JPS6232964A - Living body ceramic material and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention is directed to β-tricalcium phosphate [Ca3(PO4)2] as a biomaterial that can be used for repairing bones, teeth, and blood vessels.
] (hereinafter abbreviated as β-TCP) and a method for manufacturing the same.

B0 Summary of the Invention The present invention provides a β-'I'CP sintered body and its manufacturing capability.
The sintered body has a Ca/P ratio of 1.
The present invention relates to a calcium phosphate-based sintered body having a high bending strength, which is characterized mainly by B in the range of 50 to 1.58.

C0 Conventional technology β-TCP sintered body is made of hydroxyapatite [Ca. (PO4)6(OH),] (hereinafter HAp
17 approximates the chemical composition of

In addition, the β-TCP sintered body is known as a bioceramic material 17 that has high utility value, such as being more resistant to thermal shock than the above-mentioned HAp, and having high bending strength and fracture toughness values.

Problems that the D0 invention aims to solve It was a very difficult ceramic.

Means for Solving E0 Problems In the present invention, in order to solve the above problems, the chemical composition of pure β-TCP (Ca/P ratio 1,50) is slightly changed by changing the Ca/P ratio. A synthesized 17 sintered body was obtained,
These bending strengths were measured to clarify the correlation between Ca/P ratio and bending strength, and the best composition with respect to bending strength was determined. That is, in the present invention, regarding the β-TCP sintered body, the Ca/P ratio is set to 1.50 to 1.58, and the Ca
Me/(IJe+Ca) as a trace metal component contained in
(However!, Met, Llg, Ba, Sr) 1
/1000 or more -L, and the above-mentioned T(A p
Alternatively, by containing a small amount of Ca2P2O7, the desired β-TCP sintered body can be obtained.

Also, regarding the method for manufacturing the β-TCP sintered body, please refer to M
e/ (Me+Ca) (However, 1.Me is Mg, Ba,
Ca containing 171,000 or more of Sr)
(OHI 2 aqueous solution and H3P0. aqueous solution were mixed and reacted so that the Ca/P ratio was 1.0 to 1.65, filtered,
After drying, sintering at a temperature of 1050 to 1150°C (7℃ Ca/
P ratio is 1.50 to 1. A β-TCP sintered body of Fi8 is obtained.

In the present invention, the Ca/P ratio is 1.50 to 1.58 and 17
This is because if the bending strength is below the lower limit or above the upper limit of this range, the bending strength will decrease.
.

Ba, Sr Me/(IJe+Ca) ratio to 1/10
The reason for setting it above 00 is that if it is less than this, the sintering effect is bad and it is necessary to vary the sintering temperature. )% or less because the strength decreases if these limited amounts are exceeded.

F0 Effect As explained above, β-TCP whose composition is limited according to the present invention exhibits a higher bending strength than conventional β-TCP.

G0 Examples of the Invention The structure and effects of the present invention will be explained in more detail with reference to several examples below.

(1) Example 1 The Ca/P ratio during synthesis was 1.20, and Ra (OH) 2
Ca containing 0.01 in Ha/(Ra+ca) ratio
(OH) was added to an aqueous solution IO1 while stirring 17 to complete the reaction, including excess P, that is, the Ca/P ratio was 1.
．． A predetermined aqueous solution of n3Po7 having a concentration of 20% was gradually added dropwise to react the mixture at room temperature.

After aging, the contents thus obtained were filtered and dried in a drying mold at 80° C. for 3 days.

After that, an electric furnace using silicon carbide as a heater was used to heat the powder.
When we investigated the line diffraction, we found that I(A
p[Ca,. (PO4) e (OII) gl 3
Confirm that % is not included in β-TCP17.

3.0% (by weight) of PVA (polyvinyl alcohol) was added as a binder to this powder, mixed with a dish skimmer, passed through a sieve, and compressed using a mold at a pressure of 0.8 ton/at 17. Sintering was carried out at 1100°C using an electric furnace.

When the composition of this fired body was examined again by X-ray diffraction, it was found to be approximately the same as the X-ray diffraction peak shown in FIG. 1 described above (7).

In addition, the concentration of Ca and P in this fired body was quantified by plasma emission spectrometry (TCP), and the Ca/P ratio was 1.51.
Met.

For bending strength measurement, test pieces of 4 x 2 x 25 (mm) were prepared from a disc-shaped sintered body using a precision low-speed cutting machine.
Point bending test (span 15mm, crosshead speed 0)
．． 1mm/m1n) (results will be described later).

(11) Example 2 The Ca/P ratio during synthesis was 1.0, and Ba (OH) 2 was
Ca (O
H) A predetermined amount of the P04 aqueous solution 17 was added dropwise to the 2 aqueous solution 101 while stirring to complete the reaction.

Hereinafter, β-T was obtained using the same operations and conditions as in Example 1.
A CP sintered body was obtained, and a test piece for measuring bending strength was prepared and subjected to a three-point bending test (results will be described later). FIG. 2 shows the results of X-ray diffraction of this sintered body.

The concentration of Ca and P in the sintered body was measured by plasma emission spectroscopy (TC).
The Ca/P ratio was 1.45 as determined by the method p).

(iii) Example 3 A β-TCP sintered body was obtained using the same operations and conditions as in Example 1, with a Ca/P ratio of 1.6 during synthesis, and a test piece for measuring bending strength was prepared. , and subjected to a three-point bending test (results will be described later). FIG. 3 shows the X-ray diffraction results of this sintered body.

The concentration of Ca and P in the sintered body was determined by plasma emission spectroscopy (IC).
The Ca/P ratio was 1.54 using the L quantification method (7).

Similar to the above three examples, many P-Cs with different compositions
From the results of synthesizing compound a, the Ca/P ratio at the time of synthesis was 1.
0 to 1.65, whereas the Ca/P ratio of the sintered body is 1.42 to 1.65.
It became 1.58. Furthermore, the relationship between the Ca/P ratio and the bending strength of the sintered body was as shown in FIG. 4 (the temperature in the figure is the sintering temperature). Moreover, FIG. 5 shows the relationship between sintering temperature and bending strength.

As is clear from Fig. 4, the bending strength of the sintered body is
The highest value was obtained when the sintering temperature was 1100°C and the Ca/P ratio was 1.54, at 1600 kg/car. By X-ray diffraction, Ca2P2O□ is detected when the Ca/P ratio is less than 1.5 (see Figure 2), and HAp is detected when it is more than 1.5 (see Figure 2).
(See Figures 1 and 3).

On the other hand, Jarch et al. [M, Jarch, J., Mater, Sci., 11
The proposal for 2027 (1976)l has a Ca/P ratio of 1.65.
This data shows data near the Ca/P ratio of HAp, that is, near 1.67, and there is no data near 1.50, that is, the Ca/P ratio of β-TCP, which is limited in the present invention, near 1.50.

In addition, Akao et al. (Tokyo Medical and Dental University Medical Thermal Materials Research Report Vol. 15, 1939
6) proposed a Ca/P ratio of 1.50 to 1.67, but for a Ca/P ratio of around 1.50,
It has not been investigated in detail, and the Ca/P ratio is less than 1.5.
2P2O□ appears and no significant decrease in strength is shown.

The difference between the present invention and the proposal by Akao et al. is clear from FIG. In FIG. 5, the horizontal axis shows the sintering temperature, and the vertical axis shows the bending strength, and each Ca/P ratio is shown as 1. That is, in Akao et al.'s proposal, all of the composition examples with different Ca1P ratios were sintered at a high temperature range of 1150 to 1300°C, and when the Ca/P ratio was 1.51° to 1.56, sintering was performed at 1250°C.
Sintering is carried out at a high temperature of °C. However, in the present invention, sintering is performed at 1100°C, which is much lower than the above-mentioned 1250°C, and the bending strength is 1600 kg/c/ on average at a Ca/P ratio of 1.54.

Furthermore, in the proposal of Akao et al., if the β-TCP sample is synthesized, Ca
(OR) 2 and H3PO4 are used only. On the other hand, in the present invention, as a result of many experiments, Mg, H
a.

Adding Sr lowers the solubility, lowers the sintering temperature, and increases the strength.
(Me+Ca) (Me is Mg, Ba, Sr
) of 171,000 or more. As an experiment, the Mg/(Mg+Ca) ratio was 0.
01. Ha/ (Ba+Ca) ratio 0.01°Sr/
(Test specimens were prepared using the same operation and under the same conditions as in Experimental Example 1 with a composition in which Sr+Ca J ratio of 0.01 was added, and the bending test was performed for 17 hours. The result was 1650 kg/c/cm.

1600 kg/cTl, ]-690 kg/e/, and the maximum bending strength could be obtained by low-temperature sintering at 1100°C.

As described in detail of the H0 invention, according to the present invention, Mg, Ba, and Sr can be added to the composition of β-Tcp to lower the solubility and sintering temperature and to increase the bending strength. By setting the and Ca/T' ratio in the optimal range of 1.50 to 1.58 to obtain bending strength, and lowering the sintering humidity to 1050 to 1150°C compared to the conventional comparative example, the bending strength was 1600°C.
It was possible to obtain β-TCP of kg/e/or more. This material can be used as a bioceramic material for various purposes such as teeth, bones, blood vessels, etc.

[Brief explanation of drawings]

Figure 1 is an X-ray diffraction diagram of the β-TCP sintered body obtained in Example 1 of the present invention, and Figure 2 is the β-TCP sintered body obtained in Example 2 of the present invention.
3 is an X-ray diffraction diagram of the β-TCP sintered body obtained in Example 3 of the present invention, and Figure 4 is an X-ray diffraction diagram of the β-TCP sintered body obtained in Example 3 of the present invention. FIG. 5 is a diagram showing the relationship between the Ca/P ratio of -TCP and the bending strength. FIG. Agent Patent Attorney Masaru Sato Year 411th

Claims (4)

[Claims] (1) Ca/P is 1.50 to 1.58, Me/(
Contains 1/1000 or more of Me+Ca) (where Me is either Mg, Ba, or Sr), and Ca_1_0(P
O_4)_6(OH)_2 or Ca_2P_2O_7
A β-tricalcium phosphate [Ca_3(PO_4)_2] sintered body characterized by containing a trace amount of. (2) Above Ca_1_0(PO_4)_6(OH)_2
The β-tricalcium phosphate [Ca_3(PO_4)_2] sintered body according to claim 1, wherein the content is 4.0% (by weight) or less. (3) Claim 1, characterized in that the content of Ca_2P_2O_7 is 5.0% (by weight) or less.
β-Tricalcium phosphate [Ca_3(PO_4
)_2] Sintered body. (4) Me/(Me+Ca) (Me is Mg, Ba,
A Ca(OH)_2 aqueous solution containing a metal element with 1/1000 or less of Sr) and an H_3PO_4 aqueous solution were
Mix and react so that a/P becomes 1.0 to 1.65, filter, dry, and then sinter at a temperature of 1050 to 1150°C to make Ca/P 1.50 to 1.58. β-tricalcium phosphate [Ca_3(PO_4)_
2] Method for manufacturing a sintered body.