JPH01145064A - Preparation of inorganic bio-material - Google Patents
Preparation of inorganic bio-materialInfo
- Publication number
- JPH01145064A JPH01145064A JP62302817A JP30281787A JPH01145064A JP H01145064 A JPH01145064 A JP H01145064A JP 62302817 A JP62302817 A JP 62302817A JP 30281787 A JP30281787 A JP 30281787A JP H01145064 A JPH01145064 A JP H01145064A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- glass
- alumina
- powder
- ceramic
- 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.)
- Pending
Links
- 239000012620 biological material Substances 0.000 title claims description 28
- 239000011521 glass Substances 0.000 claims abstract description 89
- 239000000919 ceramic Substances 0.000 claims abstract description 66
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 42
- 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 36
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 12
- 238000001513 hot isostatic pressing Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 210000000988 bone and bone Anatomy 0.000 abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 36
- 239000002131 composite material Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 238000005452 bending Methods 0.000 description 16
- 229910052586 apatite Inorganic materials 0.000 description 15
- 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 description 15
- 238000000034 method Methods 0.000 description 13
- 229910052882 wollastonite Inorganic materials 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 239000010456 wollastonite Substances 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000013001 point bending Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 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 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 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 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 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
して使用される無機生体材料のｔＪ造方法に関するもの
である。本発明により得られる無機生体材料は、成形性
、機械的強度に優れているだけでなく、色調が生体骨に
近いという特長を有する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a tJ fabrication method for inorganic biomaterials used as implant materials for artificial bones, artificial tooth roots, and the like. The inorganic biomaterial obtained by the present invention not only has excellent moldability and mechanical strength, but also has a color tone similar to that of living bone.
［背景技術］
骨と化学結合を作る（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−Ｍｏ
Ｏ−８ｉ ０２−Ｐ２Ｏ５：系結晶化ガラスが知られて
いる。また、ｖａｏ−ｃａｏ−Ｐ２Ｏ５：−８ ｉ ０
２系ガラスを２００メツシユよりも細かい粒度に粉砕し
、そのガラス粉末を成形後、ガラス粉末の焼結部ｌ！Ｉ
域で熱処理し、次いでアパタイト結晶［Ｃａｔｏ （Ｐ
Ｏａ ） ｅ （Ｏｏ、５ 。[Background technology] As bioactive ceramics that create chemical bonds with bones, apatite sintered bodies and Na20- to 20-Mo
O-8i 02-P2O5: system crystallized glass is known. Also, vao-cao-P2O5:-8 i 0
After crushing the 2-type glass to a particle size finer than 200 mesh and molding the glass powder, the glass powder is sintered. I
heat treated at
Oa) e (Oo, 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（特開昭５７−１９１２５２号公報）。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
、ウオ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ためにはウオラストナイト結晶
の含為率を高めることが望ましい。そこで、ＳｉＯ２の
含有量を増やし、ウオラストナイト結晶の析出かを増し
た結晶化ガラスも知られている。F)2] and wollastonite crystals [CaSiO3] are also known (Japanese Unexamined Patent Publication No. 191252/1983). 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 SiO2 is increased and the amount of wollastonite crystals precipitated is increased.
ところで、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／ｃＩｉ、Ｎａ２
０−に２０−ＭＱＯ−ＣａＯ−ｓ １ｏ２−Ｐ２Ｏ５：
系結晶化ガラスで１０００〜１５０ＯＮｙ／ａＪ、、
ＭＱＯ−ＣａＯ−Ｐ２Ｏ５：−３ ｉ ０２系結晶化ガ
ラスで１２００〜１４００Ｋｙ／ｃｄ程度である。さら
に、ウオラストナイトを多缶に析出させたＣａ０−Ｐ２
Ｏ３−５ｉ ０２系あるいはＣａ０−Ｐ２Ｏ５：−８
ｉ ０２−ＭＱＯ，Ｙ２０３系結晶化ガラスは１７００
〜２３００Ｋｇ／ｃｉという高い曲げ強度を有している
。By the way, the bending strength of these ceramics is 1000 to 1400 Kg/cIi for apatite sintered body, Na2
0- to 20-MQO-CaO-s 1o2-P2O5:
1000-150ONy/aJ for system crystallized glass.
MQO-CaO-P2O5: -3 i02-based crystallized glass is about 1200 to 1400 Ky/cd. Furthermore, Ca0-P2 with wollastonite precipitated in multiple cans
O3-5i 02 series or Ca0-P2O5:-8
i 02-MQO, Y203 type crystallized glass is 1700
It has a high bending strength of ~2300Kg/ci.
さらに高強度化された材料として結晶化ガラス中にジル
コニア系、アルミナ系、ジルコニア−アルミナ系セラミ
ックス等を分散させたセラミックス複合結晶化ガラスが
本発明者により開発され、特許比＊＜特願昭６２−２７
１６７７号、同６２−２７１６７８号）されている。こ
のセラミックス複合結晶化ガラスは、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、アノルサイト等のアルカリ土類ケイ
酸塩結晶の１種または２種以上とを含有する結晶化ガラ
ス部分が生体親和性に寄与し、ジルコニア系、アルミナ
系、ジルコニア−アルミナ系セラミックスが機械的強度
に寄与しており、３０００υ／ｄ以上という非常に高い
曲げ強度を有しているため、生体材料として極めて有用
である。Furthermore, the present inventor has developed a ceramic composite crystallized glass in which zirconia-based, alumina-based, zirconia-alumina-based ceramics, etc. are dispersed in crystallized glass as a material with higher strength. -27
No. 1677, No. 62-271678). This ceramic composite crystallized glass has a crystallized glass portion containing apatite crystals and one or more types of alkaline earth silicate crystals such as wollastonite, diopside, forsterite, okermanite, and anorthite. Zirconia-based, alumina-based, and zirconia-alumina-based ceramics contribute to mechanical strength, and have extremely high bending strength of over 3000 υ/d, making them extremely useful as biomaterials. be.
［発明が解決しようとする問題点］
上述の特許出願においては、セラミックス複合結晶化ガ
ラスを作製するにあたって、ホットプレス法を採用して
おり、この方法は得られる結晶化ガラスの内部に欠陥の
入る可能性が少ないという特長を有する。しかし、ホッ
トプレス法では焼結体が板状の塊としてのみ得られ、成
形の任意性に欠け、複雑形状をもつ成形材料としては塊
状物の切り出しが必要であり、又切り出し加工の傷が破
壊の原因となることが多いという欠点がある。−方、セ
ラミックス複合結晶化ガラスの混合粉末を所望の形状に
成形し、次いで、結晶の生成温度域で熱処理する常圧焼
成によって得られる焼結体は相対密１１８０〜９５％で
あり、これに起因して曲げ強度は２０００〜２５００Ｋ
ｇ／ｄにとどまっており、この値は、生体材料として用
いるには必ずしも充分に満足できるものではない。[Problems to be Solved by the Invention] In the above-mentioned patent application, a hot pressing method is used to produce ceramic composite crystallized glass, and this method does not allow defects to occur inside the resulting crystallized glass. It has the advantage of having little possibility. However, in the hot press method, the sintered body is obtained only as a plate-shaped lump, which lacks flexibility in shaping, requires cutting out the lump as a molding material with a complex shape, and damage caused by the cutting process can cause damage. The disadvantage is that it often causes - On the other hand, the sintered body obtained by molding the mixed powder of ceramic composite crystallized glass into a desired shape and then heat-treating it in the crystal formation temperature range under normal pressure has a relative density of 1180 to 95%. Therefore, the bending strength is 2000-2500K
g/d, and this value is not necessarily fully satisfactory for use as a biomaterial.
そのため、所望形状のより緻密なセラミックス複合結晶
化ガラスを得るためには、高圧下での焼成が必要であり
、熱間等方加圧成形（ＨＩ Ｐ）が好適である。しかし
、通常の熱間等方加圧成形焼成装置は、モリブデンやグ
ラフフィトヒータを用いてアルゴンやヘリウム等の非酸
化性ガスを圧力媒体とするため、得られた焼結体は微量
の炭素あるいは炭化物を含有し、また焼結体が黒色化す
る。Therefore, in order to obtain a denser ceramic composite crystallized glass with a desired shape, firing under high pressure is necessary, and hot isostatic pressing (HIP) is preferred. However, since ordinary hot isostatic pressing firing equipment uses molybdenum or graphite heaters and uses non-oxidizing gas such as argon or helium as the pressure medium, the resulting sintered body contains trace amounts of carbon or It contains carbides and the sintered body turns black.
このような黒色化した材料を生体内に埋入すると還元部
分や炭化物を含有した部分の生体親和性が劣るようにな
る可能性がある。また、人工歯根を例にとれば、黒色の
人工歯根は天然歯の色調とかなり異なるため、審美性の
点で問題である。If such a blackened material is implanted into a living body, the biocompatibility of the reduced portion or the portion containing carbide may become poor. Furthermore, taking artificial tooth roots as an example, the color tone of black artificial tooth roots is quite different from that of natural teeth, which poses a problem in terms of aesthetics.
従って、本発明の目的は優れた生体親和性を備え、形状
の任意性に優れ、高強度であるだけでなく、生体骨によ
り近い色調を有する無機生体材料のｔＩ造六方法提供す
ることにある。Therefore, an object of the present invention is to provide a method for producing an inorganic biomaterial that not only has excellent biocompatibility, excellent shape flexibility, and high strength, but also has a color tone closer to that of living bone. .
［問題を解決するための手段］
本発明は、上記目的を達成されるためになされたもので
あり、本発明の無機生体材料の製造方法は、重量百分率
で
ＣａＯ１２〜５６
Ｐ２Ｏ５： １〜２７
ＳｉＯ２２２〜５０
ＭＱＯＯ〜３４
Ａｌ２Ｏ２０〜２５
の範囲で上記成分を含有し、ｃａｏ、Ｐ２Ｏ５：、Ｓｉ
Ｏ２、Ｍａｏ及びＡｌ２Ｏ３の含有量合計が９０％以上
である組成を有するガラス粉末に、ジルコニア系セラミ
ックス、アルミナ系セラミックス及びジルコニア−アル
ミナ系セラミックスからなる群から選択される少なくと
も１種のセラミックス粉末を体積百分率で５〜９５％混
合し、この混合物を成形した後、成形体を６００〜１５
００℃で予備焼成し、さらに予備焼成物を酸素を含有す
る圧力媒体ガスを用い、前記予備焼成における圧力より
も高い圧力下に９００〜１５００℃で熱間等方加圧成形
することを特徴とする。[Means for Solving the Problems] The present invention has been made to achieve the above object, and the method for producing an inorganic biomaterial of the present invention includes: CaO12-56 P2O5: 1-27 SiO222 in weight percentages. Contains the above components in the range of ~50MQOO~34Al2O20~25, cao, P2O5:, Si
A volume of at least one ceramic powder selected from the group consisting of zirconia ceramics, alumina ceramics, and zirconia-alumina ceramics is added to a glass powder having a composition in which the total content of O2, Mao, and Al2O3 is 90% or more. After mixing 5 to 95% in percentage and molding this mixture, the molded product is 600 to 15%.
The pre-calcined product is pre-fired at 00°C, and the pre-fired product is hot isostatically pressed at 900-1500°C under a pressure higher than the pressure in the pre-calcination using a pressure medium gas containing oxygen. do.
先ず、本発明の無機生体材料の製造方法において用いら
れるガラス粉末の組成に関し、その量的限定理由を以下
に述べる。First, regarding the composition of the glass powder used in the method for producing an inorganic biomaterial of the present invention, the reason for the quantitative limitation will be described below.
重量百分率で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
の含有量は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、２７％を超える
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、７ノルサイト等のアルカリ土類ケイ
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。ＳｉＯ２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易くなる。When the weight percentage of CaO is less than 12%, the amount of apatite crystals precipitated becomes extremely small. Moreover, when CaO exceeds 56%, the tendency of glass to devitrify becomes significant. Therefore, CaO
The content is limited to 12-56%. P2O5 is 1%
If the P2O5 content is less than 27%, the tendency of the glass to devitrify is significant, and if it exceeds 27%, the amount of alkaline earth silicate crystals such as wollastonite, diopside, forsterite, okermanite, and 7-norsite will decrease. is limited to 1-27%. When SiO2 is less than 22%,
The amount of alkaline earth silicate crystals precipitated is reduced. Moreover, if SiO2 exceeds 50%, the glass tends to devitrify.
従って、３ｉ０２の含量は２２〜５０％に限定される。Therefore, the content of 3i02 is limited to 22-50%.
ＭＯＯ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析出量が少なくなるので、３４％
以下に限定される。同様に、Ａｌ２Ｏ３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。MOO is not an essential component, but if it is included, the amount of apatite crystal precipitation will decrease if it is more than 34%.
Limited to: Similarly, Al2O3 is not an essential component, but if it is included, the amount of apatite crystals produced will decrease if it is more than 25%, so it is limited to 25% or less.
上記した５成分の含有量は９０％以上であり、本発明に
おいて用いられるガラスは、これら５成分に加えて、人
体に有害ではないに２０、Ｌｉ２Ｏ、ＴｉＯ２、ＺｒＯ
２，５ｒＯ１Ｎｂ２０ｓ、Ｂ２０ａ 、Ｆ２ 、Ｙ２０
ａを１０％未満の範囲内で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％以上で
あると、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場合があるので、好ましくは
１０％未満とするのがよい。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Ｙ２Ｏ３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■が低下してしまうので、Ｆ２ 、Ｙ２０３はそ
れぞれ５％以下に限定される。The content of the above-mentioned five components is 90% or more, and in addition to these five components, the glass used in the present invention contains 20, Li2O, TiO2, and ZrO, which are not harmful to the human body.
2,5rO1Nb20s, B20a, F2, Y20
One or more types of a can be contained within a range of less than 10%. If the total amount of these optional components is 10% or more, the amount of apatite crystals and alkaline earth silicate crystals produced may decrease, so it is preferably less than 10%. However, if F2 is more than 5%, the glass tends to devitrify, and if Y2O3 is more than 5%, the formation of apatite crystals and alkaline earth silicate crystals will be reduced. Limited to 5% or less.
本発明の無機生体材料の製造方法においては、上に限定
した組成範囲の母ガラスを好ましくは２００メツシユよ
りも細かい粒度に粉砕した後、これをジルコニア系セラ
ミックス、アルミナ系セラミックス及びジルコニア−ア
ルミナ系セラミックスからなる群から選択される少なく
とも１種のセラミックス粉°末と任意の公知手段で均一
に混合する。母ガラスを２００メツシユよりも細かい粒
度に粉砕した方が好ましい理由は、母ガラスが２００メ
ツシユよりも細かい粒度であると、焼結体中に気孔が残
らず、機械的強度の大きな複合結晶化ガラスを得ること
ができるからである。つまり、気孔が少なく、結晶が均
一に析出し、ジルコニア系、アルミナ系、ジルコニア−
アルミナ系セラミックス粒子が均一に分布した複合結晶
化ガラスを得るためには、２００メツシユよりも細かい
粒度な有する母ガラス粉末を用いることが重要である。In the method for producing inorganic biomaterials of the present invention, the mother glass having the composition range limited above is preferably ground to a particle size finer than 200 mesh, and then this is ground into zirconia ceramics, alumina ceramics, and zirconia-alumina ceramics. and at least one kind of ceramic powder selected from the group consisting of: The reason why it is preferable to grind the mother glass to a particle size finer than 200 mesh is that when the mother glass has a grain size finer than 200 mesh, no pores remain in the sintered body, resulting in composite crystallized glass with high mechanical strength. This is because it is possible to obtain In other words, there are fewer pores, the crystals precipitate uniformly, and zirconia, alumina, zirconia, etc.
In order to obtain a composite crystallized glass in which alumina-based ceramic particles are uniformly distributed, it is important to use a mother glass powder having a particle size finer than 200 mesh.
また母ガラスと混合されるジルコニア系、アルミナ系、
ジルコニア−アルミナ系セラミックスも同様に２００メ
ツシユよりも細かい粒度を有するものが好ましい。その
理由は、ジルコニア系、アルミナ系、ジルコニア−アル
ミナ系セラミックス粉末が２００メツシユよりも細かい
粒度であると、焼結体中に気孔が残らず、機械的強度の
大きな複合結晶化ガラスを得られるからである。つまり
、気孔が少なく、結晶が均一に分布した複合結晶化ガラ
スを得るには、２００メツシユよりも細かい粒度を有す
るガラス粉末と２００メツシユよりも細かい粒度を有す
るジルコニア系、アルミナ系、ジルコニア−アルミナ系
セラミックス微粉末を用いることパ重要である。Also, zirconia-based, alumina-based, which is mixed with the mother glass,
Similarly, it is preferable that the zirconia-alumina ceramic has a particle size finer than 200 mesh. The reason is that if the particle size of the zirconia-based, alumina-based, or zirconia-alumina-based ceramic powder is finer than 200 mesh, no pores will remain in the sintered body, and a composite crystallized glass with high mechanical strength can be obtained. It is. In other words, in order to obtain composite crystallized glass with fewer pores and uniform crystal distribution, glass powder with a particle size finer than 200 mesh and zirconia, alumina, and zirconia-alumina powders with a particle size finer than 200 mesh are required. It is important to use fine ceramic powder.
これらの配合率は体積百分率でガラス粉末９５〜５％、
セラミックス粉末５〜９５％である。その理由はこの範
囲に設定すると生体活性を損わずに強い曲げ強度を有す
る無機生体材料が得られるからである。These blending ratios are glass powder 95-5% by volume;
The ceramic powder is 5-95%. The reason for this is that by setting it within this range, an inorganic biomaterial having strong bending strength can be obtained without impairing bioactivity.
上記の如くして得られたガラス粉末とジルコニア、アル
ミナ、ジルコニア−アルミナ系セラミックス粉末との混
合物を、例えば金型成形、鋳込成形、射出成形、ラバー
プレス成形等の公知の成形手段により所望の形状に成形
した後、成形体を６５０〜１５００℃で予備焼成し、さ
らに予備焼成物を、酸素を含有する圧力媒体ガスを用い
、９００〜１５００℃で熱間等方加圧成形することによ
り、高強度で生体骨に近い色調を有する焼結体を極めて
簡便に得ることができる。A mixture of the glass powder obtained as described above and zirconia, alumina, or zirconia-alumina ceramic powder is molded into a desired shape by known molding means such as mold molding, cast molding, injection molding, and rubber press molding. After shaping into a shape, the molded body is pre-fired at 650 to 1500°C, and the pre-fired product is hot isostatically pressed at 900 to 1500°C using a pressure medium gas containing oxygen. A sintered body with high strength and a color tone similar to that of living bone can be obtained very easily.
予備焼成は上述の如く６５０〜１５００℃の温度で行な
われる。予備焼成温度を６５０〜１５００℃に限定した
理由は、６５０〜１５００℃で成形体を熱処理すると、
焼結体の相対密度は９０％以上に達し、開気孔は存在せ
ず（これは、走査望電子顕微鏡（ＳＥＭ）観察により確
認できる）、この相対密度９０％以上の開気孔のない予
備焼成物を熱間等方加圧成形すると、この加圧成形によ
り相対密度は９５％を超え、極めて緻密な成形体が得ら
れるのに対し、６５０℃未満であると、焼結が不十分で
相対密度９０％に達せず、また１５００℃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、セラミッ
クスと反応してしまうからである。予備焼成の方法とし
ては、焼成・結晶化のための常圧焼成法及び減圧焼成法
のどちらの方法でもよいが減圧焼成法の方がより相対密
度の高い予備焼成物を得ることができる点ですぐれてい
る。なお、熱間等方加圧成形により高密度な焼結体を得
るためには、予備焼成物の相対密度はできるだけ高い方
が望ましい。Prefiring is carried out at a temperature of 650 to 1500°C as described above. The reason why the pre-firing temperature was limited to 650-1500°C is that when the molded body is heat-treated at 650-1500°C,
The relative density of the sintered body reaches 90% or more, and there are no open pores (this can be confirmed by scanning electron microscopy (SEM) observation), and the pre-sintered body has no open pores and has a relative density of 90% or more. When hot isostatically pressed, the relative density exceeds 95% and an extremely dense compact is obtained; however, if the temperature is below 650°C, sintering is insufficient and the relative density is low. If it does not reach 90% and exceeds 1500℃,
This is because the crystallized glass portion may melt and form pores or react with ceramics. As for the pre-firing method, either the normal pressure calcination method or the reduced pressure calcination method for calcination and crystallization may be used, but the reduced pressure calcination method is preferable because it can obtain a pre-fired product with a higher relative density. It is excellent. Note that in order to obtain a high-density sintered body by hot isostatic pressing, it is desirable that the relative density of the pre-fired product be as high as possible.
上記予備焼成の後、得られた予備焼成物を酸素を含有す
る圧力媒体ガスを用い、９００〜１５００℃で熱間等方
加圧成形する。本発明は、この酸素雰囲気下で熱間等方
加圧成形することを主要な特徴とするものであり、これ
により黒色化が防止され生体骨に近い色調を有する無機
生体材料が得られる。After the above pre-calcination, the obtained pre-fired product is hot isostatically pressed at 900 to 1500° C. using a pressure medium gas containing oxygen. The main feature of the present invention is that hot isostatic pressing is performed in this oxygen atmosphere, thereby preventing blackening and producing an inorganic biomaterial having a color tone similar to that of living bone.
圧力媒体ガスの酸素含有部は、０．２〜４０体積％特に
０．５〜２０体積％が好ましい。その理由は、０．２％
より少ないと焼結体の表面が若干黒色化し、４０％より
多いと操作上危険であるからである。The oxygen content of the pressure medium gas is preferably 0.2 to 40% by volume, particularly 0.5 to 20% by volume. The reason is 0.2%
If the amount is less than 40%, the surface of the sintered body will be slightly blackened, and if it is more than 40%, it is dangerous to operate.
熱間等方加圧成形の温度を９００〜１５００℃に限定し
たのは、温度を９００〜１５００℃にすると、結晶を充
分に析出させて焼結体の強度を向上させることが可能と
なるのに対し、９００℃未満であると、強度向上に寄与
する結晶の析出量が少なく、また１５００℃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、セラミ
ックスと反応するからである。The temperature for hot isostatic pressing was limited to 900 to 1500°C because at a temperature of 900 to 1500°C, it is possible to sufficiently precipitate crystals and improve the strength of the sintered body. On the other hand, if the temperature is less than 900°C, the amount of precipitated crystals that contribute to improving strength will be small, and if it exceeds 1500°C, the crystallized glass portion will melt to form pores or react with ceramics.
また、熱間等方加圧成形の圧力は３００Ｋｓ／ｃｓ１以
上とするのが好ましく、その理由は３０ＯＮｇ／ｄ以上
であると気孔が残存することが少ないからである。Further, the pressure of hot isostatic pressing is preferably 300Ks/cs1 or more, because when it is 30ONg/d or more, pores are less likely to remain.
［作用］
本発明は、Ｃａｂ、Ｐ２Ｏ５： 、Ｓ ｉｏ２．ＭａＯ
，Ａｌ２Ｏ３を主成分とするガラス粉末と、ジルコニア
系、アルミナ系、ジルコニア−アルミナ系セラミックス
粉末との所定比率の混合物を成形後、６５０〜１５００
℃で予備焼成し、次いで予備焼成物を９００〜１５００
℃で熱間等方加圧成形するものであり、このような２段
階熱処理を行なうことにより、９５％を超える相対密度
を有する無機生体材料が得られるが、これらの熱処理の
過程において、先ずガラス−セラミックス混合物が焼結
温度域で焼結されて焼結体が得られ、次いで該焼結体中
のガラスがアパタイト結晶及びアルカリ土類ケイ酸塩結
晶析出温度域で結晶化して、アパタイト結晶と、アルカ
リ土類ケイ酸塩結晶の１種または２種以上とを含有する
結晶化ガラスが生成する。（なお上述の焼結温度域はガ
ラス−セラミック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し、熱収縮の開始温度と終了
温度を求めることにより決定され、また、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ガラス
−セラミックス混合物の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ガラス−セラミックス混合粉末
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、その発熱温度と
発熱終了温度を求めることにより決定される。）本発明
により得られるセラミックス複合結晶化ガラスからなる
無機生体材料は、機械的強度に優れているが、その理由
は、結晶化ガラスがウオラストナイト結晶等の機械的強
度の向上に寄与する結晶を含有しているだけでなく、結
晶化ガラス中にセラミックスが分散配合されているので
、主クラックが結晶化ガラス中に分散された高強度高靭
性なセラミックス粒子の周りを偏向して進んだ□す、セ
ラミックス粒子中にクラックが進行する際に大きな破壊
エネルギーを必要とするためである。[Function] The present invention provides Cab, P2O5:, S io2. MaO
, Al2O3 as a main component, and zirconia-based, alumina-based, and zirconia-alumina-based ceramic powders at a predetermined ratio.
Pre-fired at 900-1500°C, then the pre-fired product
It is hot isostatically pressed at a temperature of - The ceramic mixture is sintered in the sintering temperature range to obtain a sintered body, and then the glass in the sintered body is crystallized in the apatite crystal and alkaline earth silicate crystal precipitation temperature range to form apatite crystals. A crystallized glass containing one or more types of alkaline earth silicate crystals is produced. (The above-mentioned sintering temperature range is determined by heating a molded body of glass-ceramic mixed powder at a constant rate, measuring the heat shrinkage during that time, and determining the start and end temperatures of heat shrinkage. The precipitation temperature range of crystals and alkaline earth silicate crystals was determined by analyzing the X-ray diffraction data of glass-ceramic mixed powder heat-treated at the temperature of the exothermic peak in the differential thermal analysis curve of glass-ceramic mixture. (Determined by identifying the precipitated crystal corresponding to the peak and determining its exothermic temperature and exothermic end temperature.) The inorganic biomaterial made of ceramic composite crystallized glass obtained by the present invention has excellent mechanical strength. However, the reason for this is that not only does crystallized glass contain crystals that contribute to improving mechanical strength, such as wollastonite crystals, but also ceramics are dispersed in the crystallized glass, so the main cracks This is because cracks propagate in the ceramic particles by deflecting around the high-strength, high-toughness ceramic particles dispersed in the crystallized glass, which requires a large amount of fracture energy.
また本発明により得られる無機生体材料は生体親和性に
も優れているが、その理由は生体親和性に寄与するアパ
タイト等の結晶を含有するからである。The inorganic biomaterial obtained by the present invention also has excellent biocompatibility, because it contains crystals such as apatite that contribute to biocompatibility.
本発明においては、前記熱間等方加圧成形を酸素を含有
する圧力媒体ガスの雰囲気下で実施するものであり、こ
れにより得られる無機生体材料が生体骨に近い色調を有
するものになるが、その理由は、酸素雰囲気下に熱間等
方加圧成形を行なうと、非酸化性ガス雰囲気下の熱間等
方加圧成形において認められる、焼結体中の炭素や炭化
物の残留やジルコニア等の還元による黒色化を防止でき
るからである。In the present invention, the hot isostatic pressing is carried out in an atmosphere of pressure medium gas containing oxygen, and the inorganic biomaterial obtained thereby has a color tone similar to that of living bone. The reason for this is that when hot isostatic pressing is performed in an oxygen atmosphere, carbon and carbide residues and zirconia in the sintered body, which are observed in hot isostatic pressing in a non-oxidizing gas atmosphere, are removed. This is because it is possible to prevent blackening due to reduction of the like.
［実施例］ 以下実施例を挙げて本発明を更に説明する。[Example] The present invention will be further explained below with reference to Examples.
［実施例１］
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、重量百分率で、ＣａＯ４７，８％、Ｐ２Ｏ
５：６．５％、５ｉＯ２４４゜０％、ＭＱＯｌ、５％、
Ｆ２０．２％となるようにガラスのバッチを調合し、こ
れを白金るつぼに入れて１５５０℃で２時ｍｍ融した。[Example 1] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, the weight percentage was 47.8% CaO, P2O
5:6.5%, 5iO244゜0%, MQOl, 5%,
A batch of glass was prepared to have an F20.2%, and 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２０μ■以下（６２５メツシュ以上）の粒度に粉砕し
た。このガラス粉末に、共沈法により得られた２、５モ
ル％のＹ２０３を含む部分安定化ジルコニアセラミック
ス粉末（平均粒径０．３μｍ）を添加し、さらにボール
ミルを用いて数時間湿式混合し、乾燥した。このセラミ
ックス混合ガラス粉末に、有機バインダーを混合し、射
出成形により、直径５鑓の円柱状に成形した。得られた
成形物の有機バインダーの脱脂を行なった後、成形体を
電気炉に入れ、相対密度９０％以上となるように、６５
０〜１５００℃で１時間保持し、炉内で室温まで冷却し
予備焼成物を得たくなお、本実施例では装置の都合上、
予備焼成後室部まで冷却したが、必ずしも冷却する必要
はなく、冷却しなくても得られたものの特性に変わりは
ない）。さらに、２０００Ｋｇ／ｃｊの圧力をかけなが
ら、室温から１２００℃まで一定の昇温速度３℃／ｓｉ
ｎで加熱し、１２００℃で２時間保持して、酸素を５体
積％含有する圧力媒体ガスの雰囲気下に熱間等方加圧成
形を行なった。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 this glass powder, partially stabilized zirconia ceramic powder (average particle size 0.3 μm) containing 2.5 mol% Y203 obtained by coprecipitation method was added, and further wet-mixed for several hours using a ball mill. Dry. This ceramic mixed glass powder was mixed with an organic binder and molded into a cylindrical shape with a diameter of 5 mm by injection molding. After degreasing the organic binder of the obtained molded product, the molded product is placed in an electric furnace and heated to a relative density of 90% or more.
It is desired to obtain a pre-fired product by holding it at 0 to 1500°C for 1 hour and cooling it to room temperature in the furnace, but in this example, due to the equipment,
Although it was cooled down to the chamber after pre-firing, it is not necessarily necessary to cool it, and the properties of the obtained product do not change even if it is not cooled). Furthermore, while applying a pressure of 2000 Kg/cj, the temperature was raised at a constant rate of 3°C/si from room temperature to 1200°C.
n and held at 1200° C. for 2 hours to perform hot isostatic pressing in an atmosphere of pressure medium gas containing 5% by volume of oxygen.
こうして製造されたセラミックス複合結晶化ガラスの断
面を走査電子顕微１（ＳＥＭ）で観察したところ、いず
れも気孔がほとんど無く緻密であ□す、アルキメデス法
による密度測定をすると相対密度９８％以上であった。When the cross section of the ceramic composite crystallized glass produced in this way was observed using a scanning electron microscope (SEM), it was found that it was dense with almost no pores, and when the density was measured using the Archimedean method, the relative density was over 98%. Ta.
また、これらのセラミックス複合結晶化ガラスを粉砕し
、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オラストナイトが析出してい
た。Furthermore, when these ceramic composite crystallized glasses were crushed and the precipitated crystal phases were identified by powder X-ray diffraction, apatite and wollastonite were precipitated from the glass.
さらに、セラミックス複合結晶化ガラスの三点曲げ強度
試験を行なった。セラミックス複合結晶化ガラス中に含
まれるジルコニアの含有Ｉｌ（体積百分率）と三点曲げ
強度の関係を第１図に示す。図から明らかなように、結
晶化ガラス中にジルコニア系セラミックスを分散させた
セラミックス複合結晶化ガラスからなる本実施例の無機
生体材料の曲げ強度はジルコニア含有量が増すにつれて
高くなり（最高で１４５００ＰＣｇ／ａｉ）、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抜けて
高い曲げ強度を有していた。また得られた無機生体材料
は生体骨と色調を目視により比較したところ、生体骨に
極めて近い色調を有していた。Furthermore, a three-point bending strength test was conducted on the ceramic composite crystallized glass. FIG. 1 shows the relationship between the Il content (volume percentage) of zirconia contained in the ceramic composite crystallized glass and the three-point bending strength. As is clear from the figure, the bending strength of the inorganic biomaterial of this example, which is made of ceramic composite crystallized glass in which zirconia ceramics are dispersed in crystallized glass, increases as the zirconia content increases (up to 14,500 PCg/ ai), it had a much higher bending strength than conventional inorganic biomaterials with bioactive functions. Further, when visually comparing the color tone of the obtained inorganic biomaterial with that of living bone, it was found that the color tone was extremely close to that of living bone.
［実施例２］
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、重量百分率で、ＣａＯ４７，８％、Ｐ２０
Ｓ ６．５％、５ｉＯ２４４゜０％、ＭＣＪＯ１，５％
、Ｆ２０．２％となるようにガラスのバッチを調合し、
これを白金るつぼに入れて１５５０℃で２時間溶融した
。次いで融液を水中に投入し、乾燥後、ボールミルに入
れて２０μ−以下（６２５メツシｌＩＸ上）の粒度に粉
砕した。このガラス粉末に、アルミナセラミックス粉末
（平均粒径１μｍ）を添加し、さらにボールミルを用い
て数時間湿式混合し、乾燥した。[Example 2] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, CaO47.8%, P20 in weight percentage
S 6.5%, 5iO244゜0%, MCJO1.5%
, 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. The melt was then poured into water, dried, and then ground in a ball mill to a particle size of 20 μm or less (on 625 mesh IIX). Alumina ceramic powder (average particle size: 1 μm) was added to the glass powder, wet-mixed using a ball mill for several hours, and then dried.
このセラミックス混合ガラス粉末に、有機バインダーを
混合し、射出成形により、直径５履の円柱状に成形した
。得られた成形物の有機バインダーの脱脂を行なった後
、成形体を電気炉に入れ、相対密度９０％以上となるよ
うに、６５０〜１５００℃で１時間保持し、炉内で室温
まで冷却し予備焼成物を得た。さらに、２０００Ｋｓ／
ｄの圧力をかけながら、室温から１３００℃まで一定の
昇温速度３℃／■ｉｎで加熱し、１３００℃で２時間保
持して、酸素を５体積％含有する圧力媒体ガスの雰囲気
下に熱間等方加圧成形を行なった。This ceramic mixed glass powder was mixed with an organic binder and molded into a cylindrical shape with a diameter of 5 mm by injection molding. After degreasing the organic binder of the obtained molded product, the molded product was placed in an electric furnace and held at 650 to 1500°C for 1 hour so that the relative density was 90% or more, and then cooled to room temperature in the furnace. A pre-fired product was obtained. Furthermore, 2000Ks/
While applying a pressure of Isostatic pressure molding was performed.
こうして製造されたセラミツゲス複合結晶化ガラスをア
ルキメデス法により密度測定をすると相対密度９５〜９
８％であった。また、これらのセラミックス複合結晶化
ガラスを粉砕し、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オラストナイ
トが析出しており、アルミナとの反応相は認められなか
った。When the density of the ceramic composite crystallized glass produced in this way was measured by the Archimedes method, the relative density was 95 to 9.
It was 8%. In addition, when these ceramic composite crystallized glasses were crushed and the precipitated crystal phases were identified by powder X-ray diffraction, apatite and wollastonite were precipitated from the glass, and no reaction phase with alumina was observed. .
さらに、セラミックス複合結晶化ガラスの三点曲げ強度
試験を行なった。セラミックス複合結晶化ガラス中に含
まれるジルコニアの含有量（体積自分率）と三点曲げ強
度の関係を第２図に示す。図から明らかなように、結晶
化ガラス中にアルミナ系セラミックスを分散させたセラ
ミックス複合結晶化ガラスからなる本実施例の無機生体
材料は３５００〜５００ＯＮｙ／ａｊという高い曲げ強
度を有し、また生体骨に極めて近い色調を有していた。Furthermore, a three-point bending strength test was conducted on the ceramic composite crystallized glass. FIG. 2 shows the relationship between the content of zirconia (volume self-percentage) contained in the ceramic composite crystallized glass and the three-point bending strength. As is clear from the figure, the inorganic biomaterial of this example, which is made of ceramic composite crystallized glass in which alumina ceramics are dispersed in crystallized glass, has a high bending strength of 3500 to 500 ONy/aj, and also has a high bending strength of 3500 to 500 ONy/aj. It had a color tone very similar to that of
［実施例３］
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、重層百分率で、ＣａＯ４７，８％、Ｐ２０
Ｓ ６．５％、５ｉＯ２４４゜０％、ＭＯＯ１，５％、
Ｆ２０．２％となるようにガラスのバッチを調合し、こ
れを白金るつぼに入れて１５５０℃で２時間溶融した。[Example 3] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, the layer percentage was 47.8% CaO, P20
S 6.5%, 5iO244゜0%, MOO1.5%,
A batch of glass was prepared to have an F20.2%, and 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２０μ−以下（６２５メツシュ以上）の粒度に粉砕し
た。このガラス粉末に、共沈法により得られた３モル％
のＹ２Ｏ３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−アルミナセラミックス粉末（平
均粒径０．３μｍ）を添加しく体積比で、ガラス粉末；
ジルコニア−アルミナセラミックス粉末−２０： ８０
）、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 ground to a particle size of 20 μm or less (625 mesh or more). To this glass powder, 3 mol% obtained by coprecipitation method
Add zirconia-alumina ceramic powder (average particle size 0.3 μm) consisting of partially stabilized zirconia containing Y2O3 and α-alumina in a volume ratio of glass powder;
Zirconia-alumina ceramic powder-20: 80
), further wet-mixed using a ball mill for several hours, and then dried.
得られた、部分安定化ジルコニアとα−アルミナとの重
量配合比が異なるセラミックス混合ガラス粉末に、有機
バインダーを混合し、射出成形により、直径５ｍの円柱
状に成形した。得られた成形物の有機バインダーの脱脂
を行なった後、成形体を電気炉に入れ、１２００℃で１
時間保持し、炉内で室温まで冷却し予備焼成物を得た。The obtained ceramic mixed glass powders having different weight mixing ratios of partially stabilized zirconia and α-alumina were mixed with an organic binder and molded into a cylindrical shape with a diameter of 5 m by injection molding. After degreasing the organic binder of the obtained molded product, the molded product was placed in an electric furnace and heated at 1200°C for 1 hour.
The mixture was held for a period of time and cooled to room temperature in the furnace to obtain a pre-fired product.
さらに、２０００都／ｊの圧力をかけながら、室温から
１２５０℃まで一定の昇温速度３℃／ｍｉｎで加熱し、
１２５０℃で２時間保持して、酸素を５体積％含有する
圧力媒体ガスの雰囲気下に熱間等方加圧成形を行なった
。Furthermore, while applying a pressure of 2000 m/j, heating from room temperature to 1250°C at a constant temperature increase rate of 3°C/min,
The temperature was maintained at 1250° C. for 2 hours, and hot isostatic pressing was performed in an atmosphere of pressure medium gas containing 5% by volume of oxygen.
こうして製造されたセラミックス複合結晶化ガラスの断
面を走査電子顕微＆ｌＩ（ＳＥＭ）で観察したところ、
いずれも気孔がほとんど無く緻密であり、アルキメデス
法により密度測定をすると相対密度９７％以上であった
。また、これらのセラミックス複合結晶化ガラスを粉砕
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オラストナイトが析出して
いた。When the cross section of the ceramic composite crystallized glass manufactured in this way was observed using a scanning electron microscope (SEM), it was found that
All of them were dense with almost no pores, and the relative density was 97% or more when density was measured using the Archimedes method. In addition, when these ceramic composite crystallized glasses were crushed and the precipitated crystal phase was identified by powder X-ray diffraction,
Apatite and wollastonite were precipitated from the glass.
さらに、セラミックス複合結晶化ガラスの三点曲げ強度
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（重量自分率）と三点曲げ強度の
関係を第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１５３００ 幻／ｃｄもの曲げ強度を有し、これまで
の生体活性ｖ１１１を有する無機生体材料に比べて飛抜
けて高い曲げ強度を有しており、また生体骨に極めて近
い色調を有していた。Furthermore, a three-point bending strength test was conducted on the ceramic composite crystallized glass. FIG. 3 shows the relationship between the α-alumina content (weight self-percentage) contained in zirconia ceramics and three-point bending strength. As is clear from the figure, the inorganic biomaterial of this example in which the α-alumina content in the zirconia ceramic was varied from 0 to 99% by weight has a bending strength of up to 15,300 phantom/cd, It had a much higher bending strength than conventional inorganic biomaterials with bioactivity v111, and also had a color tone extremely close to that of living bone.
［実施例４］
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、これを白金るつぼに入れて１４５０〜１５
５０℃で２時ｒＷＪ溶融した。[Example 4] A batch of glass corresponding to the composition shown in Table 1 was prepared using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, and this was placed in a platinum crucible. Te1450~15
rWJ melting was performed 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２０μ譜以下（６２５メツシュ以上）の粒度に粉砕し
た。このガラス粉末に、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粉末（平均
粒径０．３μｍ）を添加しく体積比で、ガラス粉末：ジ
ルコニア粉末−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。得られた、ガラス組
成が異なるセラミックス混合ガラス粉末に、有機バイン
ダーを混合し、射出成形により、直径５ｍの円柱状に成
形した。冑られた成形物の有機バインダーの脱脂を行な
った後、成形体を電気炉に入れ、表中に示した温度で１
時間保持し、炉内で室温まで冷却し予備焼成物を得た。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). Partially stabilized zirconia powder (average particle size 0.3 μm) containing 2.5 mol% Y2O3 obtained by coprecipitation method was added to this glass powder at a volume ratio of glass powder:zirconia powder -80:20. ), further wet-mixed using a ball mill for several hours, and then dried. The obtained ceramic mixed glass powder with different glass compositions was mixed with an organic binder and molded into a cylinder with a diameter of 5 m by injection molding. After degreasing the organic binder of the molded product, the molded product was placed in an electric furnace and heated for 1 hour at the temperature shown in the table.
The mixture was held for a period of time and cooled to room temperature in the furnace to obtain a pre-fired product.
さらに、２０００ Ｋｇ／ ｃｔｉの圧力をかけながら
、室温から表中に示した温度まで一定の昇温速度３℃／
ｗｉｎで加熱し、所定温度で２時間保持し、酸素を５体
積％含有する圧力媒体ガスの雰囲気下に熱間専決加圧成
形を行なった。Furthermore, while applying a pressure of 2000 Kg/cti, the temperature was raised from room temperature to the temperature shown in the table at a constant heating rate of 3°C/cti.
The sample was heated with a 100% water bottle (Win), held at a predetermined temperature for 2 hours, and subjected to hot-pressing in an atmosphere of a pressure medium gas containing 5% by volume of oxygen.
こうして製造されたセラミックス複合結晶化ガラスの相
対密度をアルキメデス法により測定をすると９８％以上
であった。また、これらのセラミックス複合結晶化ガラ
スを粉砕し、粉末ｘ１！回折により析出結晶相を同定し
た。さらに、セラミックス複合結晶化ガラスの三点曲げ
強度試験を行なった。ガラス組成、ガラスからの析出結
晶相、予備焼成温度、熱同等方加圧成形温度及び三点曲
げ強度を表１に示す。同表から明らかなように、本実施
例の無機生体材料は３０００〜４５０ＯＮｙ／ｄという
高い曲げ強度を有し、また生体骨に極めて近い色調を有
していた。また本実施例により得られた無機生体材料は
、結晶化して生体親和性の向上に寄与するガラス粉末が
ジルコニア粉末よりも多い混合物（体積比でガス粉末：
ジルコニア粉末＝８０ ： ２０）から得られたもので
あり、強度を損わずに生体親和性に特に優れていた。The relative density of the ceramic composite crystallized glass thus produced was 98% or more when measured by the Archimedes method. In addition, these ceramic composite crystallized glasses are crushed to produce powder x1! The precipitated crystal phase was identified by diffraction. Furthermore, a three-point bending strength test was conducted on the ceramic composite crystallized glass. Table 1 shows the glass composition, crystal phase precipitated from the glass, pre-firing temperature, thermal isostatic pressing temperature, and three-point bending strength. As is clear from the table, the inorganic biomaterial of this example had a high bending strength of 3000 to 450 ONy/d, and also had a color tone extremely similar to that of living bone. In addition, the inorganic biomaterial obtained in this example was a mixture containing more glass powder than zirconia powder (volume ratio: gas powder:
It was obtained from zirconia powder (80:20) and had particularly excellent biocompatibility without losing strength.
（以下余白）
［発明の効！ｉ！］
本発明の方法により得られた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
かも非常に高い曲げ強度を有し、なおかつ生体骨に近い
色調であるので、無機生体材料として極めて有用である
。又、熱間方法加圧成形法を用いていることから、複雑
な形状に容易に成形することが可能である。(Left below) [Efficacy of invention! i! ] The inorganic biomaterial obtained by the method of the present invention contains CaO and P2O5 necessary for chemically bonding with bone, has extremely high bending strength, and has a color tone close to that of living bone. Therefore, it is extremely useful as an inorganic biomaterial. Furthermore, since hot pressure molding is used, it is possible to easily mold into complex shapes.
第１図は、本発明により得られたジルコニアセラミック
ス複合結晶化ガラスからなる無機生体材料におけるジル
コニア含有量（ｖｏ１％）と曲げ強度の関係を示すグラ
フ、第２図は本発明により得られたアルミナセラミック
ス複合結晶化ガラスからなる無機生体材料におけるアル
ミナ含有量（ｖｏ１％）と曲げ強度の関係を示すグラフ
、第３図は本発明により得られたジルコニア−アルミナ
セラミックス複合結晶化ガラスからなる無機生体材料に
おけるジルコニア−アルミナセラミックス中のアルミナ
含有［１（ｗｔ％）と曲げ強度の関係を示すグラフであ
る。FIG. 1 is a graph showing the relationship between zirconia content (VO1%) and bending strength in an inorganic biomaterial made of a zirconia ceramic composite crystallized glass obtained by the present invention, and FIG. A graph showing the relationship between alumina content (VO1%) and bending strength in an inorganic biomaterial made of a ceramic composite crystallized glass, and FIG. 3 is an inorganic biomaterial made of a zirconia-alumina ceramic composite crystallized glass obtained by the present invention. It is a graph showing the relationship between alumina content [1 (wt%)] and bending strength in zirconia-alumina ceramics.
Claims (1)
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ガラス粉末に、ジルコニア
系セラミックス、アルミナ系セラミックス及びジルコニ
ア−アルミナ系セラミックスからなる群から選択される
少なくとも１種のセラミックス粉末を体積百分率で５〜
９５％混合し、この混合物を成形した後、成形体を６５
０〜１５００℃で予備焼成し、さらに予備焼成物を酸素
を含有する圧力媒体ガスを用い、前記予備焼成における
圧力よりも高い圧力下に９００〜１５００℃で熱間等方
加圧成形することを特徴とする無機生体材料の製造方法
。(1) Contains the above components in weight percentages of CaO: 12-56 P_2O_5: 1-27 SiO_2: 22-50 MgO: 0-34 Al_2O_3: 0-25, including 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 is mixed with at least one ceramic powder selected from the group consisting of zirconia ceramics, alumina ceramics, and zirconia-alumina ceramics at a volume percentage of 5 to 5%.
After mixing 95% and molding this mixture, the molded body was heated to 65%.
Preliminary firing at 0 to 1500°C, and further hot isostatic pressing of the prefired product at 900 to 1500°C under pressure higher than the pressure in the preliminary firing using a pressure medium gas containing oxygen. Characteristic method for producing inorganic biomaterials.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62302817A JPH01145064A (en) | 1987-11-30 | 1987-11-30 | Preparation of inorganic bio-material |
| US07/159,606 US4960733A (en) | 1987-02-28 | 1988-02-24 | Inorganic biomaterial and process for producing the same |
| DE3806215A DE3806215A1 (en) | 1987-02-28 | 1988-02-26 | INORGANIC BIOMATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62302817A JPH01145064A (en) | 1987-11-30 | 1987-11-30 | Preparation of inorganic bio-material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01145064A true JPH01145064A (en) | 1989-06-07 |
Family
ID=17913454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62302817A Pending JPH01145064A (en) | 1987-02-28 | 1987-11-30 | Preparation of inorganic bio-material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01145064A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011528690A (en) * | 2008-07-21 | 2011-11-24 | ビタ・ゼーンファブリク・ハー・ラウター・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コー・カーゲー | Porous silicate ceramic body, dental restoration, and method for producing the same |
| US9681931B2 (en) | 2008-07-21 | 2017-06-20 | Vita Zahnfabrik H. Rauter Gmbh & Co., Kg | Molded member made of form-stabilized material and method for the manufacture thereof |
| CN111908797A (en) * | 2020-07-28 | 2020-11-10 | 电子科技大学 | Low-thermal-expansion cordierite-based microcrystalline glass material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62231668A (en) * | 1986-04-01 | 1987-10-12 | ホ−ヤ株式会社 | Inorganic bio-material and its production |
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1987
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62231668A (en) * | 1986-04-01 | 1987-10-12 | ホ−ヤ株式会社 | Inorganic bio-material and its production |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011528690A (en) * | 2008-07-21 | 2011-11-24 | ビタ・ゼーンファブリク・ハー・ラウター・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コー・カーゲー | Porous silicate ceramic body, dental restoration, and method for producing the same |
| US20140070435A1 (en) | 2008-07-21 | 2014-03-13 | Vita Zahnfabrik H. Rauter Gmbh & Co. Kg | Porous, silicate, ceramic body, dental restoration and method for the production thereof |
| US9681931B2 (en) | 2008-07-21 | 2017-06-20 | Vita Zahnfabrik H. Rauter Gmbh & Co., Kg | Molded member made of form-stabilized material and method for the manufacture thereof |
| US10266452B2 (en) | 2008-07-21 | 2019-04-23 | Vita Zahnfabrik H. Rauter Gmbh & Co. Kg | Porous, silicate, ceramic body, dental restoration and method for the production thereof |
| US10322973B2 (en) | 2008-07-21 | 2019-06-18 | Vita Zahnfabrik H. Rauter Gmbh & Co. Kg | Porous silicate ceramic body, dental restorations and method for the production thereof |
| CN111908797A (en) * | 2020-07-28 | 2020-11-10 | 电子科技大学 | Low-thermal-expansion cordierite-based microcrystalline glass material and preparation method thereof |
| CN111908797B (en) * | 2020-07-28 | 2022-05-03 | 电子科技大学 | Low-thermal-expansion cordierite-based microcrystalline glass material and preparation method thereof |
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