JPH01115360A - Inorganic living body material and preparation thereof - Google Patents
Inorganic living body material and preparation thereofInfo
- Publication number
- JPH01115360A JPH01115360A JP62271677A JP27167787A JPH01115360A JP H01115360 A JPH01115360 A JP H01115360A JP 62271677 A JP62271677 A JP 62271677A JP 27167787 A JP27167787 A JP 27167787A JP H01115360 A JPH01115360 A JP H01115360A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- glass
- powder
- cao
- ceramics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000011521 glass Substances 0.000 claims abstract description 80
- 239000000919 ceramic Substances 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 38
- 239000012620 biological material Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 229910052586 apatite Inorganic materials 0.000 claims description 19
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 19
- 229910052882 wollastonite Inorganic materials 0.000 claims description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010456 wollastonite Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 9
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052637 diopside Inorganic materials 0.000 claims description 5
- RBNCTJWRWOMIBO-UHFFFAOYSA-N dicalcium;magnesium;trihydroxy(trihydroxysilyloxy)silane Chemical compound [Mg+2].[Ca+2].[Ca+2].O[Si](O)(O)O[Si](O)(O)O RBNCTJWRWOMIBO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052839 forsterite Inorganic materials 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910052661 anorthite Inorganic materials 0.000 claims description 3
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005452 bending Methods 0.000 abstract description 12
- 210000000988 bone and bone Anatomy 0.000 abstract description 9
- 229910052681 coesite Inorganic materials 0.000 abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 abstract description 7
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000975 bioactive effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000013001 point bending Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 MgO1Cab Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000001226 triphosphate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、人工骨、人工歯根などのインブラント材料と
して有用な無機生体材料およびその製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an inorganic biomaterial useful as an implant material for artificial bones, artificial tooth roots, etc., and a method for producing the same.
［従来の技術およびその問題点］
セラミックスは高分子材料、金属材料に比べて生体為害
性がない点で生体材料として注目され、近年その進歩が
著しい。アルミナセラミックスは人工骨、人工歯根とし
て実用化されており、高強度であること、医学的安全性
、信頼性から高く評価されている。また、ジルコニアセ
ラミックスはアルミナセラミックスよりも強度や靭性が
高く、生体親和性もアルミナセラミックスと同様に良い
ことが報告されており、実用化への研究が進められてい
る。しかしながら、アルミナセラミックスやジルコニア
セラミックスは、骨と直接化学結合しないため、長期の
使用において、ルーズニングの起こる可能性があり、現
にそのような臨床例も数例報告されている。一方、セラ
ミックスの中には骨と化学結合をつくる、いわゆるバイ
オアクティブセラミックスが知られており、このような
セラミックスの場合、生体と一体化するのでルーズニン
グが起こらない。バイオアクティブセラミックスとして
は、アパタイト焼結体やＮａ２０−に２０ ＭｇＯＣａ
ＯＳ ｉ ０２ Ｐ２０５系結晶化ガラスが知られて
いる。また、Ｍｇ０−Ｃａ ＯＰ ２０５ Ｓ １０
２系ガラスを２００メツシュよりも細かい粒度に粉砕し
、得られたガラス粉末を成形後、ガラス粉末−の焼結温
度域で熱処理し、次いでアパタイト結晶［Ｃａ１ｏ（Ｐ
Ｏ２）６ （００，５、Ｆ）２ ］及びウオラストナ
イト結晶［ＣａＳｉＯ３］の生成温度域で熱処理して製
造される結晶化ガラスも知られている。この結晶化ガラ
スでは、アパタイト結晶が生体親和性に寄与し、ウォラ
ストナイト結晶が機械的強度に寄与する。従って、機械
的強度を上げるなめにはウオラストナイト結晶の含有率
を高めることが望ましい。そこで、Ｓ ｉ ０２の含有
量を増やし、ウォラストナイト結晶の析出量を増した結
晶化ガラスも知られている。さらに、最近では、加熱処
理によりアパタイト結晶と、ウォラストナイト、ジオプ
サイド、フォルステライト、オケルマナイト及びアノル
サイトから選ばれるアルカリ土類ケイ酸塩結晶の１種ま
たは２種以上とを析出する、２００メツシュよりも細か
い粒度を有するガラス粉末にジルコニアを５〜５０体積
％均一に混合し、混合物を成形後、この成形体が焼結し
、ガラスからアパタイト結晶と前記アルカリ土類ケイ酸
塩結晶の１種または２種以上とが析出する温度域で熱処
理して得られるジルコニア複合結晶化ガラスも知られて
いる（特開昭６２−２３１６６８号公報参照）。ところ
が、これらのセラミックスの曲げ強度は、アパタイト焼
結体で、１０００〜１４００ｋｇ／ｃＪ、 Ｎａ２０−
に２０−ＭｇＯ−ＣａＯ−３ｉ ０２ Ｐ２０５系結
晶化ガラスで１０００〜１５００ ｋｇ／ｃＪ、Ｍ ｇ
ＯＣａ ＯＰ２０５−３ｉ０２系結晶化ガラスで１２
００〜１４００ｋｇ／−程度である。また、ウオラスト
ナイトを多量に析出させなＣａ ＯＰ ２０ｓ Ｓ
ｉ ０２系あるいはＣａＯＰ２０５ Ｓ ｉ０２
ＭｇＯ，Ｙ２Ｏ３系結晶化ガラスは１７００〜２３００
ｋｇ／ｃｉ程度である。さらに、ジルコニア複合結晶
化ガラスは２３００〜３３００ｋｇ／−と比較的高い曲
げ強度を有しているものの、最も高強度なものでもアル
ミナセラミックスの曲げ強度（３０００〜５０００ｋｇ
／−）の下限程度であり、人工骨または人工歯根として
は必ずしも充分に満足できるほどのものではなく、その
使用用途についてはかなりの制限を受けているのが現状
であり、高強度でかつ生体活性機能を有する無機生体材
料が要望されている。[Prior art and its problems] Ceramics have attracted attention as biomaterials because they are less harmful to living organisms than polymeric materials and metal materials, and their progress has been remarkable in recent years. Alumina ceramics have been put into practical use as artificial bones and artificial tooth roots, and are highly evaluated for their high strength, medical safety, and reliability. In addition, it has been reported that zirconia ceramics have higher strength and toughness than alumina ceramics, and have similar biocompatibility to alumina ceramics, and research toward practical use is progressing. However, since alumina ceramics and zirconia ceramics do not chemically bond directly to bone, there is a possibility that loosening may occur during long-term use, and several such clinical cases have been reported. On the other hand, among ceramics, so-called bioactive ceramics are known that create chemical bonds with bones, and in the case of such ceramics, loosening does not occur because they are integrated with the living body. Bioactive ceramics include apatite sintered bodies, Na20-20 MgOCa
OS i 02 P205 type crystallized glass is known. Also, Mg0-Ca OP 205 S 10
The 2-type glass is crushed to a particle size finer than 200 mesh, and the resulting glass powder is molded and then heat-treated in the sintering temperature range of glass powder, followed by apatite crystal [Ca1o(P
Crystallized glass produced by heat treatment in the formation temperature range of O2)6 (00,5,F)2 ] and wollastonite crystals [CaSiO3] is also known. In this crystallized glass, apatite crystals contribute to biocompatibility, and wollastonite crystals contribute to mechanical strength. Therefore, in order to increase the mechanical strength, it is desirable to increase the content of wollastonite crystals. Therefore, crystallized glass is also known in which the content of S i 02 is increased and the amount of precipitated wollastonite crystals is increased. Furthermore, recently, more than 200 meshes have been developed which precipitate apatite crystals and one or more alkaline earth silicate crystals selected from wollastonite, diopside, forsterite, okermanite, and anorthite by heat treatment. Zirconia is uniformly mixed into glass powder having a fine particle size in an amount of 5 to 50% by volume, and after the mixture is molded, the molded body is sintered to produce apatite crystals and one or two of the above-mentioned alkaline earth silicate crystals from the glass. A zirconia composite crystallized glass obtained by heat treatment in a temperature range in which seeds or more are precipitated is also known (see JP-A-62-231668). However, the bending strength of these ceramics is 1000 to 1400 kg/cJ for apatite sintered bodies, Na20-
20-MgO-CaO-3i 02 P205-based crystallized glass with 1000-1500 kg/cJ, M g
OCa OP205-3i02 type crystallized glass 12
It is about 00 to 1400 kg/-. In addition, Ca OP 20s S, which does not precipitate a large amount of wollastonite,
i 02 series or CaOP205 S i02
MgO, Y2O3 type crystallized glass is 1700-2300
It is about kg/ci. Furthermore, although zirconia composite crystallized glass has a relatively high bending strength of 2,300 to 3,300 kg/-, even the highest strength one has a bending strength of alumina ceramics (3,000 to 5,000 kg/-).
/-), and is not necessarily fully satisfactory as an artificial bone or tooth root.Currently, there are considerable restrictions on its usage, and it is difficult to use high strength and biological materials. There is a need for inorganic biomaterials with active functionality.
従って本発明の目的は高強度でかつ生体活性べ能を有す
る新規無機生体材料を提供することにある。Therefore, an object of the present invention is to provide a novel inorganic biomaterial having high strength and bioactive properties.
［問題点を解決するための手段］
本発明は、高い生体親和性と高強度、高靭性を有するジ
ルコニア系セラミックスに、生体活性機能を有する結晶
化ガラスを分散させることによつて上記目的を達成した
ものであり、本発明の無機生体材料は、重量基準で、
ＣａＯ１２〜５６％
Ｐ２Ｏ５’ １〜２７％
ＳｉＯ２ ２２〜５０％
ＭｇＯ０〜３４％
Ａｌ２Ｏ３０〜２５％
の範囲で上記成分を含有し、Ｃａｂ、Ｐ２０５、ＳｉＯ
ＭｇＯ及びＡｌ２Ｏ３の含有量合計が２ ・
９０％以上である組成を有する結晶化ガラスを、重量基
準で１〜１００％の部分安定化ジルコニアと９９〜０％
のα−アルミナとから成るジルコニア系セラミックス中
に、結晶化ガラスとジルコニア系セラミックスとの合計
体積基準で５〜５０％分散させた複合セラミックスから
なることを特徴とする。[Means for Solving the Problems] The present invention achieves the above object by dispersing crystallized glass having a bioactive function in zirconia ceramics having high biocompatibility, high strength, and high toughness. The inorganic biomaterial of the present invention contains, on a weight basis, the above components in the following ranges: CaO 12-56% P2O5' 1-27% SiO2 22-50% MgO 0-34% Al2O30-25%; , P205, SiO
Crystallized glass having a composition in which the total content of MgO and Al2O3 is 2.90% or more is mixed with 1 to 100% partially stabilized zirconia and 99 to 0% by weight.
The present invention is characterized in that it consists of a composite ceramic in which 5 to 50% of crystallized glass and zirconia ceramics are dispersed based on the total volume in a zirconia ceramics consisting of α-alumina.
この無機生体材料は、アパタイト結晶と、ウオラストナ
イト、ジオプサイド、フォルステライト、オケルマナイ
ト及びアノルサイトから選ばれるアルカリ土類ケイ酸塩
結晶の１種または２種以上とを含有し、さらにβ−リン
酸三カルシウム結晶［β−Ｃａ３ （ｐｏ４）２ ］
を場合により含有する。This inorganic biomaterial contains apatite crystals and one or more alkaline earth silicate crystals selected from wollastonite, diopside, forsterite, okermanite, and anorthite, and further contains β-triphosphate triphosphate. Calcium crystal [β-Ca3 (po4)2]
Contains as the case may be.
本発明の無機生体材料を構成する複合セラミックスは部
分安定化ジルコニアの高強度、高靭性な点を利用したも
のである。本発明において用いられる部分安定化ジルコ
ニアとは、少量のＹ２Ｏ３、ＭｇＯ１Ｃａｂ、ＣｅＯ２
等の１種又は２種以上とを固溶した正方晶ジルコニア粒
子の応力誘起変態（マルテンサイト変態）を利用して高
強度、高靭性化を図ったものであり、１００００〜２０
０００ｋ［／ ｃａもの高強度を示す。ジルコニアを部
分安定化させるためには、Ｚ ｒ Ｏ２に対して、モル
基準で、
Ｙ２０３ ： １ 、５〜５％
ＭｇＯニア〜１０％
ＣａＯニア〜１０％
ＣｅＯ２：４〜１５％
のうちの１種または２種以上を固溶させれば良い。The composite ceramic constituting the inorganic biomaterial of the present invention utilizes the high strength and toughness of partially stabilized zirconia. The partially stabilized zirconia used in the present invention includes a small amount of Y2O3, MgO1Cab, CeO2
High strength and high toughness are achieved by utilizing stress-induced transformation (martensitic transformation) of tetragonal zirconia particles containing one or more of the following as a solid solution.
It shows a high strength of 000 k[/ca. In order to partially stabilize zirconia, one of the following on a molar basis with respect to ZrO2: Y203: 1, 5-5% MgOnia ~ 10% CaOnia ~ 10% CeO2: 4-15% Alternatively, two or more types may be dissolved in solid solution.
さらに、部分安定化ジルコニアにα−アルミナを複合さ
せると、マイクロクラッキングの効果も加わって１５０
００〜２４０００ｋｇ／−もの強度を示す。部分安定化
ジルコニア：α−アルミナの比率は重量基準で、部分安
定化ジルコニア１〜１００％、α−アルミナ９９〜０％
である。しかし、部分安定化ジルコニアが１０％より少
ないと、実施例２に示されているように、ジルコニアの
応力誘起変態による強化の効果が薄く強度の向上に効果
的でないので、好ましい範囲は部分安定化ジルコニア１
０〜１００％、α−アルミナ９０〜０％である。さらに
特に好ましい範囲は部分安定化ジルコニア２０〜１００
％、α−アルミナ８０〜０％である。Furthermore, when α-alumina is combined with partially stabilized zirconia, the effect of microcracking is added, resulting in 150%
It shows a strength of 00 to 24000 kg/-. The ratio of partially stabilized zirconia to α-alumina is based on weight: partially stabilized zirconia 1 to 100%, α-alumina 99 to 0%
It is. However, if the content of partially stabilized zirconia is less than 10%, as shown in Example 2, the strengthening effect due to stress-induced transformation of zirconia is weak and is not effective in improving strength. Zirconia 1
0 to 100%, α-alumina 90 to 0%. A particularly preferable range is partially stabilized zirconia from 20 to 100%.
%, α-alumina 80-0%.
本発明の無機生体材料を構成する複合セラミックスにお
いては、生体活性機能を有する結晶化ガラスが前記ジル
コニア系セラミックスに分散されているが、この結晶化
ガラスの組成に関し、その量的限定理由を以下に述べる
。In the composite ceramic constituting the inorganic biomaterial of the present invention, crystallized glass having a bioactive function is dispersed in the zirconia ceramic. state
重量基準でＣａＯが１２％未満では、アパタイト結晶の
析出量が極端に少なくなる。またＣａＯが５６％を超え
るとガラスの失透傾向が著しくなる。従って、ＣａＯの
含量は１２〜５６％に限定される。Ｐ２Ｏ５が１％未満
では、ガラスの失透傾向が著しく１．２７％を超えると
ウオラストナイト、ジオプサイド、）オルステライト、
オケルマナイト、アノルサイト等のアルカリ土類ゲイ酸
塩結晶の析出量が少なくなるので、Ｐ２Ｏ５の含量は１
〜２７％に限定される。Ｓ ｉ ０２が２２％未満では
、アルカリ土類ケイ酸塩結晶の析出量が少なくなる。ま
たＳｉＯ２が５０％を超えるとガラスが失透しやすくな
る。従ってＳｉＯ２の含量は２２〜５０％に限定される
。ＭｇＯは必須成分ではないが、含む場合は３４％より
多いとアパタイト結晶の生成量が少なくなるので、３４
％以下に限定される。同様に、Ａ Ｉ２０３も必須成分
ではないが、含む場合は２５％より多いとアパタイト結
晶の生成量が少なくなるので、２５％以下に限定される
。When the CaO content is less than 12% by weight, the amount of apatite crystals precipitated becomes extremely small. Moreover, when CaO exceeds 56%, the tendency of glass to devitrify becomes significant. Therefore, the content of CaO is limited to 12-56%. When P2O5 is less than 1%, the glass has a marked tendency to devitrify, and when it exceeds 1.27%, wollastonite, diopside, ) orsterite,
Since the amount of precipitated alkaline earth silicate crystals such as okermanite and anorsite is reduced, the content of P2O5 is 1.
~27%. If S i 02 is less than 22%, the amount of alkaline earth silicate crystals precipitated will be small. Moreover, if SiO2 exceeds 50%, the glass tends to devitrify. Therefore, the content of SiO2 is limited to 22-50%. MgO is not an essential component, but if it is included, the amount of apatite crystals produced will decrease if it is included.
% or less. Similarly, AI203 is not an essential component, but if it is included, the amount of apatite crystals produced will be reduced if it is more than 25%, so it is limited to 25% or less.
上記した５成分に加えてガラスは、人体に有害ではない
に２０、Ｌ ｉ ２０、Ｎ ａ ２０ 、 Ｔ ｉ Ｏ
２、ＺｒＯ２、Ｓ ｒＯ，Ｎｂ２０５ 、Ｔａ２０５、
Ｂ２０３ 、Ｆ２ 、Ｙ２０３を１０％の範囲内で１種
または２種以上含有することができる。これらの任意成
分の合計が１０％より多いときには、アパタイト結晶及
びアルカリ土類ケイ酸塩結晶の生成量が低下してしまう
場合があるので、好ましくは１０％以下とするのがよい
。ただし、Ｆ２は５％より多いとガラスが失透しやすく
なり、またＹ２０３が５％より多いとアパタイト結晶及
びアルカリ土類ケイ酸塩結晶の生成量が低下してしまう
ので、Ｆ２及びＹ ２０３はそれぞれ５％以下に限定さ
れる。In addition to the five components listed above, glass also contains 20, L i 20 , N a 20 , T i O, which are not harmful to the human body.
2, ZrO2, S rO, Nb205, Ta205,
One or more of B203, F2, and Y203 may be contained within a range of 10%. If the total amount of these optional components is more than 10%, the amount of apatite crystals and alkaline earth silicate crystals produced may decrease, so it is preferably 10% or less. However, if F2 is more than 5%, the glass tends to devitrify, and if Y203 is more than 5%, the amount of apatite crystals and alkaline earth silicate crystals produced will decrease, so F2 and Y203 are Each is limited to 5% or less.
上記組成からなる結晶化ガラスがジルコニア系セラミッ
クス中に分散される量は、結晶化ガラスとジルコニア系
セラミックスとの合計体積基準で５〜５０％に限定され
る。その理由は５％より少ないと複合化によって生体活
性機能を付加させた効果がほとんど現れず、また５０％
より多いと骨格となるジルコニア系セラミックス部分が
少なくなるため、機械的強度の向上を期待できないから
である。ガラスの配合量は５〜３０％であるのが特に好
ましい。The amount of the crystallized glass having the above composition dispersed in the zirconia ceramic is limited to 5 to 50% based on the total volume of the crystallized glass and the zirconia ceramic. The reason for this is that if it is less than 5%, the effect of adding bioactive functions by compounding will hardly appear;
This is because if the amount is too large, the zirconia-based ceramic portion that becomes the skeleton will be reduced, and no improvement in mechanical strength can be expected. It is particularly preferable that the amount of glass is 5 to 30%.
上記のごとき本発明の無機生体材料は、重量基準で、
ＣａＯ１２〜５６％
Ｐ２Ｏ５１〜２７％
ＳｉＯ２ ２２〜５０％
Ｍｇｏ ０〜３４％
Ａ １２０３ ０〜２５％
の範囲で上記成分を含有し、Ｃａ Ｏ、Ｐ ２０５．Ｓ
ｉＯ２ 、ＭｇＯ及びＡＡ２０３の含有量合計が９０％
以上である組成を有し、かつ２００メツシュよりも細か
い粒度を有するガラス粉末を、重量基準で１〜１００％
の部分安定化ジルコニアと９９〜０％のα−アルミナと
から成り、前記ガラス粉末よりも細かい粒度を有するジ
ルコニア系粉末に、ガラス粉末とジルコニア系粉末との
合計体積基準で５〜５０％混合し、この混合物を所定の
形に成形した後に、この成形体中のガラスからアパタイ
ト結晶と、ウォラストナイト、ジオプサイド、フォルス
テライト、オクルマナイト及びアノフレサイトから選ば
れるアルカリ土類ケイ酸塩結晶とが析出する温度域で熱
処理し、次いでジルコニア系粉末の焼結温度域で熱処理
することによって製造することができる。The inorganic biomaterial of the present invention as described above contains, on a weight basis, the above components in the following ranges: CaO 12-56% P2O 51-27% SiO2 22-50% Mgo 0-34% A 1203 0-25% , P 205. S
Total content of iO2, MgO and AA203 is 90%
1 to 100% by weight of glass powder having the composition above and having a particle size finer than 200 mesh.
A zirconia-based powder consisting of partially stabilized zirconia and 99-0% α-alumina and having a finer particle size than the glass powder is mixed with 5-50% based on the total volume of the glass powder and zirconia-based powder. After molding this mixture into a predetermined shape, apatite crystals and alkaline earth silicate crystals selected from wollastonite, diopside, forsterite, occlumite, and anophresite are extracted from the glass in this molded body. It can be produced by heat treatment in a temperature range where zirconia-based powder precipitates, and then heat treatment in a sintering temperature range of zirconia-based powder.
本発明の無機生体材料を製造するにあたっては、上に限
定した組成範囲のガラスを先ず２００メツシュよりも細
かい粒度（７４μｍ以下）に粉砕する。ガラスの粒度は
２５００〜６２５メツシュ（５〜２０μｍ）であるのが
特に好ましい。次いでこのガラスをジルコニア系粉末と
均一に混合し、得られた混合粉末を所望の形状に成形し
た後、得られた成形体中のガラス部分の結晶化処理を施
し、次いでジルコニアの焼結を行なうことが肝要である
。複合セラミックス中では、２００メツシュよりも粗い
粒度を有するガラス部分は欠陥となることが多く、機械
的強度の大きな複合セラミックスを得ることができない
。つまり、ジルコニア系セラミックス中に結晶化ガラス
が均一に分布した複合セラミックスを得るためには、２
００メツシュよりも細かい粒度を有する微細なガラス粉
末を用いることが重要である。In producing the inorganic biomaterial of the present invention, glass having the composition range defined above is first ground to a particle size finer than 200 mesh (74 μm or less). It is particularly preferred that the particle size of the glass is 2500 to 625 mesh (5 to 20 μm). Next, this glass is uniformly mixed with zirconia-based powder, the obtained mixed powder is molded into a desired shape, the glass portion in the obtained molded body is subjected to a crystallization treatment, and then the zirconia is sintered. That is essential. In composite ceramics, glass parts having a grain size coarser than 200 mesh often become defects, making it impossible to obtain composite ceramics with high mechanical strength. In other words, in order to obtain a composite ceramic in which crystallized glass is uniformly distributed in the zirconia ceramic, it is necessary to
It is important to use a fine glass powder with a particle size finer than 00 mesh.
本発明の無機生体材料は、第１図に示したようにジルコ
ニア系セラミックス１を骨格とし、これに結晶化ガラス
２を分散させることにより強度の向上を図っている。ジ
ルコニア系粉末がガラス粉末より大きいと、第２図に示
したようにジルコニア系セラミックス１の粒子が結晶化
ガラス２で覆われて、結晶化ガラスを骨格とする構造に
なるため、ジルコニア系セラミックスを骨格とする構造
の複合セラミックスを得ることができず、ジルコニア系
セラミックスの持つ高強度、高靭性な特徴を活かすこと
ができない。よって、用いられるジルコニア系粉末はガ
ラス粉末より細かい粒度を有することが必須である。共
沈法、加水分解法、アルコキシド法等による湿式合成に
よれば、１μｍ以下の微細なジルコニア系粉末が得られ
るが、このような微細なジルコニア系粉末は本発明の複
合セラミックスを得るに好適である。As shown in FIG. 1, the inorganic biomaterial of the present invention has a skeleton of zirconia ceramics 1, and has crystallized glass 2 dispersed therein to improve its strength. If the zirconia powder is larger than the glass powder, the particles of the zirconia ceramic 1 will be covered with the crystallized glass 2 as shown in Figure 2, resulting in a structure with the crystallized glass as the skeleton. It is not possible to obtain a composite ceramic with a structure that serves as a skeleton, and it is not possible to take advantage of the high strength and high toughness characteristics of zirconia ceramics. Therefore, it is essential that the zirconia powder used has a finer particle size than the glass powder. Wet synthesis using a coprecipitation method, a hydrolysis method, an alkoxide method, etc. can yield fine zirconia-based powders of 1 μm or less, but such fine zirconia-based powders are not suitable for obtaining the composite ceramics of the present invention. be.
本発明の方法によれば、２００メツシュよりも細かい粒
度を有するガラス粉末と、このガラス粉末よりもさらに
細かい粒度を有するジルコニア系粉末とを任意の公知手
段で混合、成形し、しかる後成形体を前記ジルコニア−
ガラス混合粉末中のガラスからアパタイト結晶及びアル
カリ土類ケイ酸塩結晶が析出する温度域で熱処理し、次
いで、ジルコニアの焼結温度域（通常１２００°Ｃ以上
）で熱処理する。ただし、焼結温度が１５００°Ｃを超
えると、結晶化ガラス部分が融解して気孔となったり、
ジルコニアと反応して生体活性機能を失ったりすること
があるので、１２００〜１５００℃の焼結温度が好まし
い。前者の熱処理はガラスからアパタイト結晶及びアル
カリ土類ケイ酸塩結晶を析出させるなめに重要であり、
後者の熱処理は気孔の少ない機械的強度の大きな複合セ
ラミックスを得るために重要である。According to the method of the present invention, a glass powder having a particle size finer than 200 mesh and a zirconia powder having a particle size even finer than this glass powder are mixed and molded by any known means, and then a molded body is formed. The zirconia
Heat treatment is performed in a temperature range where apatite crystals and alkaline earth silicate crystals are precipitated from the glass in the glass mixed powder, and then heat treatment is performed in a zirconia sintering temperature range (usually 1200° C. or higher). However, if the sintering temperature exceeds 1500°C, the crystallized glass portion may melt and form pores.
Since it may react with zirconia and lose its bioactive function, a sintering temperature of 1200 to 1500°C is preferable. The former heat treatment is important for precipitating apatite crystals and alkaline earth silicate crystals from the glass;
The latter heat treatment is important for obtaining composite ceramics with few pores and high mechanical strength.
アパタイト結晶及びアルカリ土類ケイ酸塩結晶の析出温
度域はジルコニア−ガラス混合物の示差熱分析により求
められる。示差熱分析曲線における発熱ピークの温度で
熱処理したジルコニア−ガラス混合粉末のＸ線回折デー
タを解析することにより、それぞれの発熱ピークに対応
する析出結晶を同定し、その発熱温度から発熱終了温度
までをそれぞれの結晶の析出温度域とする。The precipitation temperature range of apatite crystals and alkaline earth silicate crystals is determined by differential thermal analysis of a zirconia-glass mixture. By analyzing the X-ray diffraction data of the zirconia-glass mixed powder heat-treated at the temperature of the exothermic peak in the differential thermal analysis curve, the precipitated crystals corresponding to each exothermic peak were identified, and the temperature from the exothermic temperature to the exothermic end temperature was determined. The precipitation temperature range for each crystal.
また、焼結温度域はジルコニア−ガラス混合粉末の成形
体を一定速度で加熱し、その間の熱収縮を測定すること
により求めることができる。熱収縮の開始温度から終了
温度までが焼結温度域である。Further, the sintering temperature range can be determined by heating a molded body of zirconia-glass mixed powder at a constant rate and measuring the thermal contraction during the heating. The sintering temperature range is from the start temperature to the end temperature of thermal contraction.
熱処理方法としては任意の公知手段を用いて良いが、ホ
ットプレス法や）（ＩＰ （熱間静水圧プレス）法を用
いると焼結がより促進されて気孔が少なくなり、より機
械的強度の大きいものが得られる。Any known method may be used as the heat treatment method, but if a hot press method or IP (hot isostatic pressing) method is used, sintering will be further promoted, pores will be reduced, and mechanical strength will be greater. You can get something.
［実施例］
以下、実施例により本発明を更に説明するが、本発明は
これらの実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.
し実施例１コ
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、重量基準で、ＣａＯ４７．８％、Ｓ ｉ
０２ ４４．０％、ＭｇＯ１，５％、Ｐ２Ｏ５６，５％
、Ｆ２０．２％となるようにガラスのバッチを調合し、
これを白金ルツボに入れて１５５０℃で２時間溶融した
。Example 1 CaO 47.8%, Si
02 44.0%, MgO1.5%, P2O56.5%
, prepare a batch of glass to have an F20.2%,
This was placed in a platinum crucible and melted at 1550°C for 2 hours.
次いで融液を水中に投入し、乾燥後、ボールミルに入れ
て２０μｍ以下（６２５メツシュ以上〉の粒度に粉砕し
てガラス粉末を得た。このガラス粉末を、共沈法により
得られた２、５モル％のＹ２Ｏ３を含む部分安定化ジル
コニアからなり、α−アルミナを含まないジルコニア系
微粉末（平均粒径０，３μｍ）に添加し、さらにボール
ミルを用いて数時間湿式混合し、乾燥した。得られた、
ジルコニア系微粉末とガラス粉末との配合比の異なる多
数の混合物のそれぞれを黒鉛型に入れ、３００ｋｇ／−
の圧力をかけながら、室温から１２００℃まで一定の昇
温速度３℃／ ｍ ｉ ｎで加熱し、１２００°Ｃで２
時間保持して成形体の結晶化及び焼結を行なった。しか
る後、炉内で室温まで冷却し、複合セラミックスを得た
。Next, the melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less (625 mesh or more) to obtain a glass powder. It was added to a fine zirconia powder (average particle size 0.3 μm) consisting of partially stabilized zirconia containing mol % of Y2O3 and not containing α-alumina, further wet-mixed using a ball mill for several hours, and dried. was given,
A large number of mixtures of zirconia fine powder and glass powder with different blending ratios were each put into a graphite mold, and 300 kg/-
Heating from room temperature to 1200℃ at a constant temperature increase rate of 3℃/min while applying
The molded body was crystallized and sintered by holding for a certain period of time. Thereafter, it was cooled to room temperature in a furnace to obtain a composite ceramic.
こうして製造された各複合セラミックスの相対比重は９
８％以上であった。また、これら複合セラミックスを粉
砕し、粉末Ｘ線回折により析出結晶相を同定しなところ
、ガラスからはアパタイトとウオラストナイトが析出し
ていた。さらに、複合セラミックスを３Ｘ４Ｘ３６ｍｍ
の角柱に加工し、ＪＩＳ Ｒ１６０１に従って三点曲
げ強度試験を行なった。複合セラミックス中に含まれる
結晶化ガラスの含有層（＃禮百分率）と三点曲げ強度の
関關τ第３図に示す。図から明らかなように、ジルコニ
ア系セラミックス中に結晶化ガラスを５〜５０体積％分
散させた複合セラミックスからなる本実施例の無機生体
材料は最高で１４０００ｋｇ／−の曲げ強度を有し、こ
れまでの生体活性機能を有する無機生体材料に比べて飛
び抜けて高い曲げ強度を有している。The relative specific gravity of each composite ceramic thus manufactured was 9
It was 8% or more. Furthermore, when these composite ceramics were crushed and the precipitated crystal phase was identified by powder X-ray diffraction, apatite and wollastonite were precipitated from the glass. Furthermore, we added composite ceramics to 3X4X36mm.
A three-point bending strength test was conducted according to JIS R1601. The relationship τ between the crystallized glass content layer (#%) contained in the composite ceramic and the three-point bending strength is shown in Figure 3. As is clear from the figure, the inorganic biomaterial of this example, which is made of a composite ceramic in which 5 to 50 volume percent of crystallized glass is dispersed in zirconia ceramics, has a bending strength of up to 14,000 kg/-, which is It has a much higher bending strength than inorganic biomaterials with bioactive functions.
「実施例２コ
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、重量基準で、ＣａＯ４７，８％、ＳｉＯ２
４４．０％、ＭｇＯ１．５％、Ｐ２Ｏ５６，５％、Ｆ
２０．２％となるようにガラスのバッチを調合し、これ
を白金ルツボに入れて１５５０℃で２時間溶融した。"Example 2 Using co-oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, CaO47.8%, SiO2
44.0%, MgO1.5%, P2O56.5%, F
A batch of glass was prepared at a concentration of 20.2%, placed in a platinum crucible, and melted at 1550° C. for 2 hours.
次いで融液を水中に投入し、乾燥後、ボールミルに入れ
て２０μｍ以下（６２５メツシュ以上）の粒度に粉砕し
てガラス粉末を得た。このガラス粉末を、共沈法により
得られた３モル％のＹ２０３を含む部分安定化ジルコニ
アとα−アルミナとからなるジルコニア系微粉末（平均
粒径０．３μｍ）に添加しく体積比で、ジルコニア系微
粉末ニガラス粉末＝８０７２０＞、さらにボールミルを
用いて数時間湿式混合し、乾燥した。得られた、部分安
定化ジルコニアとα−アルミナとの配合比が異なる多数
の混合物のそれぞれを黒鉛型に入れ、３００ｋｇ／ｃＪ
の圧力をかけながら、室温から１２００°Ｃまで一定の
昇温速度３℃／ ｍ ｉ ｎで加熱し、１２００℃で２
時間保持して成形体の結晶化及び焼結を行った。しかる
後、炉内で室温まで冷却し、複合セラミックスを得た。Next, the melt was poured into water, dried, and then placed in a ball mill and pulverized to a particle size of 20 μm or less (625 mesh or more) to obtain glass powder. This glass powder was added to a zirconia-based fine powder (average particle size 0.3 μm) consisting of partially stabilized zirconia containing 3 mol% Y203 and α-alumina obtained by a coprecipitation method. The mixture was wet-mixed using a ball mill for several hours, and then dried. Each of the obtained mixtures with different blending ratios of partially stabilized zirconia and α-alumina was placed in a graphite mold and heated at 300 kg/cJ.
While applying a pressure of
The molded body was crystallized and sintered by holding for a certain period of time. Thereafter, it was cooled to room temperature in a furnace to obtain a composite ceramic.
こうして製造された各複合セラミックスの相対比重は９
６〜９９％であった。また、これら複合セラミックスを
粉砕し、粉末Ｘ線回折により析出結晶相を同定したとこ
ろ、ガラスからはアパタイトとウォラストナイトが析出
していた。さらに、複合セラミックスを３Ｘ４Ｘ３６ｍ
ｍの角柱に加工し、ＪＩＳ Ｒ１６０１に従って三点
曲げ強度試験を行なった。ジルコニア系セラミックス中
に含まれるα−アルミナ含有量（重量百分率）と三点曲
げ強度の関係を第４図に示す。図から明らかなように、
ジルコニア系セラミックス中のα−アルミナ含有量を０
〜９９重量％に亘って変動させた本実施例の無機生体材
料は最高で１５０００ｋｇ／−という曲げ強度を有し、
これまでの生体活性機能を有する無機生体材料に比べて
飛び抜けて高い曲げ強度を有している。The relative specific gravity of each composite ceramic thus manufactured was 9
It was 6-99%. Furthermore, when these composite ceramics were crushed and the precipitated crystal phase was identified by powder X-ray diffraction, apatite and wollastonite were precipitated from the glass. Furthermore, we added composite ceramics to 3x4x36m.
It was processed into a square column of m in diameter and subjected to a three-point bending strength test in accordance with JIS R1601. FIG. 4 shows the relationship between the α-alumina content (weight percentage) contained in the zirconia ceramics and the three-point bending strength. As is clear from the figure,
α-alumina content in zirconia ceramics is reduced to 0.
The inorganic biomaterial of this example varied over ~99% by weight has a bending strength of up to 15000 kg/-,
It has a much higher bending strength than conventional inorganic biomaterials with bioactive functions.
［実施例３コ
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、表−１に示す組成に相当するガラスのバッ
チを調合し、これを白金ルツボに入れて１４５０〜１５
５０℃で２時間溶融した。[Example 3 Using cooxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, a batch of glass corresponding to the composition shown in Table 1 was prepared, and this was placed in a platinum crucible. te1450~15
It was melted at 50°C for 2 hours.
次いで融液を水中に投入し、乾燥後、ボールミルに入れ
て２０μｍ以下（６２５メツシュ以上）の粒度に粉砕し
てガラス粉末を得た。このガラス粉末を、共沈法により
得られた２、５モル％のＹ２Ｏ３を含む部分安定化ジル
コニアからなり、α−アルミナを含まないジルコニア系
微粉末（平均粒径０．３μｍ）に添加しく体積比で、ジ
ルコニア系微粉末ニガラス粉末＝８０：２０）、さらに
ボールミルを用いて数時間湿式混合し、乾燥した。Next, the melt was poured into water, dried, and then placed in a ball mill and pulverized to a particle size of 20 μm or less (625 mesh or more) to obtain glass powder. This glass powder was added to fine zirconia powder (average particle size 0.3 μm), which was made of partially stabilized zirconia containing 2.5 mol% Y2O3 and did not contain α-alumina, obtained by the coprecipitation method. The mixture was wet-mixed using a ball mill for several hours, and then dried.
得られたガラス組成の異なる多数の混合物のそれぞれを
黒鉛型に入れ、３００ｋｇ／ａｄの圧力をかけながら、
室温から１２００℃まで一定の昇温速度３℃／ｍｉｎで
加熱し、１２００℃で２時間保持して成形体の結晶化及
び焼結を行なった。しかる後、炉内で室温まで冷却し、
複合セラミックスを得た。Each of the obtained mixtures with different glass compositions was put into a graphite mold, and while applying a pressure of 300 kg/ad,
The molded body was heated from room temperature to 1200°C at a constant temperature increase rate of 3°C/min and held at 1200°C for 2 hours to crystallize and sinter the molded body. After that, it is cooled to room temperature in the furnace,
Composite ceramics were obtained.
こうして製造された各複合セラミックスの相対比重は９
８〜９９．５％であった。また、これら複合セラミック
スを粉砕し、粉末ＸｕＡ回折により析出結晶相を同定し
た。さらに、複合セラミックスを３Ｘ４Ｘ３６ｍｍの角
柱に加工し、ＪＩＳ Ｒ１６０１に従って、三点曲げ
強度試験を行なった。The relative specific gravity of each composite ceramic thus manufactured was 9
It was 8-99.5%. Furthermore, these composite ceramics were ground, and the precipitated crystal phase was identified by powder XuA diffraction. Further, the composite ceramic was processed into a 3 x 4 x 36 mm square column, and a three-point bending strength test was conducted in accordance with JIS R1601.
ガラス組成、ガラスからの析出結晶相及び三点曲げ強度
を表−１に示す。同表から明らかなように、本実施例の
無機生体材料もこれまでの生体活性機能を有する無機生
体材料に比べて飛び抜けて高い曲げ強度を有している。Table 1 shows the glass composition, crystal phase precipitated from the glass, and three-point bending strength. As is clear from the table, the inorganic biomaterial of this example also has a much higher bending strength than conventional inorganic biomaterials having bioactive functions.
（以下余白）
「発明の効果Ｊ
本発明の無機生体材料は骨と化学的に結合するのに必要
なＣａＯとＰ２Ｏ５を含有し、しかも生体活性機能を有
する従来の材料と比較して飛び抜けて高い曲げ強度を有
しているので、人工骨用及び人工歯根用生体材料として
極めて有用である。(Blank below) "Effects of the Invention J The inorganic biomaterial of the present invention contains CaO and P2O5, which are necessary for chemically bonding with bone, and has an extremely high level of bioactivity compared to conventional materials. Since it has bending strength, it is extremely useful as a biomaterial for artificial bones and artificial tooth roots.
第１図は、出発原料として、ガラス粉末より細かい粒度
を有するジルコニア系粉末を用いて得られた複合セラミ
ックスからなる本発明の無機生体材料の内部の模式図、
第２図は、出発原料として、ガラス粉末より粗い粒度を
有するジルコニア系粉末を用いて得られた複合セラミッ
クスからなる比較の無機生体材料の内部の模式図、第３
図は、複合セラミックス中に含まれる結晶化ガラス含有
量（体積百分率）と曲げ強度の関係図、第４図は、ジル
コニア系セラミックス中に含まれるα−アルミナ含有ｆ
ｆ１（重量百分率）と曲げ強度の関係図である。
１・・・ジルコニア系セラミックス
２・・・結晶化ガラスFIG. 1 is a schematic diagram of the interior of the inorganic biomaterial of the present invention, which is made of a composite ceramic obtained using zirconia powder having a particle size finer than that of glass powder as a starting material;
Figure 2 is a schematic diagram of the interior of a comparative inorganic biomaterial made of composite ceramics obtained using zirconia powder with a coarser particle size than glass powder as a starting material;
The figure shows the relationship between the crystallized glass content (volume percentage) contained in composite ceramics and bending strength. Figure 4 shows the α-alumina content contained in zirconia ceramics.
It is a relationship diagram of f1 (weight percentage) and bending strength. 1... Zirconia ceramics 2... Crystallized glass
Claims (2)
ｉＯ＿２、ＭｇＯ及びＡｌ＿２Ｏ＿３の含有量合計が９
０％以上である組成を有する結晶化ガラスを、重量基準
で１〜１００％の部分安定化ジルコニアと９９〜０％の
α−アルミナとから成るジルコニア系セラミックス中に
、結晶化ガラスとジルコニア系セラミックスとの合計体
積基準で５〜５０％分散させた複合セラミックスからな
ることを特徴とする無機生体材料。(1) Contains the above components in the range of CaO 12-56% P_2O_5 1-27% SiO_2 22-50% MgO 0-34% Al_2O_3 0-25% on a weight basis, CaO, P_2O_5, S
The total content of iO_2, MgO and Al_2O_3 is 9
Crystallized glass having a composition of 0% or more is mixed into a zirconia-based ceramic consisting of 1-100% partially stabilized zirconia and 99-0% α-alumina on a weight basis, and the crystallized glass and zirconia-based ceramic An inorganic biomaterial characterized in that it consists of a composite ceramic in which 5 to 50% of the total volume of the composite ceramics is dispersed.
ｉＯ＿２、ＭｇＯ及びＡｌ＿２Ｏ＿３の含有量合計が９
０％以上である組成を有し、かつ２００メッシュよりも
細かい粒度を有するガラス粉末を、重量基準で１〜１０
０％の部分安定化ジルコニアと９９〜０％のα−アルミ
ナとから成り、前記ガラス粉末よりも細かい粒度を有す
るジルコニア系粉末に、ガラス粉末とジルコニア系粉末
との合計体積基準で５〜５０％混合し、この混合物を所
定の形に成形した後に、この成形体中のガラスからアパ
タイト結晶と、ウォラストナイト、ジオプサイド、フォ
ルステライト、オケルマナイト及びアノルサイトから選
ばれるアルカリ土類ケイ酸塩結晶の１種または２種以上
とが析出する温度域で熱処理し、次いでジルコニア系粉
末の焼結温度域で熱処理することを特徴とする無機生体
材料の製造方法。(2) Contains the above components in the range of CaO 12-56% P_2O_5 1-27% SiO_2 22-50% MgO 0-34% Al_2O_3 0-25% on a weight basis, and contains CaO, P_2O_5, S
The total content of iO_2, MgO and Al_2O_3 is 9
Glass powder having a composition of 0% or more and a particle size finer than 200 mesh, on a weight basis
A zirconia-based powder consisting of 0% partially stabilized zirconia and 99-0% α-alumina and having a finer particle size than the glass powder is added with 5-50% based on the total volume of the glass powder and the zirconia-based powder. After mixing and shaping this mixture into a predetermined shape, apatite crystals and one type of alkaline earth silicate crystals selected from wollastonite, diopside, forsterite, okermanite, and anorthite are extracted from the glass in this molded body. Alternatively, a method for producing an inorganic biomaterial, which comprises heat-treating in a temperature range where two or more types precipitate, and then heat-treating in a sintering temperature range of zirconia-based powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62271677A JPH0622574B2 (en) | 1987-10-29 | 1987-10-29 | Inorganic biomaterial and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62271677A JPH0622574B2 (en) | 1987-10-29 | 1987-10-29 | Inorganic biomaterial and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01115360A true JPH01115360A (en) | 1989-05-08 |
| JPH0622574B2 JPH0622574B2 (en) | 1994-03-30 |
Family
ID=17503336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62271677A Expired - Lifetime JPH0622574B2 (en) | 1987-10-29 | 1987-10-29 | Inorganic biomaterial and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0622574B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011178610A (en) * | 2010-03-02 | 2011-09-15 | Noritake Co Ltd | Zirconia sintered compact, sintering composition for the same and calcined object |
| US8877664B2 (en) | 2009-08-21 | 2014-11-04 | Noritake Co., Limited | Zirconia sintered body, and mixture, pre-sintered compact and pre-sintered calcined body for sintering zirconia sintered body |
| US8987157B2 (en) | 2010-08-20 | 2015-03-24 | Noritake Co., Limited | Sintered zirconia, and composition for sintering and calcined body therefor |
| RU2771017C1 (en) * | 2021-07-06 | 2022-04-25 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing bioactive ceramics based on zirconium dioxide |
-
1987
- 1987-10-29 JP JP62271677A patent/JPH0622574B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8877664B2 (en) | 2009-08-21 | 2014-11-04 | Noritake Co., Limited | Zirconia sintered body, and mixture, pre-sintered compact and pre-sintered calcined body for sintering zirconia sintered body |
| JP2011178610A (en) * | 2010-03-02 | 2011-09-15 | Noritake Co Ltd | Zirconia sintered compact, sintering composition for the same and calcined object |
| US8987157B2 (en) | 2010-08-20 | 2015-03-24 | Noritake Co., Limited | Sintered zirconia, and composition for sintering and calcined body therefor |
| RU2771017C1 (en) * | 2021-07-06 | 2022-04-25 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing bioactive ceramics based on zirconium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0622574B2 (en) | 1994-03-30 |
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