherein the step of sintering the molded body uses a double shield to maintain the internal oxygen partial pressure and the content constant. .
In one embodiment of the present invention, the beta-phase tricalcium phosphate powder is preferably calcined at 600 to 900 ° C.
In one embodiment of the present invention, it is preferable that the calcined beta-tricalcium phosphate powder and sodium are mixed by a ball mill method.
In one embodiment of the present invention, it is preferable that the mixture is mixed with ethylcellulose and then molded to produce a molded article.
A second embodiment of the present invention is directed to a method for preparing a pharmaceutical composition comprising mixing beta-phase tricalcium phosphate powder and sodium; Uniaxially pressing the mixture to produce a molded body; And sintering the shaped body at a temperature of 300 to 1230 캜; Wherein the step of sintering the shaped body is performed by using a double shield to block gas penetration, thereby maintaining the oxygen partial pressure and the content in the electric furnace at a constant level.
In one embodiment of the present invention, it is preferable to mix the beta-tricalcium phosphate powder and sodium by a ball mill method.
In the first and second embodiments of the present invention, the step of sintering the molded body is carried out at a temperature of about 100 to 500 ° C, preferably 300 ° C for 2 to 4 hours, at a temperature of 600 to 900 ° C, For 2 to 4 hours and maintained at 1000 to 1300 ° C, preferably 1230 ° C for 15 hours.
In the first and second embodiments of the present invention, it is preferable to use a high purity alumina ceramic boat for the double shield. The size of the alumina ceramic boat is not particularly limited and is proportional to the size of the electric furnace. The composition is preferably high purity alumina containing 99.7% or more of Al 2 O 3 .
In the first and second embodiments of the present invention, it is preferable that the oxygen partial pressure on the surface of the molded body is 0.19 to 0.23 based on the atmospheric pressure by the double shield.
In the first and second embodiments of the present invention, the porosity and pore size of the sintered body can be controlled by adjusting the size of sodium mixed with the beta-tricalcium phosphate powder.
In addition, the present invention provides a chip for bone tissue recovery according to the present invention.
The method of producing beta-phase tricalcium phosphate based bone chips for bone tissue repair according to the present invention minimizes the temperature change during sintering by using the double shielding technique in the sintering process and reduces sintering temperature and oxygen partial pressure The balance of the oxygen outflow and the inflow from the beta phase tricalcium phosphate shaped body can be balanced to produce a chip having a uniform composition. Therefore, it is possible to improve strength of the chip for tissue regeneration after sintering process and to manufacture in various forms, and to change the color uniformly during gamma sterilization The productivity of the present chip can be improved.
1 is a schematic process diagram of a method of manufacturing the chip according to the present invention.
2 is a photograph of the chip manufactured in Example 1 of the present invention.
3 is a photograph of the chip manufactured in Comparative Example 1 of the present invention.
4 is a photograph of planes (a) and (b) of the chip manufactured in Example 2 of the present invention.
Hereinafter, the present invention will be described in detail.
Unless defined otherwise, all technical terms used in the present invention have the following definitions and are consistent with the meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Also, preferred methods or samples are described in this specification, but similar or equivalent ones are also included in the scope of the present invention. The contents of all publications referred to herein are incorporated herein by reference.
The term "about" is used herein to refer to a reference quantity, a level, a value, a number, a frequency, a percent, a dimension, a size, a quantity, a weight, or a length of 30, 25, 20, 25, 10, 9, 8, 7, Level, value, number, frequency, percent, dimension, size, quantity, weight or length of a variable, such as 4, 3, 2 or 1%.
Throughout this specification, the words "comprises" and "comprising ", unless the context requires otherwise, include the steps or components, or groups of steps or elements, Steps, or groups of elements are not excluded.
The present chip according to the present invention is a sintered body of beta-tricalcium phosphate. The β-Tricalcium phosphate powder is a bio-ceramic which is widely used as a bone graft material together with hydroxyapatite powder. It is a kind of powder. Due to its low solubility in vivo, the hydroxyapatite has a disadvantage in that the bound bone at the interface can not grow into the inside and can not be completely replaced with bone and remains to the end.
On the other hand, beta-phase tricalcium phosphate is similar to apatite hydroxide in that it binds directly to bone, but it is gradually dissolving in vivo and eventually disappears. Beta phase tricalcium phosphate is mainly used as a bone marrow material (bone graft material, bone filler). Beta-tricalcium phosphate for bone marrow is used in dense bulk form and in the form of porous structures or granules connected by open pores. In order to use beta-tricalcium phosphate in the form of granular external fine bulk or porous structure, it is necessary to sinter to have a high relative density because it is necessary to maintain sufficient strength.
However, beta-tricalcium phosphate is difficult to sinter because it has homogeneous beta -phase and alpha -phase. That is, the β phase has a hexagonal crystal phase at a low temperature, and when the β phase is heat-treated at a temperature of 1100 ° C. to 1180 ° C., a phase transition occurs to a high-temperature phase α having a monoclinic system. This high-temperature α-phase reacts violently with water and is therefore unsuitable for use as a living implant. In addition, the phase transition to the? -Phase having a low density on the high density? Causes a fine crack in the sintered body, resulting in a reduction in the strength of the entire material. Beta phase tricalcium phosphate is preferred as an artificial bone material for the above reasons. However, in order to obtain a sintered body of beta-phase tricalcium phosphate or hydroxyapatite and a beta-phase tricalcium phosphate complex, the sintered body should be sintered at a phase transition temperature of 1180 ° C. or less. However, since the relative density is 90% or less at this temperature, it is difficult to obtain a high-density sintered body There is a problem. Therefore, in order to apply beta-tricalcium phosphate, which is excellent in bioabsorbability, as a biomaterial, it is essential to obtain a high-density sintered body.
According to the method for producing a chip according to the first embodiment of the present invention, a powder of beta-phase tricalcium phosphate (hereinafter abbreviated as? -TCP ') is first calcined. As described above, the beta-tricalcium phosphate precursor powder can be calcined to control the color change upon dispersion, strength improvement, and gamma sterilization. The calcination is preferably performed at 600 to 800 ° C for about 1 to 3 hours.
Next, the beta-tricalcium phosphate powder and sodium are mixed.
The calcined beta-tricalcium phosphate powder and sodium are mixed using a ball mill process to prepare a mixture. When ball milling is used, strength is increased by improving dispersibility.
The porosity and pore size of the sintered body can be controlled by adjusting the content and size of sodium.
Next, the mixture is mixed with an organic binder such as ethyl cellulose to prepare a molded article. The formed body can be formed as a single layer or a multilayer, and the manufacturing method is not particularly limited and can be performed by a known pressure molding method.
Finally, the formed body is sintered.
The sintering is carried out using an ordinary electric furnace at a temperature of 300 ° C. to 1,230 ° C. in an air atmosphere. Preferably maintained at 100 to 500 DEG C, more preferably at 300 DEG C for 2 to 4 hours, maintained at 600 to 900 DEG C, more preferably at 600 DEG C for 2 to 4 hours, In the range of 1000 to 1300 캜, preferably 1230 캜 for 15 hours. The reason for performing the stepwise heat treatment is to remove moisture and organic binder at about 300 ° C., to form pores by volatilizing sodium at about 600 ° C., to remove residual organic matter, and then to phase transition to a beta phase through sintering at 1230 ° C. .
In the present invention, gas infiltration into the sintering furnace is prevented through a double shield in the process of sintering the formed body, and the partial pressure and content of oxygen are kept constant, thereby reducing the strength degradation problem and uneven composition problem in the sintering process Can be solved.
Specifically, it is preferable to use a high purity alumina ceramic boat for the double shield. The size of the alumina ceramic boat is not particularly limited and is proportional to the size of the electric furnace. The composition is preferably high purity alumina containing 99% or more, more preferably 99.7% or more Al 2 O 3 .
By adopting this double shielding technique, the external air inflow is constant in the sintering process and cooling process. In order to prepare pure beta-phase tri-calcium phosphate, the temperature change during sintering at 1230 ° C for 15 hours should be minimized. When a double shield is used, the sintering temperature at the surface of the compact is also constant. In a preferred example, the oxygen partial pressure at the surface of the molded article can be kept very constant at about 0.19 to 0.23 at atmospheric pressure.
According to a second aspect of the present invention, a manufacturing method of a chip includes the following steps.
mixing? -TCP powder and sodium;
Uniaxially pressing the mixture to produce a molded body; And
Sintering the shaped body at a temperature of 300 ° C to 1,230 ° C;
As described above, the β-TCP powder and sodium are preferably mixed by a ball mill method.
In the present embodiment, a molded body is produced through uniaxial pressing without using an organic binder such as ethyl cellulose. The molding uses a mold capable of uniaxial pressing, and a commonly used disc mold can be used. In the production of the molded product, when a binder such as ethyl cellulose is used to prepare a gel, and the mixture is dyed and sintered, the strength of the formed chip can be significantly reduced due to a decrease in porosity and dispersibility of the chip . However, during uniaxial pressing, the internal pores can be reduced to improve the strength.
The step of sintering the shaped body at a temperature of 300 ° C. to 1,230 ° C. is also the same as that described in the first embodiment.
The chip of the present invention manufactured according to the above-described method has improved strength compared to the conventional chip, and the color can be changed constantly during gamma sterilization before use to improve productivity. Confirmation of suitability such as crushing / pore generation, sorting / weighing, ultrasonic cleaning and pH measurement is made for the manufactured chip, and sterilized and stored.
Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples. However, the present invention is not limited thereto.
[ Example 1] Manufacturing of the present chip according to the first embodiment
500 g weight% of β-TCP was calcined at 600 ° C. and mixed with 300 g% by weight of sodium having an average particle size (D50) in the range of 1 to 50 μm through a ball mill. The pH of sodium is in the range of 6.7-7.3. The mixture was mixed with 30 g% by weight of ethyl cellulose to prepare a compact. The compact was maintained at 300 ° C. for 3 hours, maintained at 600 ° C. for 3 hours, and sintered at 1230 ° C. for 15 hours to obtain This chip was manufactured. At this time, double shielding was performed using alumina ceramic boat. The manufactured chip was sterilized and then photographed and shown in Fig.
Here, as shown in FIG. 5, an alumina ceramic boat used a boat having a height of about 50 mm and a length of about 100 mm and a length of about 200 mm. The thickness is about 5 mm. The alumina ceramic boat uses high purity alumina containing 99.7% or more Al2O3.
[ Comparative Example One]
The chip was prepared and γ-sterilized in the same manner as in Example 1 except that the β-TCP powder was not calcined in Example 1. The color change after sterilization is shown in Fig.
[ Example 2] Manufacturing of the present chip according to the second embodiment
100 g of β-TCP powder was mixed with 60 g of sodium having an average particle size (D50) in the range of 1-50 μm through a ball mill method. The pH of sodium is in the range of 6.7-7.3. The mixture was placed in a disk-shaped uniaxial pressing mold and molded to obtain a molded article. The formed body was held at 300 캜 for 3 hours, held at 600 캜 for 3 hours, and sintered at 1230 캜 for 15 hours to manufacture the chip according to the present invention. At this time, double shielding was performed using alumina ceramic boat. The manufactured chip was sterilized and then photographed and shown in FIG.
The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (11)
Mixing the calcined beta-tricalcium phosphate powder with sodium having an average particle size of 1 to 50 mu m;
Molding the mixture to produce a molded body; And
Sintering the shaped body at a temperature of 300 ° C to 1,230 ° C; Lt; / RTI >
Wherein the step of sintering the shaped body is performed by using a double shield to block gas penetration and maintain the internal oxygen partial pressure and the content constant.
Wherein the beta-tricalcium phosphate powder is calcined at 600 to 900 ° C.
Wherein the calcined beta-tricalcium phosphate powder and sodium are mixed by a ball mill method.
Wherein the mixture is mixed with ethylcellulose and then molded to produce a molded article.
Uniaxially pressing the mixture to produce a molded body; And
Sintering the shaped body at a temperature of 300 ° C to 1,230 ° C; Lt; / RTI >
Wherein the step of sintering the molded body is performed by using a double shield to block gas penetration and to keep the oxygen partial pressure and the content in the electric furnace constant.
Wherein the beta-phase tricalcium phosphate powder and sodium are mixed by a ball mill method.
Wherein the step of sintering the shaped body is carried out at 300 ° C for 3 hours, maintained at 600 ° C for 3 hours, and maintained at 1230 ° C for 15 hours.
Characterized in that a high purity alumina ceramic boat is used for said double shield.
Wherein the oxygen partial pressure of the surface of the formed body is 0.19 to 0.23 at atmospheric pressure by the double shield.
And adjusting the content and size of sodium to adjust the porosity and pore size of the sintered body.
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| KR1020150060193A KR101923257B1 (en) | 2015-04-29 | 2015-04-29 | Method for preparing beta-tricalcium phosphate bone chip with a composition uniformity and bone chip therefrom |
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| KR1020150060193A KR101923257B1 (en) | 2015-04-29 | 2015-04-29 | Method for preparing beta-tricalcium phosphate bone chip with a composition uniformity and bone chip therefrom |
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| KR20160128585A KR20160128585A (en) | 2016-11-08 |
| KR101923257B1 true KR101923257B1 (en) | 2018-11-28 |
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| KR102448241B1 (en) * | 2020-05-13 | 2022-09-28 | (주)바이오리진 | porous materials of biphasic calcium phosphate having dual structure and manufacturing method thereof and manufacturing method of synthetic bone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001518359A (en) | 1997-10-07 | 2001-10-16 | ドクトル．ハー．ツェー．ロベルト マシーズ スティフツング | Surgical hydraulic cement |
| KR100783587B1 (en) | 2007-01-19 | 2007-12-11 | 인하대학교 산학협력단 | Preparation method of beta-tricalcium phosphate powders and compacts thereof |
| KR101345805B1 (en) | 2012-09-04 | 2014-01-03 | 주식회사 바이오알파 | Injectable, self-hardening and porous calcium phosphate bone graft substitute and additive inducing macro-pores in hardening |
| KR101357673B1 (en) | 2012-09-03 | 2014-02-04 | 한국기계연구원 | The scaffold composition for regeneration of hard tissue having magnesium phosphate, scaffold for regeneration of hard tissue comprising the same and preparation methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101280891B1 (en) | 2009-11-03 | 2013-07-02 | (주)애니캐스팅 | Method of preparation of a bone chip for bone tissue regeneration and a bone chip for bone tissue regeneration made by the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001518359A (en) | 1997-10-07 | 2001-10-16 | ドクトル．ハー．ツェー．ロベルト マシーズ スティフツング | Surgical hydraulic cement |
| KR100783587B1 (en) | 2007-01-19 | 2007-12-11 | 인하대학교 산학협력단 | Preparation method of beta-tricalcium phosphate powders and compacts thereof |
| KR101357673B1 (en) | 2012-09-03 | 2014-02-04 | 한국기계연구원 | The scaffold composition for regeneration of hard tissue having magnesium phosphate, scaffold for regeneration of hard tissue comprising the same and preparation methods thereof |
| KR101345805B1 (en) | 2012-09-04 | 2014-01-03 | 주식회사 바이오알파 | Injectable, self-hardening and porous calcium phosphate bone graft substitute and additive inducing macro-pores in hardening |
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