JP2506826B2 - Granular inorganic molded body and method for producing the same - Google Patents
Granular inorganic molded body and method for producing the sameInfo
- Publication number
- JP2506826B2 JP2506826B2 JP62251845A JP25184587A JP2506826B2 JP 2506826 B2 JP2506826 B2 JP 2506826B2 JP 62251845 A JP62251845 A JP 62251845A JP 25184587 A JP25184587 A JP 25184587A JP 2506826 B2 JP2506826 B2 JP 2506826B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- granular
- particles
- granular inorganic
- inorganic molded
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 72
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 68
- 239000001506 calcium phosphate Substances 0.000 claims description 68
- 235000011010 calcium phosphates Nutrition 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 14
- 210000000988 bone and bone Anatomy 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000002706 hydrostatic effect Effects 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 26
- 229920005830 Polyurethane Foam Polymers 0.000 description 18
- 239000011496 polyurethane foam Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 239000008187 granular material Substances 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 13
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 13
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- -1 calcium phosphate Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 208000031872 Body Remains Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004421 molding of ceramic Methods 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 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 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、リン酸カルシウム、金属酸化物およびその
混合物等の無機化合物からなる顆粒状無機成形体および
その製造方法に関する。顆粒状無機成形体は骨欠損部の
充填材として、また、固定化酵素や触媒の担体として有
用である。TECHNICAL FIELD The present invention relates to a granular inorganic molded article made of an inorganic compound such as calcium phosphate, a metal oxide and a mixture thereof, and a method for producing the same. The granular inorganic molded body is useful as a filler for bone defects and as a carrier for immobilized enzymes and catalysts.
（従来の技術） 顆粒状無機成形体の代表的なものである顆粒状リン酸
カルシウム成形体は、新生骨の形成を促進し、生体の骨
組織と一体化し得る性質をもつているため、骨充填材と
して利用することが試みられている。(Prior Art) A granular calcium phosphate molded body, which is a typical granular inorganic molded body, has the property of promoting the formation of new bone and being able to be integrated with the bone tissue of the living body. It has been tried to use as.
顆粒状リン酸カルシウム成形体の製造方法としては、
（ａ）湿式法で製造したリン酸カルシウムの乾燥物をそ
のまま、または仮焼した後破砕し、ふるいにかけて所望
の大きさにする方法（ジヤーナル・オブ・アメリカン・
ケミカル・ソサエテイ89,5535（1967），特開昭61-2055
8号等）、（ｂ）リン酸カルシウム粉末を高速度攪拌機
でアルコール等を媒体とし加湿しながら攪拌をくりかえ
し、所望の大きさの顆粒体とする方法（特開昭61-4574
8）等が知られている。As a method for producing a granular calcium phosphate molded body,
(A) A dry method of calcium phosphate produced by a wet method, as it is or after calcination, crushing and sieving to a desired size (Journal of American
Chemical Society 89 , 5535 (1967), JP-A-61-2055
No. 8), (b) calcium phosphate powder is repeatedly stirred with a high speed stirrer while moistening with alcohol as a medium to obtain granules having a desired size (JP-A-61-4574).
8) etc. are known.
（発明が解決しようとする問題点） 上記の如き方法で得られた顆粒状リン酸カルシウム成
形体は、個々の粒子がまちまちの形状をしているため、
骨充填材として用いた場合に充填状態が一定でなく、安
定した性能を示さないことが多いという問題があつた。
さらに上記（ａ）の方法で得られた顆粒状リン酸カルシ
ウム成形体には角があるため、骨欠損部に充填する場合
には骨細胞を刺激し、これを壊死させる恐れがあり、ま
た上記（ｂ）の方法で得られた顆粒状リン酸カルシウム
成形体は焼成後も高密度のものは得がたく、骨充填材と
して用いるには機械的強度が弱いという問題もあつた。(Problems to be Solved by the Invention) The granular calcium phosphate compact obtained by the method as described above has individual particles having various shapes,
When it is used as a bone filler, the filling state is not constant and stable performance is often not exhibited.
Further, since the granular calcium phosphate molded body obtained by the method (a) has horns, it may stimulate bone cells and cause necrosis when they are filled in the bone defect portion. The granular calcium phosphate compact obtained by the method (1) has a problem that it is difficult to obtain a high density one even after firing, and the mechanical strength is weak to be used as a bone filling material.
また、これらの方法で所望の大きさの顆粒状物を得よ
うとすると、（ａ）、（ｂ）いずれの場合にも多量の粉
末が発生し、歩留まりが悪いという問題があつた。Further, when trying to obtain a granular material having a desired size by these methods, a large amount of powder is generated in both cases (a) and (b), and there is a problem that the yield is poor.
したがつて、本発明の目的は、骨充填材等として有用
な形状のそろつた顆粒状無機成形体とくにリン酸カルシ
ウム成形体を得ることである。また、本発明の別の目的
はかかる顆粒状無機成形体を高収率で製造することであ
る。Therefore, an object of the present invention is to obtain a granular inorganic molded product having a uniform shape, particularly a calcium phosphate molded product, which is useful as a bone filler or the like. Another object of the present invention is to produce such a granular inorganic molded article in high yield.
（問題点を解決するための手段） 本発明によれば上記目的の１つは、最大径をＤとし、
最大径に対し垂直方向の最大の長さをＡとしたとき、A/
Dが0.5〜0.9であり、かつＤに交わるＡの位置がＤの中
心より両側0.3Dの範囲内に入る粒子の数が全粒子数の80
％以上であることを特徴とする顆粒状無機成形体を提供
することによって達成され、また上記目的の他の１つ
は、三次元網状構造を有する有機多孔体の中に焼成可能
な無機粉末を入れて加圧成形を行って、多孔体の孔の中
に顆粒状の無機成形体を形成し、しかる後該有機多孔体
を焼去するとともに、該無機成形体を焼成することを特
徴とする顆粒状無機成形体の製造法を提供することによ
って達成される。(Means for Solving Problems) According to the present invention, one of the above objects is to set the maximum diameter to D,
If the maximum length in the vertical direction with respect to the maximum diameter is A, then A /
D is 0.5 to 0.9, and the number of particles in which the position of A intersecting D falls within 0.3D on both sides from the center of D is 80 of the total number of particles.
% Or more, it is achieved by providing a granular inorganic molded body, and another one of the above objects is to provide a calcinated inorganic powder in an organic porous body having a three-dimensional network structure. It is characterized in that it is put in and pressure-molded to form a granular inorganic molded body in the pores of the porous body, and thereafter the organic porous body is burned off and the inorganic molded body is burned. This is achieved by providing a method for producing a granular inorganic molded body.
本発明の顆粒状無機成形体を構成する無機成分として
は、下記の如きリン酸カルシウムを主成分とするものお
よび金属酸化物を主成分とするものがあげられる。Examples of the inorganic component that constitutes the granular inorganic molded body of the present invention include those containing calcium phosphate as a main component and those containing a metal oxide as a main component as described below.
（１）正リン酸カルシウム、ヒドロキシアパタイト、リ
ン酸四カルシウム、オキシアパタイト、ピロリン酸カル
シウム、フツ素アパタイト、ヒドロキシアパタイトの水
酸基の一部がフツ素イオンで置換された化合物およびこ
れらの混合物等のリン酸カルシウム。とくに、正リン酸
カルシウムならびにヒドロキシアパタイトもしくはこれ
らの混合物が好ましい。他の無機粉末たとえばアルミ
ナ、ジルコニア等の金属酸化物を上記リン酸カルシウム
粉末に少量（約20重量％以下）混合することも可能であ
る。(1) Calcium phosphate such as orthocalcium phosphate, hydroxyapatite, tetracalcium phosphate, oxyapatite, calcium pyrophosphate, fluorine apatite, a compound in which a part of hydroxyl groups of hydroxyapatite is substituted with fluorine ion, and a mixture thereof. Particularly, calcium orthophosphate, hydroxyapatite, or a mixture thereof is preferable. It is also possible to mix a small amount (less than about 20% by weight) of another inorganic powder, for example, a metal oxide such as alumina or zirconia, with the calcium phosphate powder.
（２）アルミナ、ジルコニア、チタニア、シリカ、シリ
カアルミナまたはこれらの混合物等の金属酸化物。(2) A metal oxide such as alumina, zirconia, titania, silica, silica-alumina or a mixture thereof.
本発明の顆粒状無機成形体は、前述のように最大径を
Ｄとし、最大径に対し垂直方向の最大の長さをＡとした
とき、A/Dが0.5〜0.9であり、かつＤに交わるＡの位置
がＤの中心より両側0.3Dの範囲内に入る粒子の数が全粒
子数の80％以上であることを特徴としていることから、
粒子群を構成している個々の粒子の形状が一定してお
り、このため、常に安定した性能が得られる。かかる粒
子形状の測定は、電子顕微鏡写真にもとづいて行うこと
ができる。The granular inorganic molded body of the present invention has an A / D of 0.5 to 0.9 and a D of 0.5 when the maximum diameter is D and the maximum length in the direction perpendicular to the maximum diameter is A as described above. Since the number of particles where the position of intersecting A falls within 0.3D on both sides from the center of D is 80% or more of the total number of particles,
The shape of the individual particles constituting the particle group is constant, and therefore stable performance is always obtained. The particle shape can be measured based on an electron micrograph.
A/Dが0.5以下のときには、顆粒状成形体は角を有して
いるためにくだけ易く、また、A/Dが0.9以上の顆粒状成
形体の場合には、かかる成形体をち密に充填するのが容
易ではなく、また、充填された成形体が動き易いという
問題がある。さらにまた、上記の如き粒子数が80％以下
の場合には、一定した充填状態を得ることが困難であ
る。When the A / D is 0.5 or less, it is easy to scrape because the granular molded product has corners, and when the granular molded product has an A / D of 0.9 or more, it is densely packed. There is a problem that it is not easy to do, and the filled molded body is easy to move. Furthermore, when the number of particles is 80% or less as described above, it is difficult to obtain a constant filling state.
本発明の顆粒状無機成形体は以下に述べるように三次
元網状構造を有する有機多孔体の孔のなかに無機粉末を
入れて加圧成形し、ついで、有機多孔体を焼去すること
により得られるため、本発明の顆粒状無機成形体は前述
のように個々の粒子の形状がそろつており、角がないだ
けでなく、さらに、加圧する圧力および焼成温度によつ
ては成形体そのものが高密度であり、用いる有機多孔体
の孔の形状によつては、多面体状であり、また、粒子表
面には線状のみぞが見られることもあるのが特徴であ
る。The granular inorganic molded body of the present invention is obtained by putting the inorganic powder in the pores of the organic porous body having a three-dimensional network structure as described below, pressure molding, and then burning off the organic porous body. Therefore, in the granular inorganic molded body of the present invention, the shape of each particle is uniform as described above, and not only there are no corners, but also the molded body itself is high depending on the pressure to be applied and the firing temperature. The density is a feature, and depending on the shape of the pores of the organic porous material used, it is a polyhedron shape, and linear grooves may be seen on the particle surface.
本発明の顆粒状無機成形体は、前述の如きリン酸カル
シウム、金属酸化物を主成分とする無機化合物の粉末を
有機多孔体の孔のなかで加圧成形することにより得られ
るが、本発明において用いられる原料粉末の大きさは通
常0.5μ〜500μのものが用いられ、とくに１〜200μが
好ましく、得ようとする顆粒の大きさによつて適宜選択
される。また、粉末中の水分は５％以下であることが望
ましい。The granular inorganic molded body of the present invention can be obtained by pressure-molding powder of an inorganic compound containing calcium phosphate or a metal oxide as a main component as described above in the pores of an organic porous body. The size of the raw material powder to be used is usually 0.5 μ to 500 μ, particularly preferably 1 to 200 μ, and is appropriately selected depending on the size of the granules to be obtained. The water content in the powder is preferably 5% or less.
本発明において用いられる三次元網状構造の有機多孔
体としては、たとえばポリウレタン発泡体があげられ
る。該ポリウレタン発泡体のセルの大きさおよび形状は
発泡体の製造条件により調節することができ、したがつ
て顆粒状無機成形体の大きさおよび形状は該ポリウレタ
ン発泡体のセルの大きさおよび形状を選択することによ
り、変化させることができる。かかる発泡体を用いるこ
とにより、通常の顆粒体の大きさである最大径が0.1〜2
mmまでの顆粒状無機成形体を製造することが可能であ
る。こゝで、三次元網状構造をもつ多孔体は該ポリウレ
タン発泡体に限定されるものではなく、該ポリウレタン
発泡体と同様のセルの大きさおよび形状をもつ有機多孔
体であればいずれも使用可能であり、ポリエチレン、ポ
リスチレン製のものなども用いられる。空孔率はできる
だけ大きいことが好ましく、所望の形状の無機成形体が
収率よく得られる。空孔の孔径分布は均一なものである
ことが、形状のそろつた粒子群を高収率で得るために必
要であるが、市販されている三次元網状構造を有する多
孔体は通常本発明の顆粒状無機成形体を得るに十分な均
一性を有している。Examples of the organic porous body having a three-dimensional network structure used in the present invention include polyurethane foam. The size and shape of the cells of the polyurethane foam can be adjusted depending on the production conditions of the foam, and thus the size and shape of the granular inorganic molded article can be adjusted to the size and shape of the cells of the polyurethane foam. It can be changed by selecting it. By using such a foam, the maximum diameter, which is the size of a normal granule, is 0.1 to 2
It is possible to produce granular inorganic compacts up to mm. Here, the porous body having a three-dimensional network structure is not limited to the polyurethane foam, and any organic porous body having the same cell size and shape as the polyurethane foam can be used. Also, polyethylene, polystyrene, etc. may be used. It is preferable that the porosity be as large as possible, and an inorganic molded article having a desired shape can be obtained in good yield. It is necessary for the pore size distribution of the pores to be uniform in order to obtain a uniform group of particles in a high yield, but a commercially available porous body having a three-dimensional network structure is usually used in the present invention. It has sufficient homogeneity to obtain a granular inorganic molded body.
上記の有機多孔体に無機粉末が充填され、加圧成形が
行われる。加圧成形としてはセラミツクの成形において
用いられている等方圧力成形、なかでも静水圧成形が好
ましい。静水圧成形において、有機多孔体はラバー型
（通常ゴム製であるが、ゴム以外の弾性体でつくられて
いてもよい）に密着して挿入され、これに無機粉末が充
填される。The above organic porous body is filled with inorganic powder, and pressure molding is performed. As the pressure molding, isotropic pressure molding, which is used in the molding of ceramics, is preferably hydrostatic molding. In the hydrostatic molding, the organic porous body is inserted in close contact with a rubber mold (which is usually made of rubber, but may be made of an elastic body other than rubber), and is filled with inorganic powder.
該無機粉末が充填された多孔体が挿入されたラバー型
は静水圧成形法（ラバープレス法ともいう）によりプレ
スされるが、プレス圧は通常300kg/cm2〜6000kg/cm2で
ある。プレス圧が300kg/cm2以下では、充分な強度をも
つ成形体を得ることが難しい。また、プレス圧が6000kg
/cm2以上では、以後焼成した場合に部分的に顆粒状無機
焼結体にひびわれが起こつて好ましくない。上記のよう
な加圧成形が行われることにより無機粉末は多孔体の孔
のなかで顆粒状となる。Although the rubber-type porous material inorganic powder is filled is inserted is pressed by a hydrostatic pressing method (also referred to as a rubber press method), press pressure is usually 300kg / cm 2 ~6000kg / cm 2 . If the pressing pressure is 300 kg / cm 2 or less, it is difficult to obtain a molded product having sufficient strength. Also, the press pressure is 6000 kg
If it is / cm 2 or more, the granular inorganic sintered body is partially cracked when it is subsequently fired, which is not preferable. By performing the pressure molding as described above, the inorganic powder becomes granular in the pores of the porous body.
加圧成形が行われたあと、有機多孔体を焼去すること
により顆粒状の無機成形体を取り出すことができる。同
時に無機成形体は焼成され、高密度となり、機械的強度
が増す。After the pressure molding is performed, the granular inorganic molded body can be taken out by burning off the organic porous body. At the same time, the inorganic molded body is fired to have a high density and mechanical strength.
リン酸カルシウム成形体の場合には、加熱は500℃以
上、1400℃以下で行われることが好ましく、さらに好ま
しくは加熱温度は600℃以上、1300℃以下である。500℃
以下では、リン酸カルシウム焼結体中に有機多孔体の炭
素が残存し、好ましくない。1400℃以上では得られたリ
ン酸カルシウム焼結体にひび割れがおこり易い。多孔性
の顆粒状リン酸カルシウム焼結体が必要な場合には900
℃以下の温度で、また、緻密な顆粒物（相対密度90％以
上）が必要な場合には900℃以上の温度で焼成すること
が望ましい。また、金属酸化物成形体の場合には、加熱
は、500℃以上、2000℃以下で行われることが好まし
い。500℃以下では、金属酸化物焼結体中に有機多孔体
の炭素が残存し、好ましくない。200℃以上では得られ
た金属酸化物焼結体にひび割れがおこり易い。多孔性の
顆粒状金属酸化物焼結体が必要な場合には例えばアルミ
ナでは1300℃以下の温度で、また、緻密な顆粒物（相対
密度90％以上）が必要な場合には1300℃以上の温度で焼
成することが望ましい。In the case of a calcium phosphate compact, heating is preferably performed at 500 ° C or higher and 1400 ° C or lower, and more preferably the heating temperature is 600 ° C or higher and 1300 ° C or lower. 500 ° C
In the following, carbon of the organic porous body remains in the calcium phosphate sintered body, which is not preferable. At 1400 ° C or higher, the obtained calcium phosphate sinter tends to crack. 900 if porous granular calcium phosphate sinter is required
It is desirable to calcine at a temperature of ℃ or lower, or at a temperature of 900 ℃ or higher when a dense granule (relative density of 90% or higher) is required. In the case of a metal oxide molded body, heating is preferably performed at 500 ° C or higher and 2000 ° C or lower. If the temperature is 500 ° C. or lower, carbon of the organic porous material remains in the metal oxide sintered body, which is not preferable. Cracks are likely to occur in the obtained metal oxide sintered body at 200 ° C or higher. When a porous granular metal oxide sintered body is required, for example, at a temperature of 1300 ° C or lower for alumina, and at a temperature of 1300 ° C or higher when dense granules (relative density of 90% or more) are required. It is desirable to fire at.
（発明の効果） 以上のように、三次元網目構造を有する有機多孔体の
孔のなかに無機粉末を入れて加圧成形を行ない、しかる
後有機多孔体を焼去することにより、形状のそろつた顆
粒状無機成形体を高収率で得ることができる。本発明の
方法により得られた顆粒状物は形状がそろつているため
充填状態が安定しているだけでなく、角がないので骨充
填材として優れたものである。また、加圧条件・焼成条
件によつては相対密度90％以上の高密度を有し、機械的
強度の高いものが得られる。さらにまた、用いる有機多
孔体の孔の形状によつては、得られた顆粒状物は多面体
形状を有しており、顆粒体表面には線状のみぞがみられ
ることもある。また、本発明の方法は、顆粒状物が高収
率で得られるだけでなく、操作が簡単であるというのも
利点である。(Effects of the Invention) As described above, the inorganic powder is put into the pores of the organic porous body having a three-dimensional network structure to perform pressure molding, and then the organic porous body is burned off to obtain a uniform shape. The granular inorganic molded body can be obtained in high yield. The granular material obtained by the method of the present invention has a uniform shape because of its uniform shape, and it is excellent as a bone filler because it has no corners. Further, depending on the pressurizing condition and the firing condition, a material having a high density of 90% or more in relative density and high mechanical strength can be obtained. Further, depending on the shape of the pores of the organic porous material used, the obtained granular material has a polyhedral shape, and linear grooves may be seen on the surface of the granular material. Further, the method of the present invention is advantageous not only in that a granular product can be obtained in a high yield, but also that the operation is simple.
（実施例） 実施例１ 太平化学（株）製リン酸カルシウム粉末（Ca/P原子比
＝1.67、粉末の粒径５〜20μ、比表面積59m2/g）を、ラ
バー型（内容積2cm×5cm×5cm）に挿入したブリヂスト
ン製ポリウレタンフオーム「エバーライトスコツトフイ
ルター」（HR-13、セル数11〜16ケ/25mm、空孔率97％）
10個にそれぞれ充填しこれをラバープレスにより2000kg
/cm2の圧力でプレスした。ラバープレス後、該リン酸カ
ルシウム粉末を含むポリウレタンフオーム（該リン酸カ
ルシウム粉末はフオームの孔の中で顆粒状になつてい
る）を電気炉に入れ、500℃で３時間、さらに1200℃ま
で昇温してから２時間焼成した。このようにして得られ
た顆粒状リン酸カルシウム焼結成形体をふるいにかけ、
12〜28メツシユ（目開き580〜1400μ）の楕円球状リン
酸カルシウム焼結体326gを得た。ポリウレタンフオーム
10個に充填したリン酸カルシウム粉末340gに対し、得ら
れた顆粒状リン酸カルシウム焼結体の収率は96％であつ
た。また、該リン酸カルシウム焼結体の相対密度は、窒
素圧入法で測定した結果、98.3％であり、高密度のもの
が得られた。Example 1 Calcium phosphate powder manufactured by Taihei Chemical Co., Ltd. (Ca / P atomic ratio = 1.67, powder particle size 5 to 20 μm, specific surface area 59 m 2 / g) was put into a rubber mold (internal volume 2 cm × 5 cm ×). Bridgestone polyurethane foam "Everlight Scott Filter" (HR-13, 11 to 16 cells / 25 mm, porosity 97%)
2000kg each with 10 pieces filled with rubber press
Pressed at a pressure of / cm 2 . After rubber pressing, the polyurethane foam containing the calcium phosphate powder (the calcium phosphate powder is in the form of granules in the pores of the foam) is placed in an electric furnace, and the temperature is raised to 1200 ° C for 3 hours at 500 ° C. It was baked for 2 hours. Sieve the granular calcium phosphate sinter compact thus obtained,
326 g of an elliptic spherical calcium phosphate sinter having a size of 12 to 28 mesh (opening of 580 to 1400 μ) was obtained. Polyurethane foam
The yield of the obtained granular calcium phosphate sinter was 96% with respect to 340 g of calcium phosphate powder filled in ten pieces. The relative density of the calcium phosphate sinter was 98.3% as a result of measurement by the nitrogen press-in method, and a high density was obtained.
得られたリン酸カルシウム焼結体50個を電子顕微鏡写
真（倍率26倍、粒子４〜６個を一枚の写真にとる。写真
枚数10）により観察し、ＤおよびＡを測定した結果A/D
は0.76であり、また、Ｄに交わるＡの位置がＤの中心よ
り両側0.3Dの範囲内に入る粒子の数は全粒子数の92％で
あつた。50 pieces of the obtained calcium phosphate sinters were observed by an electron microscope photograph (magnification: 26 times, 4 to 6 particles are taken in one photograph. The number of photographs is 10), and D and A were measured. A / D
Was 0.76, and the number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 92% of the total number of particles.
この顆粒を犬の顎骨に形成した空洞内に充填し、30日
後と殺し、標本を作成した。本標本により組織を観察し
た結果、該リン酸カルシウム成形体の間隙は完全に新生
骨により満たされていた。The granules were filled in the cavity formed in the jawbone of a dog and killed after 30 days to prepare a specimen. As a result of observing the tissue with this sample, the voids of the calcium phosphate molded body were completely filled with new bone.
実施例２ 実施例１において太平化学（株）製リン酸カルシウム
粉末のかわりに三井東圧化学（株）製ヒドロキシアパタ
イト粉末HCA-100S（Ca/P原子比＝1.67、粉末の粒径10〜
100μ、比表面積６m2/g）を使用する以外は、実施例１
と同様の方法で顆粒状ヒドロキシアパタイト焼結体を製
造した。ポリウレタンフオームに充填した該ヒドロキシ
アパタイト粉末362gに対し、得られた12〜28メツシユ
（目開き580〜1400μ）楕円球状ヒドロキシアパタイト
焼結成形体は333gであり、収率は92％であつた。また、
該ヒドロキシアパタイト焼結体の相対密度は94.5％であ
つた。Example 2 Instead of the calcium phosphate powder manufactured by Taihei Chemical Co., Ltd. in Example 1, hydroxyapatite powder HCA-100S manufactured by Mitsui Toatsu Chemicals, Inc. (Ca / P atomic ratio = 1.67, particle size of powder 10 to
Example 1 except using 100μ, specific surface area 6m 2 / g)
A granular hydroxyapatite sintered body was manufactured in the same manner as in. With respect to 362 g of the hydroxyapatite powder filled in the polyurethane foam, the obtained 12-28 mesh (opening 580-1400μ) elliptic spherical hydroxyapatite sintered compact was 333 g, and the yield was 92%. Also,
The relative density of the hydroxyapatite sintered body was 94.5%.
実施例１と同様にして、該ヒドロキシアパタイト焼結
体のＤおよびＡを測定した結果A/Dは0.72であり、ま
た、Ｄに交わるＡの位置がＤの中心より両側0.3Dの範囲
内に入る粒子の数は全粒子数の85％であつた。As a result of measuring D and A of the hydroxyapatite sintered body in the same manner as in Example 1, A / D was 0.72, and the position of A intersecting with D was within 0.3D on both sides from the center of D. The number of entering particles was 85% of the total number of particles.
実施例３ 市販硝酸カルシウム［Ca(NO3)2・4H2O］2500gを蒸溜
水7lに溶解し、この溶液に28％アンモニア水7.9lを徐々
に加え、さらにこの溶液を蒸溜水3lで希釈した。一方、
市販リン酸水素アンモニウム［(NH4)2HPO4］840gを10l
の蒸溜水に溶解し、さらにこの溶液に28％アンモニア水
4.8lと蒸溜水10lとを追加した。前者の硝酸カルシウム
水溶液を20℃に保ちながら、該水溶液中に後者のリン酸
水素アンモニウムの水溶液（20℃）を攪拌下に滴々加え
て反応させた。滴下が終つた後、さらに攪拌を続けなが
ら上記混合液を加熱し（80℃）、還流下に20分保持し、
冷却後さらに２日間静置した。続いて該溶液をポリプロ
ピレン製濾布（1000メツシユ）をとりつけた遠心脱水機
で脱水し（2000G）、さらに蒸溜水でアルカリ性を示さ
なくなるまで洗滌した。このようにして得られたリン酸
カルシウム濾過ケーク体を乾燥後乳バチで粉砕し、140
メツシユのふるいを通過させてリン酸カルシウム粉末92
0gを得た。該リン酸カルシウム粉末を、実施例１と同様
のラバー型に挿入したブリヂストン製ポリウレタンフオ
ーム「エバーライトスコツトフイルター」（HR-20、セ
ル数17〜25ケ/25mm、空孔率97％）18個にそれぞれ充填
し、３個１組として第１表のように６種のプレス圧によ
りラバープレスし、これらを電気炉に入れ1100℃まで昇
温し、さらに1100℃で２時間焼成した。EXAMPLE 3 Commercially available calcium nitrate [Ca (NO3) 2 · 4H 2 O] 2500g was dissolved in distilled water 7l, gradually added 28% aqueous ammonia 7.9l to the solution and further diluting the solution with distilled water 3l . on the other hand,
Commercially available ammonium hydrogen phosphate [(NH4) 2 HPO 4 ] 840 g 10 l
Dissolved in distilled water and 28% ammonia water in this solution.
4.8 l and distilled water 10 l were added. While maintaining the former aqueous solution of calcium nitrate at 20 ° C., the latter aqueous solution of ammonium hydrogen phosphate (20 ° C.) was added dropwise to the solution under stirring to react. After the dropping was completed, the above mixed solution was heated (80 ° C.) while continuing stirring, and kept under reflux for 20 minutes,
After cooling, it was allowed to stand for another 2 days. Subsequently, the solution was dehydrated by a centrifugal dehydrator equipped with a polypropylene filter cloth (1000 mesh) (2000 G), and further washed with distilled water until it did not show alkalinity. The calcium phosphate filter cake thus obtained was dried and then crushed with a dairy bee,
Pass through a mesh sieve and calcium phosphate powder 92
I got 0g. Bridgestone polyurethane foam "Everlight Scott Filter" (HR-20, cell number 17-25 cells / 25 mm, porosity 97%) inserted into the same rubber mold as in Example 1 into 18 pieces of the calcium phosphate powder. Each of them was filled, and rubber was pressed by 6 kinds of pressing pressure as shown in Table 1 as a set of 3 pieces, and these were placed in an electric furnace, heated to 1100 ° C., and further baked at 1100 ° C. for 2 hours.
このように焼成して得られた楕円球状リン酸カルシウ
ム焼結成形体をふるいにかけ、20〜42メツシユ（目開き
400〜830μ）の楕円球状リン酸カルシウム焼結体を第１
表に示すような収率で得た。なお、該リン酸カルシウム
焼結体のＸ線回析線はヒドロキシアパタイトと一致して
いた。The spheroidal calcium phosphate sintered compact obtained by firing in this way is sieved, and 20 to 42 mesh (opening)
400-830μ) elliptic spherical calcium phosphate sinter
The yield was as shown in the table. The X-ray diffraction line of the calcium phosphate sinter was in agreement with that of hydroxyapatite.
比較例１ 実施例３と同様の方法でリン酸カルシウム濾過ケーク
体を作製した。該リン酸カルシウムを乾燥後、ハンマー
ミルで破破し、得られた破砕状リン酸カルシウムを実施
例３と同様の温度で焼成した。 Comparative Example 1 A calcium phosphate filter cake was prepared in the same manner as in Example 3. After the calcium phosphate was dried, it was ruptured with a hammer mill, and the obtained crushed calcium phosphate was calcined at the same temperature as in Example 3.
このようにして焼成して得られた破砕状リン酸カルシ
ウム焼結成形体をふるいにかけ20〜42メツシユ（目開き
400〜830μ）の顆粒状リン酸カルシウム焼結成形体420g
を取得した。ゼラチン状リン酸カルシウム沈澱物の理論
値1060gに対し、得られた顆粒状リン酸カルシウム焼結
体の収率は40％であつた。該リン酸カルシウム焼結体の
相対密度は99.2％であつたが、顆粒のほとんどは鋭い角
をもつていた。実施例１と同様にして該顆粒状リン酸カ
ルシウム焼結体のＤおよびＡを測定した結果、A/Dは0.5
2であり、また、Ｄに交わるＡの位置がＤの中心より両
側0.3Dの範囲内に入る粒子の数は全粒子数の52％であつ
た。The crushed calcium phosphate sinter compacts obtained by firing in this way are sieved to 20-42 mesh (opening).
400 ~ 830μ) granular calcium phosphate sintered compact 420g
Got The yield of the obtained granular calcium phosphate sinter was 40% based on the theoretical value of 1060 g of gelatinous calcium phosphate precipitate. The relative density of the calcium phosphate sinter was 99.2%, but most of the granules had sharp corners. When D and A of the granular calcium phosphate sinter were measured in the same manner as in Example 1, the A / D was 0.5.
The number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 52% of the total number of particles.
該顆粒を実施例１と同様にして犬の顎骨内に埋込し、
実施例１と同様の期間埋入後、組織を観察した結果該リ
ン酸カルシウム焼結体の間隙には新生骨とともに多数の
結合組織が認められた。The granules were embedded in the jawbone of a dog in the same manner as in Example 1,
After embedding for the same period as in Example 1, the tissue was observed, and as a result, many connective tissues were found in the gaps of the calcium phosphate sintered body together with the new bone.
比較例２ 実施例３において遠心脱水機で脱水・洗滌して得られ
たリン酸カルシウム沈澱物を濾過ケーク体のまゝ実施例
１と同様の温度で乾燥させた。乾燥後のリン酸カルシウ
ム濾過ケーク体を直径30cmの乳バチに入れ、リン酸カル
シウムの乾燥体の95％以上が８メツシユ（目開き2.0m
m）のふるいを通過するようにし、かつ、16〜32メツシ
ユ（500〜1000μ）の間のリン酸カルシウム乾燥体の量
が最大となるよう破砕をおこなつた。破砕により得られ
た顆粒状のリン酸カルシウム乾燥体を電気炉に入れ実施
例１と同様の温度で焼成した。このようにして得られた
リン酸カルシウム焼結体を再びふるいにかけ実施例１と
同様の大きさである20〜42メツシユ（目開き400〜830
μ）の顆粒状リン酸カルシウム焼結成形体を350g取得し
た。ゼラチン状リン酸カルシウム沈澱物の理論値1060g
にたいし得られた顆粒状リン酸カルシウム焼結体の収率
は33％であつた。残りのリン酸カルシウム焼結体はその
ほとんどが60メツシユ（目開き250μ）を通過した。該
リン酸カルシウム焼結体の相対密度は99.3％であつた
が、顆粒のほとんどは鋭い角をもつていた。Comparative Example 2 The calcium phosphate precipitate obtained by dewatering and washing with a centrifugal dehydrator in Example 3 was dried at the same temperature as in Example 1 for the filter cake. The dried calcium phosphate filter cake is put into a dairy bee with a diameter of 30 cm, and 95% or more of the dried calcium phosphate cake is 8 mesh (opening 2.0 m
The crushing was carried out so that the amount of dried calcium phosphate between 16 to 32 mesh (500 to 1000 μ) was maximized. The granular calcium phosphate dry body obtained by crushing was placed in an electric furnace and fired at the same temperature as in Example 1. The calcium phosphate sinter thus obtained was sieved again and the size was the same as in Example 20-42 mesh (opening 400-830).
(350 μg) of granular calcium phosphate sinter compact of (μ) was obtained. Theoretical value of gelatinous calcium phosphate precipitate 1060g
The yield of the obtained granular calcium phosphate sinter was 33%. Most of the remaining calcium phosphate sinter passed through 60 mesh (opening 250μ). The relative density of the calcium phosphate sinter was 99.3%, but most of the granules had sharp corners.
実施例４ 実施例１において太平化学社製β−正リン酸カルシウ
ム粉末（Ca/P＝1.50、比表面積１m2/g）を使用する以外
は、実施例１と同様の方法で楕円球状のリン酸カルシウ
ム焼結成形体を製造した。ポリウレタンフオームに充填
した該β−正リン酸カルシウム355gに対し、得られた12
〜28メツシユの楕円球状リン酸カルシウム焼結体は319g
であり、収率は90％であつた。また、該リン酸カルシウ
ム焼結体は90％であつた。また、該リン酸カルシウム焼
結体の相対密度は90.3％であつた。Example 4 An oval-shaped calcium phosphate sinter composition was obtained in the same manner as in Example 1 except that β-orthocalcium phosphate powder (Ca / P = 1.50, specific surface area 1 m 2 / g) manufactured by Taihei Chemical Co., Ltd. was used. A feature was manufactured. The amount of 12 obtained with respect to 355 g of the β-orthocalcium phosphate filled in the polyurethane foam
~ 319 g of 28 mesh spheroidal calcium phosphate sinter
And the yield was 90%. The calcium phosphate sintered body was 90%. The relative density of the calcium phosphate sinter was 90.3%.
実施例１と同様にしてＤおよびＡを測定した結果、A/
Dは0.72であり、また、Ｄに交わるＡの位置がＤの中心
より両側0.3Dの範囲内に入る粒子の数は全粒子の86％で
あつた。As a result of measuring D and A in the same manner as in Example 1, A /
D was 0.72, and the number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 86% of all particles.
実施例５ セントラル硝子（株）製ヒドロキシアパタイトAN粉末
（Ca/P＝1.67、比表面積36m2/g、粉末の粒径10〜30μ）
を使用する以外は、実施例１と同様の方法で、該ヒドロ
キシアパタイト粉末をポリウレタンフォーム10個にそれ
ぞれ充填し、これをラバープレスによりプレスした後、
電気炉に入れ、600℃で３時間焼成した。このようにし
て得られた楕円球状ヒドロキシアパタイト焼結成形体を
ふるいにかけ、12〜28メツシユの楕円球状リン酸カルシ
ウム焼結体295gを得た。ポリウレタンフオーム10個に充
填したヒドロキシアパタイト332gに対し、得られた顆粒
状リン酸カルシウム焼結体の収率は89％であつた。ま
た、該リン酸カルシウム焼結体の相対密度は52％であ
り、該ヒドロキシアパタイト焼結体は70〜250Åの細孔
直径をもつ細孔容積が全細孔容積の83％である多孔体で
あつた。Example 5 Central Glass Co., Ltd. hydroxyapatite AN powder (Ca / P = 1.67, specific surface area 36 m 2 / g, powder particle size 10 to 30 μ)
In the same manner as in Example 1 except that, was used to fill 10 polyurethane foams with the hydroxyapatite powder, which were pressed by a rubber press.
It was put in an electric furnace and fired at 600 ° C. for 3 hours. The spheroidal hydroxyapatite sinter compact thus obtained was sieved to obtain 295 g of an spheroidal calcium phosphate sinter of 12 to 28 mesh. The yield of the obtained granular calcium phosphate sinter was 89% with respect to 332 g of hydroxyapatite filled in 10 polyurethane foams. The relative density of the calcium phosphate sintered body was 52%, and the hydroxyapatite sintered body was a porous body having a pore diameter of 70 to 250 Å and 83% of the total pore volume. .
実施例１と同様にしてＤおよびＡを測定した結果、A/
Dは0.75であり、また、Ｄに交わるＡの位置がＤの中心
より両側0.3Dの範囲内に入る粒子の数は全粒子の82％で
あつた。As a result of measuring D and A in the same manner as in Example 1, A /
D was 0.75, and the number of particles where the position of A intersecting with D falls within 0.3D on both sides from the center of D was 82% of all particles.
実施例６ 第一稀元素化学工業（株）製部分安定化ジルコニア粉
末（比表面積６m2/g、Y2O3 3mol％）を、ラバー型（内
容積2cm×5cm×5cm）に挿入したブリヂストン製ポリウ
レタンフオーム「エバーライトスコツトフイルター」
（HR-13、セル数11〜16ケ/25mm、空孔率97％）10個にそ
れぞれ充填し、これをラバープレスにより2000kg/cm2の
圧力でプレスした。ラバープレス後、該ジルコニア粉末
を含むポリウレタンフオーム（該ジルコニア粉末はフオ
ームの孔の中で顆粒状になつている）を電気炉に入れ、
500℃、2-3時間、さらに1500℃まで昇温してから２時間
焼成した。このようにして得られた顆粒状ジルコニア焼
結成形体をふるいにかけ８〜28メツシユ（目開き580〜2
400μ）の楕円球状ジルコニア焼結体570gを得た。ポリ
ウレタンフオーム10個に充填したジルコニア粉末602gに
対し、得られた顆粒状ジルコニア焼結体の収率は95％で
あつた。また該ジルコニア焼結体の相対密度は窒素圧入
法で測定した結果99％であり、高密度のものが得られ
た。Example 6 Bridgestone in which partially stabilized zirconia powder (specific surface area 6 m 2 / g, Y 2 O 3 3 mol%) manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. was inserted into a rubber mold (internal volume 2 cm × 5 cm × 5 cm). Polyurethane foam "Everlight Scott Filter"
(HR-13, number of cells 11 to 16 cells / 25 mm, porosity 97%) were filled in 10 pieces respectively and pressed by a rubber press at a pressure of 2000 kg / cm 2 . After rubber pressing, put a polyurethane foam containing the zirconia powder (the zirconia powder is in the form of granules in the pores of the foam) in an electric furnace,
It was fired at 500 ° C for 2-3 hours, further heated to 1500 ° C, and then fired for 2 hours. The granular zirconia sintered compact thus obtained is sieved to obtain 8-28 mesh (opening of 580-2
570 g of an elliptic spherical zirconia sintered body of 400 μ) was obtained. The yield of the obtained granular zirconia sintered body was 95% based on 602 g of zirconia powder filled in 10 polyurethane foams. Further, the relative density of the zirconia sintered body was 99% as a result of measurement by the nitrogen press-in method, and a high density was obtained.
実施例１と同様にして該顆粒状ジルコニア焼結体のＤ
およびＡを測定した結果、A/Dは0.68であり、また、Ｄ
に交わるＡの位置がＤの中心より両側0.3Dの範囲内に入
る粒子の数は全粒子の82％であつた。D of the granular zirconia sintered body was obtained in the same manner as in Example 1.
As a result of measuring A and A, A / D is 0.68, and D
The number of particles in which the position of A intersecting with each other falls within 0.3D on both sides from the center of D was 82% of all particles.
実施例７ 触媒化学（株）製アルミナ粉末（比表面積145m2/g）
を使用し、電気炉の温度を1800℃で焼成する以外は実施
例１と同様の方法で顆粒状アルミナ焼結体を製造した。
ポリウレタンフオームに充填した該アルミナ粉末310gに
対し、得られた12〜28メツシユ（目開き580〜1400μ）
楕円球状アルミナ焼結成形体は279gであり、収率は90％
であつた。また、該アルミナ焼結体の相対密度は96％で
あつた。Example 7 Alumina powder (specific surface area: 145 m 2 / g) manufactured by Catalyst Chemical Co., Ltd.
A granular alumina sintered body was manufactured in the same manner as in Example 1 except that the above was used and the temperature of the electric furnace was fired at 1800 ° C.
Obtained 12-28 mesh (mesh opening 580-1400μ) with respect to 310g of the alumina powder filled in the polyurethane foam.
Oval spherical alumina sintered compact is 279g, yield 90%
It was. The relative density of the alumina sintered body was 96%.
実施例１と同様にして該アルミナ焼結体のＤおよびＡ
を測定した結果、A/Dは0.78であり、また、Ｄに交わる
Ａの位置がＤの中心より両側0.3Dの範囲内に入る粒子の
数は全粒子の91％であつた。In the same manner as in Example 1, D and A of the alumina sintered body were obtained.
As a result, A / D was 0.78, and the number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 91% of all particles.
実施例８ 実施例７において電気炉の温度を1200℃で焼成する以
外は実施例７と同様の方法で顆粒状アルミナ焼結体を製
造した。得られた８〜24メツシユ（目開き720〜2400
μ）顆粒状アルミナ焼結体の収率は87％であつた。ま
た、該アルミナ焼結体の相対密度は72％であり、該アル
ミナ焼結体は1200〜1600Åの細孔直径をもつ細孔容積が
全細孔容積の81％である多孔体であつた。Example 8 A granular alumina sintered body was produced in the same manner as in Example 7 except that the electric furnace was fired at 1200 ° C. Obtained 8-24 mesh (opening 720-2400
μ) The yield of the granular alumina sintered body was 87%. The relative density of the alumina sintered body was 72%, and the alumina sintered body was a porous body having a pore diameter of 1200 to 1600Å and 81% of the total pore volume.
実施例１と同様にして該アルミナ焼結体のＤおよびＡ
を測定した結果、A/Dは0.82であり、また、Ｄに交わる
Ａの位置がＤの中心より両側0.3Dの範囲内に入る粒子の
数は全粒子の84％であつた。In the same manner as in Example 1, D and A of the alumina sintered body were obtained.
As a result, A / D was 0.82, and the number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 84% of all particles.
実施例９ セントラル硝子（株）製ヒドロキシアパタイトAN粉末
と第一稀元素化学工業（株）製部分安定化ジルコニア粉
末との混合物（重量比で10:1）を使用する以外は、実施
例１と同様の方法で楕円球状の（リン酸カルシウム＋ジ
ルコニア）混合物焼結成形体を製造した。ポリウレタン
フオームに充填した該混合粉末320gに対し、得られた12
〜28メツシユの楕円球状（リン酸カルシウム＋部分安定
化ジルコニア）混合物焼結体は285gであり、収率は89％
であつた。また、該（リン酸カルシウム＋ジルコニア）
混合物焼結体の相対密度は93％であつた。Example 9 Example 1 was repeated except that a mixture of hydroxyapatite AN powder manufactured by Central Glass Co., Ltd. and partially stabilized zirconia powder manufactured by Daiichi Rare Element Chemical Co., Ltd. (10: 1 by weight) was used. In the same manner, an elliptic spherical (calcium phosphate + zirconia) mixture sintered compact was produced. The obtained powder was added to 320 g of the mixed powder filled in the polyurethane foam.
~ 28 mesh ellipsoidal (calcium phosphate + partially stabilized zirconia) mixture sintered body is 285g, yield 89%
It was. In addition, the (calcium phosphate + zirconia)
The relative density of the mixture sintered body was 93%.
実施例１と同様にして該（リン酸カルシウム＋ジルコ
ニア）混合物焼結体のＤおよびＡを測定した結果、A/D
は0.70であり、また、Ｄに交わるＡの位置がＤの中心よ
り両側0.3Dの範囲内に入る粒子の数は全粒子の86％であ
つた。As a result of measuring D and A of the (calcium phosphate + zirconia) mixture sintered body in the same manner as in Example 1, A / D
Was 0.70, and the number of particles in which the position of A intersecting with D falls within 0.3D on both sides from the center of D was 86% of all particles.
第１図は本発明の方法により得られた顆粒状リン酸カル
シウム焼結成形体の粒子構造の一例を示す電子顕微鏡写
真である。FIG. 1 is an electron micrograph showing an example of the particle structure of a granular calcium phosphate sinter compact obtained by the method of the present invention.
Claims (8)
最大の長さをＡとしたとき、 A/Dが0.5〜0.9であり、かつＤに交わるＡの位置がＤの
中心より両側0.3Dの範囲内に入る粒子の数が全粒子数の
80％以上であることを特徴とする顆粒状無機成形体。1. When the maximum diameter is D and the maximum length in the direction perpendicular to the maximum diameter is A, A / D is 0.5 to 0.9, and the position of A intersecting D is from the center of D. The number of particles falling within 0.3D on both sides is the total number of particles.
A granular inorganic molded product characterized by being 80% or more.
第１項記載の顆粒状無機成形体。2. The granular inorganic molded product according to claim 1, which has a relative density of 90% or more.
の範囲第１項記載の顆粒状無機成形体。3. The granular inorganic molded product according to claim 1, which contains calcium phosphate as a main component.
第１項記載の顆粒状無機成形体。4. The granular inorganic molded product according to claim 1, which comprises a metal oxide as a main component.
焼成可能な無機粉末を入れて加圧成形を行うことによ
り、多孔体の孔の中に顆粒状の無機成形体を形成し、し
かる後該有機多孔体を焼去するとともに、該無機成形体
を焼成することを特徴とする顆粒状無機成形体の製造
法。5. A granular inorganic compact is formed in the pores of the porous body by placing a calcinable inorganic powder in an organic porous body having a three-dimensional network structure and performing pressure molding. Then, the organic porous material is burned off, and the inorganic molded material is calcined, and a method for producing a granular inorganic molded material.
範囲第５項記載の製造法。6. The method according to claim 5, wherein the pressure molding is hydrostatic molding.
５項記載の製造法。7. The method according to claim 5, wherein the firing is performed at 500 ° C. or higher.
最大の長さをＡとしたとき、 A/Dが0.5〜0.9であり、かつＤに交わるＡの位置がＤの
中心より両側0.3Dの範囲内に入る粒子の数が全粒子数の
80％以上である顆粒状無機成形体からなる骨充填材。8. When the maximum diameter is D and the maximum length in the direction perpendicular to the maximum diameter is A, A / D is 0.5 to 0.9 and the position of A intersecting D is from the center of D. The number of particles falling within 0.3D on both sides is the total number of particles.
Bone filling material consisting of 80% or more granular inorganic moldings.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-238947 | 1986-10-06 | ||
| JP23894786 | 1986-10-06 | ||
| JP6742887 | 1987-03-20 | ||
| JP62-67428 | 1987-03-20 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH013047A JPH013047A (en) | 1989-01-06 |
| JPS643047A JPS643047A (en) | 1989-01-06 |
| JP2506826B2 true JP2506826B2 (en) | 1996-06-12 |
Family
ID=26408644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62251845A Expired - Lifetime JP2506826B2 (en) | 1986-10-06 | 1987-10-05 | Granular inorganic molded body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2506826B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036013A1 (en) * | 1999-11-15 | 2001-05-25 | Phillips-Origen Ceramic Technology, Llc. | Process for producing rigid reticulated articles |
| GB0318901D0 (en) | 2003-08-12 | 2003-09-17 | Univ Bath | Improvements in or relating to bone substitute material |
| CN113354289A (en) * | 2021-05-20 | 2021-09-07 | 深圳市基克纳科技有限公司 | Lead-free porous material and preparation method and application thereof |
-
1987
- 1987-10-05 JP JP62251845A patent/JP2506826B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS643047A (en) | 1989-01-06 |
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