JPH01224214A - Production of hydroxyapatite - Google Patents

Abstract

PURPOSE:To obtain stable high-purity hydroxyapatite, by calcining animal bones at a specific temperature in an oxidizing atmosphere and then carrying out physical and chemical treatment. CONSTITUTION:Animal bones are calcined at a temperature within the range of 600-1,200 deg.C in an oxidizing atmosphere, then finely pulverized, dipped in a phosphoric acid ion-containing solution and washed with water. A solution in about 0.01-5% concentration is preferably used as the phosphoric acid ion- containing solution used for dipping. For example, H3PO4, KH2PO4, K2HPO4, Na3PO4 and (NH4)3PO4, can be used as a phosphoric acid source.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing hydroxyapatite, which is attracting attention for its use as a layer absorbing agent and as an IJK material as a substitute material for biorigid fibers.

[Conventional technology and its problems]

Hydroxyapatite (Ca5e(OH)!(PO4h)
) is a 10-charged Ca group (Ca site)
It has a crystal plane with - charged 2po, group (P site), so it has C0OH group, NH,
It has the ability to absorb into biological molecules (proteins) that have groups, and its use as a layer absorbing agent for separation is attracting attention.

In addition, hydroxyapatite is originally considered to be a major component of bones and teeth, and the use of artificially prepared apatite as a prosthesis for bone and tooth defects is becoming concrete.

As for the artificial production method of this apatite, Limbo salt, calcium salt production/mafc is apatite precursor J[
(Ca) (Pot, Ca5(PO4)z, Ca4
A dry method in which solid phase interaction is carried out at high temperature in the presence of H(PO4)3), a wet method in which liquid phase interaction is also carried out in the atmosphere, and a hydrothermal method at high temperature and pressure. Anti-G
A hydrothermal reaction is known.

The dry method is a method for producing apatite by causing a 1!0 phase reaction between calcium salt and phosphate in the presence of apatite pre-assembled 'XQ' at high temperature, but the particle size and mixing state of the powder to be reacted are If it is not uniform, a distribution may occur in the solid phase reaction, and abamate may not be completely formed, such as containing amorphous apatite7? −.

In the hydrothermal reaction, 100 to 500
The reaction was carried out under hydrothermal conditions of 200 to 500 atmospheres with calcium salt (1"), but the reaction equipment and equipment costs were expensive due to the harsh conditions.

The wet method is a method of producing apatite by ripening the apatite precursor obtained in the process of neutralizing phosphorous salt with alkali in an A-denko, but it takes a very long time to ripen it into apatite. -〇On the other hand, as a method for producing apatite, a method using abatite contained in natural products is also known. For example, N.J.
J bone is directly used as a prosthesis in the defective part of human bone, and animal bone is burned and crushed and used as raw material for artificial bone. However, the composition of animal bone depends on the type and location. In particular, the distribution of carbonate apatite content can be seen depending on factors such as age. When a carbonate apatite raw material containing a large amount of electricity is fired, Cot is removed during the firing process, resulting in apatite in which CaO remains partially. When these materials are used as adsorbents or raw materials for artificial bones, they come into contact with liquids and elute alkali, leading to concerns that they may reduce absorbency and adversely affect living organisms.

[Purpose of the invention]

The present invention aims to solve the problems in the prior art described above and to produce stable and highly pure apatite at a low cost.

[Structure of the invention]

The present invention is a method for producing hydroxyapatite, which comprises pulverizing animal bones into fine particles in a defeated atmosphere at a temperature within the range of 600 to 1200°C, immersing them in a solution containing phosphate ions, and then washing them with water. be.

As a result of intensive research on the production method of apatite, the inventors have developed a stable and highly pure apatite that can be used for all animal bones (livestock bones, fish bones) that have not been previously used for M-effects. Manufacturer @ completely invented.

Bone is made up of 65 parts of inorganic material and 35 parts of organic material.The composition of the inorganic material varies depending on the type of animal, body part, age, etc., but dried human bone samples are A representative example is shown in Table-1.

Table 1 Inorganic composition of human bones and teeth The inorganic salts that make up bones (bone minerals in living organisms are
(OH)z(POa)s CCa(OH)2・3Ca3
(PO4)2], and the other charcoal is apatite [caco
, -5ca, (poa)z].

In the present invention, stable and highly pure apatite can be obtained by calcining the whole animal bone in an atmosphere at a predetermined temperature and then performing all physicochemical treatments.

The present invention is refreshing! is as follows.

The beef bones, which have been previously cleaned and degreased, are fired in the air at about 1000°C. Beef bones are processed by G8 to remove fibrous protein, co2-gung, sugars, etc., and are sterilized at the same time. Eliapatite has good crystallinity during firing (XIIM
The diffraction peak becomes sharp), and the material becomes easier to crush.

However, in the process of g8 formation, each component in bone mineral releases CO, H, Ot-, and partially (CaOj 5Cas (
PO4)! ]. Therefore, after pulverizing the calcined ninety bones with a pulverizer, sieving and classifying as necessary, crushing them in a bath containing phosphorus ions, and applying the immersion treatment.
The CaO content that gradually tries to dissolve in the liquid is removed by phosphate ion/
Fix and stabilize. Excess phosphoric acid is removed by water treatment.

To further promote CaO content and abaphytization, use a high concentration of 1 and Ca(OH)3.

It is best to immerse it in an enemy containing KHlPOa. Through this immersion process, the Ayu Sho structure becomes closer to pure apatite. The pH of the immersion liquid is 17~17 to increase the maturation rate of apatite.
9. The concentration of TF must be maintained at 9.9%.
OH) I j 1) NaOH'i is added, and the presence of phosphorus ions is preferably added at a time when violet ions that can react with the CaO content in the calcined bone mineral are excessive.

After the soaking process, it is separated from the soaked Tjt dragon and washed with water.
Wash out impurities such as excess base metal and storm metal.

As the phosphoric acid-containing solution to be immersed, it is preferable to use a bath liquid having an α of about 1 to 5%. Phosphorus as a source
, H3PO4, K1HO4, K1HPO4, Na1PO
4.

(NH4) spo4 etc. are used.

Incidentally, the degree of roasting IJA is preferably 600 to 1200°C.

Illegally: Utilizing bone minerals in animal bones, firing and then chemically treating the apatite, it is possible to produce apatite with high purity.Furthermore, the structure of this apatite is Since it uses gold that originally existed in bones, is it possible to provide a material that is preferable as a raw material for artificial bones and artificial tooth roots? IJ 1 Washed beef bone 100fi in air, 50 each
0℃, 600℃, 1200℃.

After baking at 1,600℃, grinding with a grinder to give 150 to 10
The particle size was adjusted to 0 μm, and this was heated to KH, Po, 5 at room temperature.
% solution for about 5'0 minutes. Thereafter, each bone was washed with 10 times more water than the beef bones. The X-ray diffraction pattern and Ca/P ratio of the valley sample were measured and the results are shown in Figure 1.

At 500℃, the peak of apatite is unclear, but
When fired at 600° C. or higher, the apatite peak became sharp (good crystallinity), which was 90, that is, the crystallinity became good. In addition, pure apatite had a low Ca/P ratio of 2.15, but the Ca/P ratio became almost constant at temperatures above 600°C. Note that when firing at 1300°C, bath melting occurred in some parts, making recovery of the material difficult and unsuccessful. 600. Samples fired at 1000°C do not elute alkali even when immersed in fresh water.

Implementation Ga 2 Beef bone 100~4 is calcined in the air at 600℃, then crushed in a crusher, the particle size is reduced to 10~20 Jlm, and the powder is crushed at 10℃, 20℃, 601℃, 80℃. of Ca(O
H) Soaked in 1% K1HPO42.5% solution for 2 hours, then washed with water. Also at 80℃ KE snow POa 2
．． A sample that had been immersed in a 5'% M solution for 2 hours and then washed with water was also obtained, and the X-diffraction diagram of the Kuotani sample is shown in Figure 7 and Figure 2.

As a result, when immersed in a V solution containing slaked lime and phosphorous ions at a temperature of 600°C or higher, the crystallinity of apatite was excellent. - In the case of no immersion tf, the apatite had poor crystallinity, and when immersed in fresh water, alkaline t' bathed out.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the calcining temperature of beef bone, the X-ray diffraction pattern of the product, and the Ca/'P ratio, Figure 2 is the X-ray diffraction diagram of the calcining temperature of beef bone, the temperature of immersion in PO4 solution, and the product. and Ca/P ratio.

Claims (1)

[Claims] 1. A method for producing hydroxyapatite, which comprises firing animal bones in an oxidizing atmosphere at a temperature within the range of 600 to 1200°C, pulverizing them, immersing them in a phosphate ion-containing solution, and washing them with water.