WO2013122336A1

WO2013122336A1 - Method for preparing tricalcium phosphate using pore forming agent, and tricalcium phosphate prepared thereby

Info

Publication number: WO2013122336A1
Application number: PCT/KR2013/000529
Authority: WO
Inventors: 김승수
Original assignee: 한국화학연구원
Priority date: 2012-02-17
Filing date: 2013-01-23
Publication date: 2013-08-22
Also published as: KR20130095017A; KR101345794B1

Abstract

The present invention relates to a method for preparing tricalcium phosphate using a pore forming agent, and tricalcium phosphate prepared thereby, and more specifically, provides a method for preparing tricalcium phosphate using a pore forming agent, comprising the steps of: (step 1) mixing a source material for tricalcium phosphate and a pore forming agent; (step 2) calcining the mixture mixed in step 1 at 1,200-1,400 ℃; and (step 3) cooling the calcined product calcined in step 2. According to the present invention, the method for preparing tricalcium phosphate using a pore forming agent forms pores in tricalcium phosphate by adding a pore forming agent and allows air to smoothly come in and out through the formed pores, and thus can further improve cooling efficiency.

Description

【Specification】

[Name of invention]

Method for preparing tricalcium phosphate using pore-forming agent and calcium phosphate triphosphate prepared accordingly

Technical Field

The present invention relates to a method for preparing tricalcium phosphate using a pore generating agent and to a tricalcium phosphate prepared according to the present invention. Specifically, the third type calcium phosphate (α- Tricalcium phosphate, α-TCP).

Background Art

<2> Calcium Phosphate Bone Cement is a biomedical device used in orthopedic dentistry and plastic surgery as bone joints, bone fillers, and bone tissue growth promoters. It is a kind of material that can be injected into the affected area using a syringe. Invasive theraphy has recently been widely practiced. Phosphate kalseum golsi ^"Moment when woke clinical wrist and a fracture or bone defect occurs, etc. joint near the skull, spine, such as knees, and used mainly for the purpose of bone layered and bonded, especially in recent years, the spine augmentation in osteoporosis patients Phosphate bone cement is used on the back.

<3> Calcium phosphate bone cement usually contains brusite cement and apatite

(apatite) is classified as cement. Brucite cement has the advantage of fast curing time, but the low mechanical strength and high biodegradation rate make it difficult to use for bone reinforcement. On the other hand, apatite cement has a high mechanical strength and a low biodegradation rate, which is suitable for bone tissue augmentation. In general, however, apatite cements have a problem of slow curing time. Therefore, various methods are used to enhance the curing time as follows: 1) microparticle formation of the semicoating; 2) reducing the liquid phase ratio; 3) use of high solubility semi-aerated water; 4) use of nuclear material; 5) Lower solubility of the final product (M. Bohner, J. Mater. Chem., 17, 3980, (2007)).

<4>

<5> α-type tricalcium phosphate is the only self-curing calcium phosphate which hardens only in calcium phosphate compounds and is used as a raw material for apatite cement. It is greatly influenced by its purity. Synthesis of a type-based tricalcium phosphate is generally prepared by reacting 1 mol of carbonate and 2 mol of dicalcium phosphate anhydrus (dicalcium phosphate anhydrous, DCPA, DCP) ^at a temperature of 1300 ^° C and then cooling it. At this time, in the silver below about 1150 ^° C, β-type triphosphate When the breast is more stable and the product is slowed down, a large amount of α-type tricalcium phosphate is converted into β-type tricalcium phosphate, thereby lowering the production and purity of the α-type calcium triphosphate. The reaction is also lowered.

That is, there is a problem that the purity of the α-type tricalcium phosphate may decrease depending on the angle conditions, but conventionally, cooling at room temperature or the angle conditions are not clearly disclosed (E. Ferni indez, et. al., Journal of Biomedical Materials Research, Vol. 32, 367-374 (1996); Tobias J. Brunner, et.al., J. Mater. Chem., 2007, 17, 40724078; Saint-Jean, et.al. , Journal of Materials Science: Materials in Medicine (2005), 16 (11), 993-1001; M. Bohner, W02009 / 132466).

<7>

<8> A. Bigi et al prepared α-type triphosphate by reacting calcium carbonate with dicalcium phosphate dihydrate (DCPD), but the purity of α-type triphosphate according to cooling conditions It is not mentioned at all (Biomaterials 23 (2002) 1849). In addition, U.S. Patent Publication No. 2003-465595 and Kevor S. TenHuisen et al. Reported that calcium nitrate tetrahydrate and a 隱 onium hydrogen phosphate were reacted to form α-type tricalcium phosphate. Although it has been prepared, it does not mention the purity of α-type tricalcium phosphate under different conditions (Kevor S. Ten Huisen and Paul W. Brown, Biomaterials 19 (1998) 2209-2217). Furthermore, Hugo Leonardo Rocha Alves et al prepared the α-type crab triphosphate by reacting calcium carbonate and calcium pyrophosphate. (J Mater Sci: Mater Med (2008) 19: 2241).

Meanwhile, in International Publication No. W096 / 14265 and US Patent No. 5709742, 1 mol of calcium carbonate and 2 mol of dicalcium phosphate anhydrous (DCPA, DCP) were reacted in a crucible at 1300 ^° C. after that, but the nyaenggak to prepare a third calcium phosphate α type ^"using a nyaenggak gas or liquid, the produced α-type to destroy the triphosphate calcium mechanically the production of α-type third calcium phosphate by improving the cooling speed Increasing methods have been disclosed.

However, when preparing α-type tricalcium phosphate as described above, there are the following problems:

<ιι> 1) In case of cooling by using nitrogen gas as cold gas, if the gas velocity is increased to make the angle faster, the manufactured calcium phosphate powder There is a problem that is scattered.

2) In case of mechanical destruction to improve the angle of rotation of the α-type tricalcium phosphate produced, it is necessary to separate the a-type tricalcium phosphate from the crucible used, but since the crucible is very hot over 1000 V There is a problem that is difficult to work, and also the operation of breaking high temperature α-type tricalcium phosphate is also very dangerous and inconvenient.

3) When water is used as a cold liquid, α-type tricalcium phosphate is converted into a hydroxide hydroxide when it comes into contact with water. When using other organic solvents, α-type tricalcium phosphate with 1000 V or more is used. Contact may cause a fire. In addition, while chlorine solvents are not a fire hazard, they are highly toxic and dangerous to use. When cooling with liquid nitrogen, α-calcium phosphate (alpha) of 1000 ^° C or higher comes into contact with liquid nitrogen. Liquid nitrogen boils and drops come up, so workers have a dangerous problem.

<14>

On the other hand, when calcium carbonate and dibasic calcium phosphate dihydrate are used as raw materials for the production of tricalcium phosphate, 4 moles of water (¾0) is generated in the reaction, and the resulting water is vaporized. Pores are formed. On the other hand, when calcium carbonate and dicalcium phosphate anhydride are used as raw materials, one mole of water (0) is generated in the reaction and relatively few pores are formed. In order to compensate for this, there is a method of preparing tricalcium phosphate by further adding water to the raw material, but there is a problem of poor production efficiency due to the large amount of vaporized material (water) to be vaporized.

<16>

In the meantime, the present inventors are working to develop a method for safely and efficiently producing high purity α-type tricalcium phosphate, and forming pores in the triphosphate by adding a pore generating agent, By using dry ice as a solvent, α-type tricalcium phosphate was rapidly engraved without phase change to develop a manufacturing method capable of safely producing high-purity α-type tricalcium phosphate and completed the present invention.

[Detailed Description of the Invention; 1

[Technical problem]

It is an object of the present invention to provide a method for preparing tricalcium phosphate using a pore-generating agent and tricalcium phosphate prepared accordingly.

[Technical Solution] In order to achieve the above object, the present invention

<20> a step of mixing a raw material of tricalcium phosphate and a pore forming agent (step 1);

<2i> calcination to the temperature of 1200 to 1400 ^° C. mixed in step ^ 1 (step 2); And

Provided is a method for preparing tricalcium phosphate using a pore-generating agent comprising the step (step 3) of calcining the calcined body calcined in step 2 above.

<23>

In another aspect, the present invention provides tricalcium phosphate prepared by the above method.

Advantageous Effects

In the method for preparing tricalcium phosphate using the pore generating agent according to the present invention, the pores are added to the tricalcium phosphate by adding a pore generating agent, and air can be smoothly introduced and exited through the formed pores. The efficiency can be further improved. In addition, when fast cooling is carried out using dry ice as a refrigerant, high purity α-type tricalcium phosphate can be safely manufactured, and the prepared tricalcium phosphate has excellent semi-permanence, and thus a bone cement composition including the same. Has the effect of exhibiting the Faron curing time.

[Brief Description of Drawings]

Figure 1 is a photograph of the third phosphate prepared in Example 1 according to the present invention observed with a scanning electron microscope;

Figure 2 is a photograph of the third phosphate prepared in Example 3 according to the present invention observed with a scanning electron microscope;

Figure 3 is a photograph of the third phosphate prepared in Example 4 according to the present invention observed with a scanning electron microscope;

4 is a photograph of a third calcium phosphate prepared in Example 6 according to the present invention observed with a scanning electron microscope;

5 is a photograph of a third calcium phosphate prepared in Example 7 according to the present invention observed with a scanning electron microscope;

6 is a photograph of observing the tricalcium phosphate prepared in Comparative Example 1 with a scanning electron microscope;

7 is a photograph of a crab triphosphate prepared in Comparative Example 2 observed with a scanning electron microscope.

[Best form for implementation of the invention] <33> The present invention

Step (1) of mixing a raw material of a tricalcium phosphate and a pore forming agent;

Calcination of the mixture mixed in step 1 to a temperature of 1200 to 1400 ^° C. (step 2); And

<37>

Hereinafter, the method for preparing tricalcium phosphate according to the present invention will be described in detail for each step.

<39>

In the method for preparing tricalcium phosphate according to the present invention, step 1 is a step of mixing a raw material of the tricalcium phosphate and a pore forming agent.

<4i> 3 as a starting material for the preparation of calcium phosphate are the acid kalseum (CaC0 ₃₎ and the use of dibasic calcium phosphate hydrates, and or acid kalseum (CaC0 ₃₎ and a second phosphate kalseum anhydrous (CaHP0 ₄₎ The carbon carbonate (CaC0 ₃ ) and the calcium pyrophosphate (Ca ₂ 0 ₇ P ₂ ) can also be used as raw materials.

As a raw material, a plurality of pores can be formed in the tricalcium phosphate prepared by using dicalcium phosphate hydrate, dicalcium phosphate anhydride or calcium pyrophosphate together with calcium carbonate as described above. . This means that as the raw materials react at a high temperature, moisture (0) is generated, and as the generated moisture is vaporized, pores are formed in which the water escapes.

In this case, in step 1, a pore forming agent is mixed with the raw material and more pores are formed in the third phosphate prepared through this. The pores formed by the pore-generating agent further improves the cooling efficiency when the tricalcium phosphate is removed, thereby improving the production efficiency of the tricalcium phosphate.

The pore generating agent is not particularly limited as long as it is an organic substance vaporized or burned at a high temperature. However, since the raw material begins to react at around 800 ^° C., the pore generating material is mostly burned at a temperature of 800 ^° C. or less. It is preferable that it is a substance which does not affect. In addition, the low toxicity of the combustion material of the pore generating material is preferred. - Accordingly, the pore-generating agent may be polylactic acid or polyglycolic acid.

(polyglycolic acid), polyhydroxyalkanoate, polyester, nylon, acrylic resin, polyvinyl alcohol, polyurethane, polyglycol, naphthalene Cellulose, alginic acid, carrageenan, starch, carbohydrates, sugar, etc. may be used. They are mostly burned and removed at temperatures below 800 ^° C, and have the advantage of generating little toxic substances during combustion.

In step 1, the addition amount of the pore generating material is not particularly limited, but if an excessive amount is used, the volume of the pore generating material to be combusted may be large and the production efficiency may be lowered. Therefore, preferably it is preferably mixed at a ratio of 20 to 500% by volume relative to the volume of the tricalcium phosphate raw material, and more preferably at a ratio of 50 to 200% by volume. If the amount of the pore-generating agent is less than 20% by volume, open pores are not generated, and thus, the corner air does not penetrate well into the third phosphate. In addition, when the addition amount of the pore-generating agent exceeds 500 volume ¾, while the pores are formed smoothly, there is a problem that the production efficiency is lowered because there are too many materials to burn.

<47>

On the other hand, in performing the mixing of the raw materials, the calcium carbonate and the dicalcium phosphate hydrate, or the calcium carbonate and the dicalcium phosphate anhydride, or the calcium carbonate and the pyramid pyrophosphate are 1: 1 to 2 It is preferable to mix in molar ratio, and it can determine within the said range according to the chemical equivalence ratio of the chemical reaction in which tricalcium phosphate is formed. If the mixing is performed at a molar ratio outside the above range, there is a problem in that a compound other than the tertiary phosphate is formed when the mixing is performed at a ratio less than.

<4>

The mixing of the step 1 is preferably carried out through the homogenous mixing of the raw materials and the ball milling which can be micronized, but is not limited thereto, and a mixing method capable of homogeneously mixing the raw materials is provided. It can be carried out by appropriate selection.

<51>

In the method for preparing tricalcium phosphate according to the present invention, step 2 is a step of calcining the mixture mixed in step 1 to a temperature of 1200 to 1400 ^° C.

Calcium triphosphate can be prepared by reacting the raw materials through the calcination of step 2, and reacting to tricalcium phosphate when using bibasic calcium phosphate anhydride as the raw material. Is shown in Scheme 1 below.

2CaHP0 ₄ + CaCO _s ¹³⁰⁰ ° ^O »Ca ₃ (P0 ₄ ) ₂ + C0 ₂ + H ₂ 0 As shown in the above formula 1, when using dibasic calcium phosphate anhydride and calcium carbonate as raw materials, Reaction forms a tricalcium phosphate, which simultaneously produces one mole of carbon dioxide and one mole of water (¾0). One mole of water is vaporized, and the site where the water is present is formed by pores. In addition, when dibasic calcium phosphate dihydrate is used as a semi-acupuncture as a raw material, 1 mole of carbon dioxide and 4 moles of water are generated and vaporized, and 1 mole of tricalcium phosphate is produced as shown in the following semi-excited formula 2. .

<Scheme 2>^'

1300 ° C

2CaHP0 ₄ 2H ₂ 0 + CaC0 ₃ ^ Ca ₃ (P0 ₄ ) ₂ + C0 ₂ + 4H ₂ 0 Furthermore, when calcium carbonate and calcium pyrophosphate are used as a reaction product, 1 mole is used as in Scheme 3 below. Tricalcium phosphate of is produced.

CaC0 ₃ + Ca ₂ P ₂ 0 ₇ ¹ Ca ₃ (P0 ₄ ) ₂ + C0 ₂

That is, in the case of using the dicalcium phosphate dihydrate as a raw material, more pores may be formed in the prepared calcium triphosphate as 4 moles of water is vaporized and removed. As the third phosphate prepared as described above contains many pores, cold air can easily enter the third phosphate when the third calcium phosphate is encapsulated, thereby allowing the cooling to be performed more smoothly. On the other hand, in the case of using dicalcium phosphate anhydride as a raw material, relatively small pores are formed as one mole of water is formed and vaporized, and when using calcium pyrophosphate as a raw material, It is not easy to form pores because no water is formed.

However, as the pore-generating agent mixed with the raw material is burned and removed in step 1, the site where the pore-generating agent was present is formed as pores, and crab diphosphate anhydride or chamomile pyrophosphate is used as the raw material. Even if used, it is possible to form pores in the third phosphate produced. As the pores formed as described above, the outside air flows smoothly during the next engraving process to improve cooling efficiency, thereby improving production efficiency.

<73>

In the step 2, the calcination is preferably carried out in silver to 1200 to 1400 ^° C ᅳ because the β-type triphosphate is more stable at a temperature below 1150 ° C, α type In order to improve the purity of the third phosphate, it is preferable to perform the calcination of step 2 at a temperature of 1200 to 1400 ^° C. If the calcination of step 2 is carried out at a temperature of less than 1200 ^° C, there is a problem that a lot of β-type tricalcium phosphate is formed, and when the calcination is performed at a temperature exceeding 1400 ^° C of unnecessary level There is a problem that a time and economic loss for heating to a high temperature occurs.

In addition, the calcination of step 2 is preferably performed for 6 to 10 hours. When the calcination is performed for less than 6 hours, the reaction to calcium triphosphate may not be completely performed, and when the calcination is performed for more than 10 hours, there is a problem that a loss of process time occurs.

<76>

<77>

In the method for preparing tricalcium phosphate according to the present invention, step 3 is a step of focusing the calcined body calcined in step 2 above.

Incidental tricalcium phosphate formed through the calcination of step 2 is a very important process element to maintain the purity of the α-type tricalcium phosphate. That is, since β-type tricalcium phosphate is more stable at a temperature of 1150 or less, a large amount of β-type tricalcium phosphate may be formed when tri-calcium phosphate formed through calcination. Therefore, in step 3 according to the present invention, the third calcium phosphate formed through the calcination of step 2 is detected, and in particular, the calcined body calcined in step 2 using dry ice is fed. Cooling to minimize the formation of β-type tricalcium phosphate to produce tricalcium phosphate showing high purity of α-type tricalcium phosphate.

<80>

On the other hand, as described above, the angle of incidence in the prior art refers to simply cooling to room temperature, there is no mention of the feeding means. In addition, as disclosed in International Publication No. WO 96/14265 and U.S. Patent No. 5709742, using a gas or a liquid, each of the α-type triphosphate is mechanically destroyed to improve the angle of rotation. There are the following problems

<82>

1) the problem of powders being scattered by the gas when cold using nitrogen gas;

2) the problem of separating the high temperature crucible and breaking the high temperature _α- type tricalcium phosphate is very dangerous when mechanically broken to improve the angular velocity;

3) In case of using water, α-type crab calcium phosphate is changed into a hydroxide hydroxide in contact with water, and in case of using other organic solvents, there is a risk of fire, and chlorine solvents are toxic. dangerous to increase use issues, and the use of liquid ^nitrogen. When cooling is performed, liquid nitrogen boils and pops up the room as α-type tricalcium phosphate of 1000 ^° C or more comes into contact with liquid nitrogen, which poses a dangerous problem for workers.

<86>

On the other hand, in step 3 according to the present invention, by performing the engraving using dry ice, it is possible to quench the crater triphosphate formed through the calcination of the step 2 to the high purity α-type triphosphate Can be manufactured and can prevent any safety problems. .

At this time, the angle of the step 3 according to the present invention can be performed at a cooling rate of 50 to 200 ^° C / min using dry ice, through which it is possible to produce a high purity α-type calcium triphosphate have. When the ^angle of incidence of step 3 is performed at an ^angle of incidence of less than 50 ^° C / min, β-type tricalcium phosphate may be formed during the angle of incidence, and the angle of incidence of step 3 exceeds 200 ^° C / min. In the case where the excitation speed is performed at an excitation speed, an excessive amount of dry ice is used to increase the process cost.

<89>

In addition, the present invention It provides a third phosphate prepared by the above production method.

<92>

The tricalcium phosphate according to the present invention includes a plurality of pores formed through a pore generating agent, and thus, _a- type tricalcium phosphate (α-Tricalcium phosphate, α-TCP) may be smoothly generated. Can you see it? Since the α-type tricalcium phosphate generates apatite, which is the same substance as bone tissue in vivo, it may exhibit high biocompatibility when applied to bone cement and thus may be used in various medical fields such as implants.

In addition, the crab tricalcium phosphate according to the present invention contains α-type tricalcium phosphate (a—Tricalcium phosphate, α-TCP) 80% or more. This is because the third type phosphate according to the present invention is quenched through the dry ice, thereby preventing the formation of the β-type third phosphate. The α-type tricalcium phosphate has better reaction properties than the β-type triphosphate, and thus exhibits a faster curing rate, and is more preferable to apply to bone cement because it is cured without the use of an acidic substance. That is, it can be seen that the tricalcium phosphate according to the present invention contains α-type triphosphate with high purity and thus is suitable for application to bone cement.

<95>

<%> Furthermore, the present invention

Provided is a bone cement composition comprising the tricalcium phosphate.

<98>

The bone cement composition comprising α-type tricalcium phosphate with high purity and exhibiting high porosity may exhibit excellent biocompatibility and fast curing rate, and thus various medical fields Can be applied to

[Form for live action of invention]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following examples.

<101>

d02> <Example 1> Preparation of the system tricalcium phosphate 1

d03> Step 1: 1 mole (100.09 g) of calcium carbonate (CaC0 ₃ ), dicalcium phosphate dihydrate

The did (CaHP0 ₄ 2H ₂ 0) ₂ mol (344.18 g) and charged to naphthalene 100 g of the ball-milling device with ethanol and was heunhap for 8 hours, followed by drying and then separating a common compound remove ^ethanol.

ΐΙ04> Step 2: The tricalcium phosphate was prepared by placing the mixture in which mixing was performed in Step 1 in a crucible and calcining for 12 hours in an electric furnace at a temperature of 1300 ^° C.

ί106>

step 3: The third calcium phosphate calcined and prepared in step 2 was separated from the crucible, and immediately placed in a container containing an appropriate amount of dry ice, and the top of the container was covered with an appropriate amount of dry ice, and left for 20 minutes. The excursion was performed.

cl08>

Example 2 Preparation of Tricalcium Phosphate 2

ciio> 1 mole (100.09 g) of calcium carbonate (CaC0 ₃ ) in step 1 of Example 1, dicalcium phosphate

Tricalcium phosphate was prepared in the same manner as in Example 1 except that 2 mol (272.12 g) of (CaHP0 ₄ ) and 100 g of naphthalene were mixed with water.

<111>

di.2> Example 3 Preparation of Tricalcium Phosphate 3

cii3> In step 1 of Example 1, 1 mol (100.09 g) of calcium carbonate (CaC0 ₃ ), 1 mol (254 g) of calcium pyrophosphate (CP ₂ 0 ₇ ), and 70 g of cellulose powder were common. Except for the combined, it was carried out in the same manner as in Example 1 to prepare a crab calcium phosphate.

ί114>

cii5> Example 4 Preparation of Tricalcium Phosphate 4

1 mole (100.09 g) of calcium carbonate (CaC0 ₃ ) in step 1 of Example 1, dicalcium phosphate

A tertiary phosphate was prepared in the same manner as in Example 1, except that 2 mol (272.12 g) of (CaHP0 ₄ ) and 100 g of polyvinyl alcohol beads were mixed.

: 117>

118> <Example 5> Triphosphate box production 5

: 1 mol (100.09 g) of calcium carbonate (CaC0 ₃ ) in step 1 of Example 1, dibasic calcium phosphate

Tricalcium phosphate was prepared in the same manner as in Example 1 except that 2 mol (272.12 g) of (CaHP0 ₄ ) and 100 g of polylactic acid beads were mixed.

: 120>

Example 6 Preparation of Tricalcium Phosphate 6 ci22> except that the sum of the calcium carbonate (CaC0 ₃₎ phosphate with 1 mol (100.09 g), calcium pie (C¾P ₂ 0 ₇₎ 1 mole (254 g) and starch beads 100 g in step 1 of Example 1 common Was prepared in the same manner as in Example 1 to prepare a tricalcium phosphate.

cl23>

<Example 7> Preparation of Tricalcium Phosphate 7

In step 1 of Example 1, 1 mol (100.09 g) of calcium carbonate (CaC0 ₃ ), 1 mol (254 g) of calcium pyrophosphate (Ca ₂ P ₂ 0 ₇ ), and 150 g of alginic acid beads were mixed. Except that was carried out in the same manner as in Example 1 to prepare a third phosphate.

ί126>

<127> <Comparative Example 1>

ci28> In Step 1 of the Example 1 acid kalseum (CaC0 ₃₎ 1 mole (100.09 g) and a second phosphate knife thoracic (CaHP0 ₄₎ 2 moles (272.12 g) is put into a ball mill together with ethanol 8 hours common combined And, d29> The third calcium phosphate was prepared in the same manner as in Example 1, except that in step 3 of Example 1, using a fan at room temperature without using dry ice.

<130>

ί131> <Comparative Example 2>

In step 1 of Example 1, add 1 mol (100.09 g) of calcium carbonate (CaC0 ₃ ) and 1 mol (254 g) of calcium pyrophosphate (Ca ₂ P ₂ 0 ₇ ) together with ethane in a ball mill. With the time mixture,.

In Example 3, the third calcium phosphate was prepared in the same manner as in Example 1, except that dry ice was not used in the first step and phase angle was performed using an electric fan in the silver.

<134>

135> <Comparative Example 3>

d36> as in Example Calcium Carbonate in step 1 of the first (CaC0 ₃₎ and the above embodiment except that the combined common to one mole (100.09 g) and phosphate dibasic calcium (CaHP0 ₄₎ 2 moles (272.12 g) Example 1 In the same manner, tricalcium phosphate was prepared.

<137>

l38><Experimental Example 1> Scanning electron microscope observation <i39> The microstructures of the third phosphates prepared in Examples 1, 3, 4, 6 and 7 and Comparative Examples 1 and 2 were observed using a scanning electron microscope (JSM-840A, JEOL Ltd.). The results are shown in FIGS. 1 to 7.

1 to 7, the tricalcium phosphate prepared in Examples 1, 3, 4, 6 and 7 exhibited higher porosity than the tricalcium phosphate prepared in Comparative Examples 1 and 2. It can be seen that. As such, the reason why the tricalcium phosphate prepared in the above examples shows high porosity is that a plurality of pores are formed by adding a pore generating agent. It can be easily penetrated to the inside, thereby reducing the cornering time.

<141>

<Example 2> Purity analysis of _£ 1 type 3 phosphate

X-ray diffractometer (D / Max-2200 Ultima / PC) using an X-ray diffractometer (D / Max-2200 Ultima / PC) to analyze the third component phosphate prepared in Examples 1 and 2, Comparative Example 1 and Comparative Example 2 Assays and assays were prepared by performing ray diffraction analysis and pure α- and β-type tricalcium phosphate special reagents. X-ray diffraction analysis results (2Θ = 27.80 peak area and 2Θ) The purity of α-type tricalcium phosphate was calculated by substituting the peak area of = 22.86, and the calculated purity of α-type tricalcium phosphate is shown in Table 1 below.

d.44>

ίΙ45> 【Table 1】

d46> As shown in Table 1, it was found that the purity of the α-type tricalcium phosphate of the third calcium phosphate prepared in Examples 1 to 7 was higher than that of the third calcium phosphate prepared in Comparative Examples 1 to 3. Can be. Through this, it can be seen that the purity of the α-type triphosphate can be improved by forming pores using the pore-generating agent, and performing rapid ablation using dry ice.

Claims

[Range of request]

[Claim 11

Mixing the raw material of the third phosphate and the pore forming agent (step 1);

. Calcining the mixture blended in step 1 to a temperature of 1200 to 1400 ^° C. (step 2); And

The method for producing a third phosphate decay using a ¾ pore generating agent comprising the step (step 3) of cooling the calcined calcined body in step 2.

[Claim 2]

The method of claim 1, wherein the raw material of step 1 is a process for producing a third a calcium phosphate with a pore-generating agent, characterized in that the calcium carbonate (CaC0 ₃₎ and a second calcium phosphate dihydrate (CaHP0 ₄ .2¾0).

[Claim 3]

The method of claim 1, wherein the raw material of step 1 is calcium carbonate (CaC0 ₃ ) and dicalcium phosphate anhydride (CaHPO).

[Claim 4]

The method of claim 5, wherein the raw material of step 1 is calcium carbonate (CaC0 ₃ ) and calcium pyrophosphate (calcium pyrophosphate, C¾0 ₇ P ₂ ) characterized in that the method for producing crab triphosphate using a pore generating agent .

[Claim 5]

[5] The method of claim 3 or 4, wherein the raw material of step 1 further comprises distilled water.

[Claim 6]

According to claim U, wherein the pore generating agent of step 1 polylactic acid (polylactic acid), polyglycolic acid (polyglycolic acid), polyhydroxyalkanoate (polyhydroxyalkanoate), polyester, nylon, acrylic resin, polyvinyl alcohol, polyurethane, polyglycol, naphthalene, cellulose, alginic acid, carbon Carrageenan 제조 Method of producing tricalcium phosphate using a pore generator, characterized in that the one selected from the group consisting of starch, carbohydrate and sugar.

[Claim 7]

The method of claim 1, wherein the calcining of step 2 is carried out for 6 to 10 hours.

[Claim 8]

The method of claim 1, wherein the step 3 of the step 3 is performed using dry ice.

[Claim 9]

Tricalcium phosphate prepared by the method of claim U.

[Claim 10]

The tricalcium phosphate of claim 9, wherein the tricalcium phosphate comprises at least 80% of an α-tricalcium phosphate (α-TCP).

[Claim 11]

A bone cement composition comprising the tricalcium phosphate of claim 9.