KR100481189B1 - A preparation method of hydroxy apatite with improved antimicrobial property - Google Patents
A preparation method of hydroxy apatite with improved antimicrobial property Download PDFInfo
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- KR100481189B1 KR100481189B1 KR10-2002-0041930A KR20020041930A KR100481189B1 KR 100481189 B1 KR100481189 B1 KR 100481189B1 KR 20020041930 A KR20020041930 A KR 20020041930A KR 100481189 B1 KR100481189 B1 KR 100481189B1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Abstract
본 발명은 항균력이 우수한 수산화 아파타이트의 제조방법에 관한 것으로서, 칼슘염과 인산염을 사용하여 침전법으로 수산화 아파타이트를 제조하는 방법에 있어서 침전된 수산화 아파타이트를 일정조건하에서 동결건조시킴으로써 건조과정에서 수산화 아파타이트 자체의 응집현상을 억제시켜 분산력을 개선함으로써 항균제의 담체로 사용시 항균특성을 향상시킬수 있는 수산화 아파타이트의 제조방법에 관한 것이다.The present invention relates to a method for preparing hydroxide apatite having excellent antimicrobial activity. In the method for preparing hydroxide apatite by precipitation using calcium salt and phosphate, the precipitated hydroxide apatite is lyophilized under certain conditions. The present invention relates to a method for preparing hydroxide apatite that can improve antimicrobial properties when used as a carrier of an antimicrobial agent by suppressing the coagulation phenomenon of the present invention.
Description
본 발명은 항균력이 우수한 수산화 아파타이트의 제조방법에 관한 것으로서, 칼슘염과 인산염을 사용하여 침전법으로 수산화 아파타이트를 제조하는 방법에 있어서 침전된 수산화 아파타이트를 일정조건하에서 동결건조시킴으로써 건조과정에서 수산화 아파타이트 자체의 응집현상을 억제시켜 분산력을 개선함으로써 항균제의 담체로 사용시 항균특성을 향상시킬수 있는 수산화 아파타이트의 제조방법에 관한 것이다.The present invention relates to a method for preparing hydroxide apatite having excellent antimicrobial activity. In the method for preparing hydroxide apatite by precipitation using calcium salt and phosphate, the precipitated hydroxide apatite is lyophilized under certain conditions. The present invention relates to a method for preparing hydroxide apatite that can improve antimicrobial properties when used as a carrier of an antimicrobial agent by suppressing the coagulation phenomenon of the present invention.
은 이온 등 전이금속 이온들의 항균 효과는 여러 연구를 통해 확인되었다. 이들이 이온 상태로 있도록 하려면 수용액이나 이온교환 특성이 있는 담체에 보관하여야 하는데, 특히 이온 교환성 담체를 사용할 경우 고체 상태의 재료에도 항균 특성을 내재화할 수 있는 길이 열리므로 항균 재료의 사용범위를 크게 넓힐 수 있을 것이다. 상기 이온 교환성 담체로는 이온 교환 특성이 있는 인산 지르코늄, 제올라이트, 수산화 아파타이트 등이 좋은 특성을 가진 것으로 알려져 있다. 이들 재료는 세라믹스 특유의 내열성, 내산화성이 있어 유기 재료내에서 안정한데, 이와 같은 특성은 기존의 화합물계에서는 찾아볼 수 없는 것이므로 항균 재료로서의 새로운 응용분야를 개척할 수 있는 가능성이 있다. Antimicrobial effects of transition metal ions such as silver ions have been confirmed through various studies. To keep them in an ionic state, they must be stored in aqueous solutions or carriers with ion-exchange properties. Especially, the use of ion-exchangeable carriers opens the way to internalize antimicrobial properties even in solid-state materials. Could be. The ion exchange carrier is known to have good properties such as zirconium phosphate, zeolite, apatite hydroxide and the like having ion exchange properties. These materials are stable in organic materials due to the heat resistance and oxidation resistance peculiar to ceramics. Since such characteristics are not found in existing compound systems, there is a possibility of pioneering new applications as antibacterial materials.
상기 무기계 항균제의 담체로서 사용되는 수산화 아파타이트(Ca10(PO4)6(OH) 2)는 척추동물의 뼈나 치아의 주성분으로 우수한 생체 친화성을 가지는 것으로 다음과 같은 방법으로 제조되고 있다.Hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ), which is used as a carrier of the inorganic antimicrobial agent, has excellent biocompatibility as a main component of bones and teeth of vertebrates, and has been manufactured by the following method.
현재 알려져 있는 수산화 아파타이트의 제조방법으로는 공기중 또는 수증기 분위기의 1000 ℃ 정도의 고온에서 칼슘염과 인산염을 반응시키는 고상반응법, 오토클레이브를 사용하여 고온, 고압으로 장시간 반응시키는 수열법, 그리고 수용성 인산염과 칼슘염을 수용액 중에서 반응시키는 침전법 등의 습식법이 있다. 이러한 방법들 중에서 고상반응법은 조성의 제어는 용이하지만 균일성이나 소결체 특성면에서는 결점이 많은 방법이다. 수열법은 결정성이 뛰어난 소결체가 얻어지지만, 미세한 입자를 얻는 것은 곤란하다. 침전법은 제조과정이 간단하고 치밀한 소결체를 제조하기 위한 입자 크기 등의 분말 특성이 우수하여 상기 방법들 중에서 가장 많이 사용되고 있으나, 건조과정에서 자체 응집체의 발생으로 제조된 미세한 입자의 장점으로 살리지 못하는 문제점이 있다.Known methods for producing hydroxide apatite include solid-phase reactions in which calcium salts and phosphates are reacted at high temperatures in the air or steam atmosphere at about 1000 ° C., hydrothermal methods in which high-temperature and high pressure reactions are carried out using an autoclave, and water solubility. Wet methods, such as the precipitation method which makes a phosphate and a calcium salt react in aqueous solution, are mentioned. Among these methods, the solid phase reaction method is easy to control the composition, but has many disadvantages in terms of uniformity and sintered body properties. In the hydrothermal method, a sintered compact having excellent crystallinity is obtained, but it is difficult to obtain fine particles. Precipitation method is the most widely used among the above methods because the manufacturing process is simple and has excellent powder characteristics such as particle size for producing a compact sintered compact, but the problem of not being able to make use of the fine particles produced by the generation of self aggregates during the drying process There is this.
이에, 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 칼슘염과 인산염을 사용하여 침전법으로 수산화 아파타이트를 제조하는 방법에 있어서 침전된 수산화 아파타이트를 일정조건하에서 동결건조시킴으로써 건조과정에서 수산화 아파타이트 자체의 응집현상을 억제시켜 은이온 교환량을 증가시킴으로서 항균력이 개선됨을 알게되어 본 발명을 완성하였다.Thus, the present inventors in order to solve the above problems by using a calcium salt and phosphate in the method of producing hydroxide apatite by precipitation method, the precipitated hydroxide apatite by lyophilization under certain conditions, the aggregation of the hydroxide apatite itself in the drying process The present invention was found to improve the antibacterial activity by increasing the amount of silver ions exchanged by suppressing the phenomenon.
따라서, 본 발명은 항균제의 담체로 사용시 항균특성을 향상시킬 수 도록 수산화 아파타이트를 처리하는 방법을 제공하는데 그 목적이 있다. Therefore, an object of the present invention is to provide a method for treating hydroxide apatite to improve the antimicrobial properties when used as a carrier of the antimicrobial agent.
본 발명은 칼슘염과 인산염을 사용하여 침전법으로 수산화 아파타이트를 제조함에 있어, 침전된 수산화 아파타이트를 -100 ∼ -40 ℃, 30 ∼ 50 mmTorr에서 동결건조 후 은이온을 도입하는 항균성 수산화 아파타이트의 제조방법을 그 특징으로 한다.In the present invention, in the preparation of hydroxide apatite by precipitation method using calcium salt and phosphate, preparation of antimicrobial hydroxide apatite to introduce silver ions after freeze-drying the precipitated hydroxide apatite at -100 ~ -40 ℃, 30 ~ 50 mmTorr The method is characterized by that.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 무기계 항균제의 항균 특성을 극대화하기 위해 항균제의 담체로 사용되는 수산화 아파타이트의 제조시 동결건조를 도입하여 담체의 비표면적이 극대화되도록 하는데 그 특징이 있다.The present invention is characterized by maximizing the specific surface area of the carrier by introducing lyophilization in the preparation of hydroxide apatite used as a carrier of the antimicrobial agent to maximize the antimicrobial properties of the inorganic antimicrobial agent.
본 발명에 따른 수산화 아파타이트의 제조방법은 다음과 같은 침전법을 사용하여 제조된다.The method for preparing hydroxide apatite according to the present invention is prepared using the following precipitation method.
먼저, 칼슘염을 물에 용해시켜 칼슘 용액을 제조하는 단계; 인산염을 물에 용해시켜 인산염 용액을 제조하는 단계; 상기 인산염 용액과 칼슘 용액을 혼합하여 교반하는 단계; 생성된 침전물을 동결건조하여 수산화 아파타이트를 얻는 단계; 동결건조된 분말을 0.1 M Ag(NO3)용액에 분산시켜 이온교환을 하는 단계로 이루어져 있다.First, dissolving the calcium salt in water to prepare a calcium solution; Dissolving phosphate in water to prepare a phosphate solution; Mixing and stirring the phosphate solution and calcium solution; Lyophilizing the resulting precipitate to obtain apatite hydroxide; The lyophilized powder is dispersed in 0.1 M Ag (NO 3 ) solution and ion exchanged.
이때, 상기 칼슘염으로는 질산칼슘(Ca(NO3)2·4H2O)이 바람직하며, 인산염으로는 인산수소암모늄((NH4)2HPO4)을 사용하는 것이 좋다. 그리고, Ca:P의 조성비가 10:6이 되도록 인산염을 첨가한다.In this case, calcium nitrate (Ca (NO 3 ) 2 .4H 2 O) is preferable as the calcium salt, and ammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) is preferably used as the phosphate salt. And phosphate is added so that a composition ratio of Ca: P may be set to 10: 6.
특히, 본 발명은 상기 침전된 수산화 아파타이트 -100 ∼ -40 ℃, 30 ∼ 50 mmTorr에서 동결건조함으로써 수분의 승화를 유도한다. In particular, the present invention induces sublimation of moisture by lyophilization at the precipitated apatite hydroxide -100 ~ -40 ℃, 30 ~ 50 mmTorr.
상기 조건은 반응용액이 동결된 후 액화되지 않고 기화를 일으키는 조건으로써 빠른 속도의 승화를 유도하는데 적합하여 선택하였다. The above conditions were selected to be suitable for inducing high-speed sublimation as a condition for evaporation without liquefaction after the reaction solution was frozen.
본 발명은 침전된 수산화 아파타이트를 동결건조 시킴으로서 종래 고온건조시에 비해 액상을 거치지 않고 수분을 제거하므로 응집체의 형성을 방지할 수 있다. 액상은 건조과정에서 부피가 감소하면서 수산화 아파타이트의 표면적을 최소화하기 위하여 액적을 형성하는데, 이때 액적내에 남아있는 분말이 응집체를 형성하게 된다. 동결건조시에는 이러한 액적이 생성되지 않도록 현탁액을 동결시킨 후 용매를 승화시키는 과정을 거치므로 응집체의 형성을 최소화하고 보다 다량의 은이온을 교환할 수 있다.The present invention can prevent the formation of aggregates by lyophilizing the precipitated hydroxide apatite to remove moisture without passing through the liquid phase compared to the conventional high temperature drying. The liquid phase forms droplets in order to minimize the surface area of the hydroxide apatite while decreasing its volume during drying, in which the powder remaining in the droplets forms aggregates. In lyophilization, the suspension is frozen after sublimation to prevent the formation of such droplets, thereby minimizing the formation of aggregates and exchanging larger amounts of silver ions.
이하, 본 발명을 실시예에 의거하여 더욱 상세하게 설명하겠는 바, 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
실시예Example
Ca(NO3)2·4H2O와 (NH4)2HPO4의 0.5M 수용액을 각각 제조한 후, Ca:P의 조성비가 10:6이 되도록 혼합하여 6시간 동안 1000 rpm에서 교반하였다. 반응이 끝난 후, 침전된 생성물은 -50 ℃, 40 mmTorr에서 동결 건조하고 0.1 M Ag(NO3)용액에 분산시켜 은이온이 수산화 아파타이트 입자내로 이온 교환되도록 하였다.0.5M aqueous solutions of Ca (NO 3 ) 2 .4H 2 O and (NH 4 ) 2 HPO 4 were prepared, respectively, and mixed so that the composition ratio of Ca: P was 10: 6, followed by stirring at 1000 rpm for 6 hours. After the reaction was completed, the precipitated product was freeze-dried at -50 ℃, 40 mmTorr and dispersed in 0.1 M Ag (NO 3 ) solution to allow the silver ion to be ion exchanged into the hydroxide apatite particles.
비교예 Comparative example
Ca(NO3)2·4H2O와 (NH4)2HPO4의 0.5M 수용액을 각각 제조한 후, Ca:P의 조성비가 10:6이 되도록 혼합하여 1000 rpm에서 6시간 교반하였다. 반응이 끝난 후, 침전된 생성물을 세척하여 120 ℃에서 24시간동안 건조하고 0.1 M Ag(NO3)용액에 분산시켜 은이온이 수산화 아파타이트 입자내로 이온 교환되도록 하였다.After preparing 0.5M aqueous solution of Ca (NO 3 ) 2 .4H 2 O and (NH 4 ) 2 HPO 4 , respectively, the mixture was mixed so that the composition ratio of Ca: P was 10: 6 and stirred at 1000 rpm for 6 hours. After the reaction, the precipitated product was washed, dried at 120 ° C. for 24 hours, and dispersed in a 0.1 M Ag (NO 3 ) solution to allow silver ions to ion exchange into apatite hydroxide particles.
시험예 1Test Example 1
상기 실시예 및 비교예에 의해 제조된 수산화 아파타이트의 수용액(0.1 g/ml)에 분산제로 0.01 ml/g의 다반 씨(Darvan C)를 첨가하여 분산상태를 투과전자현미경(TEM)으로 측정하였으며, 그 결과를 도 1에 나타내었다.The dispersion state was measured by transmission electron microscopy (TEM) by adding 0.01 ml / g of Darvan C as a dispersant to an aqueous solution (0.1 g / ml) of hydroxide apatite prepared according to the examples and comparative examples. The results are shown in FIG.
도 1에 나타난 바와 같이, 본 발명에 따른 실시예의 수산화 아파타이트는 응집이 심하지 않아 쉽게 분산됨을 확인할 수 있었으며, 이에 반해 비교예의 경우는 응집체가 생성되어 분산제를 첨가하여도 일부 분산된 입자와 응집체가 혼재함을 확인할 수 있었다.As shown in Figure 1, the hydroxide apatite of the embodiment according to the present invention was confirmed that the agglomeration is not easy to disperse, on the contrary, in the case of the comparative example, the agglomerates are formed, even if some dispersed particles and agglomerates are mixed even if a dispersant is added. Could confirm.
시험예 2Test Example 2
상기 실시예 및 비교예에 의해 제조된 수산화 아파타이트를 분산시킨 현탁액으로 입도 분석기를 이용하여 분말의 응집정도를 분석하여, 그 결과를 다음 도 2에 나타내었다.In the suspension prepared by dispersing the apatite hydroxide prepared in Examples and Comparative Examples, the degree of aggregation of the powder was analyzed using a particle size analyzer, and the results are shown in FIG. 2.
도 2에서 실시예는 평균 입경 약 20 nm로 매우 분말의 1차 입자크기에 근접하지만 응집이 심한 비교예는 평균 입경이 50 nm에 달함을 알 수 있다. In Example 2, the average particle size is about 20 nm, very close to the primary particle size of the powder, but it can be seen that the comparative example of the severe aggregation reaches an average particle diameter of 50 nm.
시험예 3Test Example 3
상기 실시예 및 비교예에 의해 건조된 수산화 아파타이트 분말 5 g을 0.1M AgNO3 용액 50 ml에 분산시켜 Ag 이온을 도입한 후 대장균 E.Coli.를 대상으로 최소발육저지농도(MIC)를 측정하여 항균력을 측정한 결과를 도 3에 나타내었다.5 g of the dried apatite powder dried by the above Examples and Comparative Examples was dispersed in 50 ml of 0.1M AgNO 3 solution to introduce Ag ions, and then the minimum growth inhibition concentration (MIC) was measured for E. coli. The results of measuring the antimicrobial activity are shown in FIG. 3.
도 3에서 실시예는 MIC가 100 ppm이지만 비교예에서는 MIC가 500 ppm으로 동결건조한 실시예가 보다 작은 양으로도 발육을 저지하여 높은 항균력을 가짐을 알 수 있다. In FIG. 3, the MIC is 100 ppm, but in the Comparative Example, the MIC freeze-dried at 500 ppm may inhibit growth even in a smaller amount, and thus have high antibacterial activity.
상술한 바와 같이, 본 발명에 따른 수산화 아파타이트는 건조과정에서 동결건조를 이용함으로써 수산화 아파타이트 자체의 응집현상을 억제시켜 은이온 도입을 증가시킴으로써 보다 강력한 항균제의 제조에 유용하게 사용할 수 있다.As described above, the hydroxide apatite according to the present invention can be usefully used in the preparation of stronger antibacterial agents by increasing the introduction of silver ions by inhibiting the aggregation phenomenon of the hydroxide apatite itself by using lyophilization in the drying process.
도 1은 본 발명의 실시예 및 비교예에 따른 수산화 아파타이트의 분산상태를 투과 전자현미경으로 측정한 것이다.1 is a measurement of the dispersion state of the apatite hydroxide in accordance with Examples and Comparative Examples of the present invention by transmission electron microscope.
도 2는 본 발명의 실시예 및 비교예에 따른 수산화 아파타이트의 입도 분포를 나타낸 사진이다.Figure 2 is a photograph showing the particle size distribution of the hydroxide apatite according to the Examples and Comparative Examples of the present invention.
도 3은 본 발명의 실시예 및 비교예에 따른 은이온 교환 수산화 아파타이트의 항균력을 보여주는 결과이다.Figure 3 is a result showing the antimicrobial activity of silver ion exchange hydroxide apatite according to the Examples and Comparative Examples of the present invention.
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| US5009898A (en) * | 1988-09-29 | 1991-04-23 | Kabushiki Kaisha Sangi | Antimicrobial hydroxyapatite powders and methods for preparing them |
| JPH04170960A (en) * | 1990-11-06 | 1992-06-18 | Sangi Co Ltd | Antibacterial hydroxyapatite |
| KR950003166A (en) * | 1993-07-10 | 1995-02-16 | 김동학 | Method for preparing hydroxyapatite |
| KR960012708A (en) * | 1994-09-30 | 1996-04-20 | 양승택 | Variable sample pulse generator for measuring received power |
| JPH1017310A (en) * | 1996-07-03 | 1998-01-20 | Ehime Pref Gov | Collagen, production of hydroxyapatite and its product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5009898A (en) * | 1988-09-29 | 1991-04-23 | Kabushiki Kaisha Sangi | Antimicrobial hydroxyapatite powders and methods for preparing them |
| JPH04170960A (en) * | 1990-11-06 | 1992-06-18 | Sangi Co Ltd | Antibacterial hydroxyapatite |
| KR950003166A (en) * | 1993-07-10 | 1995-02-16 | 김동학 | Method for preparing hydroxyapatite |
| KR960012708A (en) * | 1994-09-30 | 1996-04-20 | 양승택 | Variable sample pulse generator for measuring received power |
| JPH1017310A (en) * | 1996-07-03 | 1998-01-20 | Ehime Pref Gov | Collagen, production of hydroxyapatite and its product |
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