JPH0665635B2 - Molding material - Google Patents
Molding materialInfo
- Publication number
- JPH0665635B2 JPH0665635B2 JP60066693A JP6669385A JPH0665635B2 JP H0665635 B2 JPH0665635 B2 JP H0665635B2 JP 60066693 A JP60066693 A JP 60066693A JP 6669385 A JP6669385 A JP 6669385A JP H0665635 B2 JPH0665635 B2 JP H0665635B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- molding
- tricalcium phosphate
- molding material
- porous
- 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
- 239000012778 molding material Substances 0.000 title claims description 25
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 22
- 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 claims description 22
- 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 18
- 239000001506 calcium phosphate Substances 0.000 claims description 16
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 15
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 15
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052586 apatite Inorganic materials 0.000 description 9
- 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 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0016—Granular materials, e.g. microballoons
- C04B20/002—Hollow or porous granular materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、比較的高い硬度の多孔質水酸アパタイト系成
形材料に関するものである。さらに詳しくいえば、本発
明は、遅効性肥料、各種タンパク質の吸着分離用クロマ
トグラフィー充てん剤、担体、人工骨のインプラント素
材、湿度センサーのような電子材料として有用な多孔質
水酸アパタイト組成物から成る新規な成形材料に関する
ものである。TECHNICAL FIELD The present invention relates to a porous hydroxyapatite-based molding material having a relatively high hardness. More specifically, the present invention relates to a slow-acting fertilizer, a chromatographic packing for adsorptive separation of various proteins, a carrier, an implant material for artificial bone, and a porous hydroxyapatite composition useful as an electronic material such as a humidity sensor. The present invention relates to a novel molding material.
従来の技術 従来のアパタイト成形体の製造法としては、カルシウム
塩水溶液とリン酸塩水溶液とを、９０〜１００℃でpHを
８付近に保持しながら脱炭酸雰囲気中で混合し、沈澱生
成したゲル状物を熟成した後、ろ過洗浄してゲル中の不
純物を除去し、乾燥、粉砕して粉末状アパタイトを合成
し、該粉末状アパタイトを焼結法等により成形体とする
方法が知られている。2. Description of the Related Art As a conventional method for producing an apatite compact, an aqueous solution of calcium salt and an aqueous solution of phosphate are mixed in a decarboxylation atmosphere while maintaining a pH of about 8 at 90 to 100 ° C. to form a gel by precipitation. After aging the powder, the impurities in the gel are removed by filtration and washing, dried and crushed to synthesize powdery apatite, and a method of forming the powdery apatite into a compact by a sintering method or the like is known. There is.
この方法によると、アパタイトの合成に際し、水溶液の
混合、ゲル状物のろ過洗浄、乾燥、粉砕と多工程並びに
多くの装置を必要とするばかりでなく、その操業も細心
の注意と熟練とを必要とした。また、焼結法によって成
形する場合には、1000℃以上の高温を必要とし、しかも
得られる成形体はち密構造のものとなり、多孔性のコン
トロールも困難である等多くの欠点を有している。According to this method, when synthesizing apatite, not only is it necessary to mix an aqueous solution, to filter and wash the gel-like material, to dry it, to pulverize it, and to use many devices, but also its operation requires meticulous attention and skill. And Further, in the case of molding by a sintering method, a high temperature of 1000 ° C. or higher is required, and the molded body obtained has a dense structure, and it has many drawbacks such as difficulty in controlling the porosity. .
これまで、このような欠点を改良したアパタイト成形材
料としては、リン酸三カルシウムの粉末を水に分散さ
せ、これを型内で沈降させたのち１００℃以下で固化さ
せたもの（特公昭５６−４９８６９号公報）、α−リン
酸三カルシウムに易水溶性の化合物と水とを加えて混練
し、酸を添加して水硬化したもの（特開昭５９−８８３
５１号公報）などの水酸アパタイト系成形材料が知られ
ている。Up to now, as an apatite molding material in which such defects have been improved, a powder of tricalcium phosphate dispersed in water, precipitated in a mold and then solidified at 100 ° C. or lower (Japanese Patent Publication No. 56- No. 49869), an easily water-soluble compound and water are added to α-tricalcium phosphate, and the mixture is kneaded, and an acid is added to water-cur it (JP-A-59-883).
Hydroxyapatite-based molding materials such as JP-A No. 51) are known.
しかしながら、このような水酸アパタイト系成形材料
は、自然沈降による成形方法を用いているため気孔径の
制御に難点があり、また強度や硬度の点で十分とはいえ
ず、硬度を要求される個所での使用が制限されるのを免
れない。However, such a hydroxyapatite-based molding material has a difficulty in controlling the pore diameter because it uses a molding method by spontaneous precipitation, and is not sufficient in terms of strength and hardness, and hardness is required. Inevitably restricted use in places.
発明が解決しようとする問題点 本発明の目的は、従来の多孔質アパタイト成形材料と同
等若しくはより高い気孔率、化学量論比の水酸アパタイ
ト含有率を有し、気孔径の制御が比較的容易で、しかも
高い硬度をもつ新規なリン酸カルシウム系成形材料を提
供することにある。Problems to be Solved by the Invention An object of the present invention is to have a porosity equal to or higher than that of a conventional porous apatite molding material, and a hydroxyapatite content of a stoichiometric ratio, and to control the pore diameter relatively. An object of the present invention is to provide a novel calcium phosphate-based molding material that is easy and has high hardness.
問題点を解決するための手段 本発明者らは、多孔質水酸アパタイトを主原料とし、従
来の水酸アパタイト系多孔質成形材料に匹敵する高い気
孔率、化学量論比の水酸アパタイト含有率を有すると共
に、気孔率の制御が容易で、より高い強度及び硬度を有
する成形材料を開発するために、鋭意研究を重ねた結
果、多孔質水酸アパタイトに所定割合のリン酸三カルシ
ウムを配合した混合物を、加圧下に水硬化させることに
より、その目的を達成しうることを見出し、この知見に
基づいて本発明をなすに至った。Means for Solving the Problems The present inventors have used porous hydroxyapatite as a main raw material, and have a high porosity and stoichiometric ratio of hydroxyapatite comparable to those of conventional hydroxyapatite-based porous molding materials. Possibility and easy control of porosity, as a result of intensive research to develop a molding material having higher strength and hardness, as a result, a predetermined proportion of tricalcium phosphate was added to porous hydroxyapatite. It was found that the object can be achieved by water-curing the above mixture under pressure, and the present invention has been completed based on this finding.
すなわち、本発明は、多孔質水酸アパタイト１００重量
部とリン酸三カルシウム１０〜１００重量部との混合物
の加圧水硬化物から成る成形材料を提供するものであ
る。That is, the present invention provides a molding material comprising a pressurized water-cured product of a mixture of 100 parts by weight of porous hydroxyapatite and 10 to 100 parts by weight of tricalcium phosphate.
リン酸三カルシウムには低温安定相（β相）と、高温安
定相（α相）、及びそれを急冷して得られる準安定相が
存在するが、本発明においては、これらのいずれを用い
てもよい。特に好ましいのは反応活性の高い準安定相の
ものである。このリン酸三カルシウムは、粒径0.2mm以
下の細粒として用いるのが好ましい。この粒径がこれよ
りも大きいものを用いると、十分な硬度をもつ硬化物が
得られない。Tricalcium phosphate has a low temperature stable phase (β phase), a high temperature stable phase (α phase), and a metastable phase obtained by rapidly cooling it. In the present invention, any of these is used. Good. Particularly preferred is a metastable phase having high reaction activity. This tricalcium phosphate is preferably used as fine particles having a particle size of 0.2 mm or less. If one having a particle size larger than this is used, a cured product having sufficient hardness cannot be obtained.
また、多孔質水酸アパタイトとしては、一般的な乾式
法、湿式法、水熱法など任意の方法に従って得られる合
成アパタイトを用いることができるし、また脊椎動物の
骨、歯から回収された生体アパタイトを粉砕し、常法に
従って焼成して得られる多孔質水酸アパタイトも用いる
ことができる。Further, as the porous hydroxyapatite, it is possible to use a synthetic apatite obtained by any method such as a general dry method, a wet method, and a hydrothermal method, and a bone recovered from a vertebrate bone or tooth. Porous hydroxyapatite obtained by crushing apatite and firing according to a conventional method can also be used.
本発明においては、多孔質水酸アパタイト１００重量部
に対し、リン酸三カルシウム１０〜１００重量部の割合
で混合した混合物が用いられる。これよりも、リン酸三
カルシウムの量が少ないと十分な硬度が得られないし、
またこれよりもリン酸三カルシウムの量が多くなると、
気孔率の低下が著しく、多孔質水酸アパタイトに基づく
各種の望ましい性質例えば種々のタンパク質に対する吸
着率や人工骨材としての生体同化性がそこなわれるよう
になる。In the present invention, a mixture of 100 parts by weight of porous hydroxyapatite and 10 to 100 parts by weight of tricalcium phosphate is used. If the amount of tricalcium phosphate is smaller than this, sufficient hardness cannot be obtained,
Also, if the amount of tricalcium phosphate is higher than this,
The porosity is remarkably lowered, and various desirable properties based on the porous hydroxyapatite, for example, the adsorption rate for various proteins and the bioassimilation property as an artificial aggregate come to be impaired.
本発明の成形材料は、例えば多孔質水酸アパタイトとリ
ン酸三カルシウムの混合物を水中に分散させ、成形用の
型に充てんし、水硬反応を行わせる。この際、水硬反応
を加減するために、ベンゼンスルホン酸ナトリウム、カ
ルボキシメチルセルロースナトリウム、ラウリル硫酸ナ
トリウム、ゼラチン、ポリビニルアルコール、塩化ナト
リウム、硫酸ナトリウム、塩化アンモニウム、尿素、酢
酸ナトリウムのような水溶性化合物を添加することがで
きる。この水硬反応は、加圧及び加温することによって
行われる。この場合の圧力としては通常２〜１０kg/cm2
の範囲が用いられる。この圧力を加えずに自然沈降させ
た場合は十分な硬度を有する成形体を得ることが困難で
ある。また、硬化温度としては１００℃以下、好ましく
は４０〜８０℃の温度が用いられる。加圧時間は、多く
の場合数分程度で十分であるが、必要ならばさらに長い
加圧を行うこともできる。このように加圧して成形した
のち、さらに前記の温度に１〜５時間程度保持すること
によって水硬反応を完結させる。In the molding material of the present invention, for example, a mixture of porous hydroxyapatite and tricalcium phosphate is dispersed in water, the mixture is filled in a mold for molding, and a hydraulic reaction is carried out. At this time, in order to moderate the hydraulic reaction, water-soluble compounds such as sodium benzenesulfonate, sodium carboxymethyl cellulose, sodium lauryl sulfate, gelatin, polyvinyl alcohol, sodium chloride, sodium sulfate, ammonium chloride, urea, and sodium acetate are used. It can be added. This hydraulic reaction is performed by applying pressure and heating. The pressure in this case is usually 2 to 10 kg / cm 2
The range of is used. It is difficult to obtain a molded product having a sufficient hardness when it is allowed to spontaneously settle without applying this pressure. Further, as the curing temperature, a temperature of 100 ° C. or lower, preferably 40 to 80 ° C. is used. In most cases, a pressurizing time of about several minutes is sufficient, but longer pressurizing can be performed if necessary. After pressurizing and molding in this way, the hydraulic reaction is completed by further maintaining the above temperature for about 1 to 5 hours.
このようにして、高い硬度を有し、しかも多孔質アパタ
イト材料として望ましい性質を保持した成形材料を得る
ことができる。In this way, it is possible to obtain a molding material having a high hardness and maintaining the desired properties as a porous apatite material.
発明の効果 本発明の成形材料は、従来の多孔質水酸アパタイトに欠
けていた高い硬度を有する上に、多孔質水酸アパタイト
が本来有する望ましい性質をそのまま維持しているの
で、遅効性肥料、クロマトグラフィー充てん材、担体、
人工骨材料、湿度センサーのような電子材料、生体材料
などとしても用いることができる。Effect of the Invention The molding material of the present invention has a high hardness, which is lacking in conventional porous hydroxyapatite, and maintains the desired properties that the porous hydroxyapatite originally has, so that a slow-acting fertilizer, Chromatographic packing material, carrier,
It can also be used as an artificial bone material, an electronic material such as a humidity sensor, and a biomaterial.
実施例 次に実施例により本発明をさらに詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
実施例１ 多孔質水酸アパタイト粉末（粒径0.5〜1.0mm）とリン酸
三カルシウム粉末（粒径0.105mm以下）とを重量比で
１：２ないし１０：１の割合で混合した８種の混合物の
それぞれ2.5gを、脱イオン水1.5mlに分散させ、１０ml
容量のふた付試験管に入れ、4.8kg/cm2で１分間、加圧
成形したのち、成形物を８０℃において３時間加温して
硬化させた。Example 1 Eight kinds of porous hydroxyapatite powder (particle size 0.5 to 1.0 mm) and tricalcium phosphate powder (particle size 0.105 mm or less) were mixed in a weight ratio of 1: 2 to 10: 1. Disperse 2.5 g each of the mixture in 1.5 ml deionized water, 10 ml
It was placed in a test tube with a lid and pressure-molded at 4.8 kg / cm 2 for 1 minute, and then the molded product was heated at 80 ° C. for 3 hours to be cured.
このようにして、８種の硬質水酸アパタイト系成形材料
を得た。In this way, eight kinds of hard hydroxyapatite-based molding materials were obtained.
実施例２ 実施例１における成形圧力4.8kg/cm2の代りに7.3kg/cm2
を用いること以外は、全く実施例１と同様にして、８種
の硬質水酸アパタイト系成形材料を得た。Example 2 Instead of the molding pressure of 4.8 kg / cm 2 in Example 1, 7.3 kg / cm 2
Eight kinds of hard hydroxyapatite-based molding materials were obtained in exactly the same manner as in Example 1 except that
実施例３ 実施例１における脱イオン水1.5mlの代りに、0.5Ｍ塩化
アンモニウム水溶液1.5mlを用い、硬化温度を４０℃に
すること以外は、全く実施例１と同様にして８種の成形
材料を得た。Example 3 Eight molding materials were used in the same manner as in Example 1 except that 1.5 ml of 0.5 M ammonium chloride aqueous solution was used instead of 1.5 ml of deionized water in Example 1 and the curing temperature was 40 ° C. Got
実施例４ 実施例３における成形圧力4.8kg/cm2の代りに7.3kg/cm2
を用いること以外は、全く実施例３と同様にして、８種
の成形材料を得た。Example 4 Instead of the molding pressure of 4.8 kg / cm 2 in Example 3, 7.3 kg / cm 2
Eight types of molding materials were obtained in exactly the same manner as in Example 3 except that was used.
実施例５ 実施例１で用いた粒径0.105mm以下のリン酸三カルシウ
ム粉末の代りに、粒径0.105〜0.25mmの範囲のリン酸三
カルシウム粉末を用いること以外は、全く実施例１と同
様にして、８種の成形材料を得た。Example 5 The same as Example 1 except that tricalcium phosphate powder having a particle size of 0.105 to 0.25 mm is used in place of the tricalcium phosphate powder having a particle size of 0.105 mm or less used in Example 1. Then, eight kinds of molding materials were obtained.
比較例１ 実施例１で用いたものと同じ８種の混合物を、それぞれ
脱イオン水８mlに分散させ、自然沈降させたのち、８０
℃で３時間加温することにより、８種の成形材料を得
た。Comparative Example 1 The same eight kinds of mixtures as those used in Example 1 were dispersed in 8 ml of deionized water and spontaneously precipitated, and then 80
Eight types of molding materials were obtained by heating at 0 ° C. for 3 hours.
比較例２ 比較例１における脱イオン水８mlの代りに、0.5Ｍ塩化
アンモニウム水溶液８mlを用い、自然沈降させたのち、
４０℃で３時間加温することにより、８種の成形材料を
得た。Comparative Example 2 Instead of 8 ml of deionized water in Comparative Example 1, 8 ml of 0.5 M ammonium chloride aqueous solution was used, and the mixture was allowed to spontaneously precipitate.
Eight types of molding materials were obtained by heating at 40 ° C. for 3 hours.
比較例３ 実施例５で用いたものと同じ８種の混合物を、それぞれ
脱イオン水８mlに分散させ、自然沈降させたのち、８０
℃で３時間加温することにより、８種の成形材料を得
た。Comparative Example 3 The same eight kinds of mixtures as those used in Example 5 were dispersed in 8 ml of deionized water and spontaneously precipitated, and then 80
Eight types of molding materials were obtained by heating at 0 ° C. for 3 hours.
参考例 実施例１〜５及び比較例１〜３で得た成形材料につい
て、ＪＩＳ Ｔ６６０４−１９７６に従い、直径２mm質
量３００g)のビッカー針を用いて針入度を試験した。こ
の結果を次表に示す。なお、表中の記号は以下の意味を
もつ。Reference Example The molding materials obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were tested for penetration by using a Vickers needle having a diameter of 2 mm and a mass of 300 g) according to JIS T6604-1976. The results are shown in the table below. The symbols in the table have the following meanings.
○…針跡は全く認められない。 ○: No needle trace is observed.
△…かすかに針跡が認められる。 Δ: A slight needle trace is recognized.
×…明瞭に針跡が認められる。 X: Clear needle marks are recognized.
この表から明らかなように、リン酸三カルシウムの量が
多い場合は自然沈降により成形しても高い硬度を示す
が、この量が全体の５０重量％以下になると、自然沈降
により成形したものは十分な硬度を示さないのに対し、
加圧成形したものは、いずれも高い硬度を示す。 As is clear from this table, when the amount of tricalcium phosphate is large, high hardness is exhibited even when molded by natural sedimentation, but when this amount is 50% by weight or less of the whole, those molded by natural sedimentation are While it does not show sufficient hardness,
All of the pressure-molded products show high hardness.
なお、リン酸三カルシウムの量が５０重量％よりも多い
試料は、気孔率、化学量論比の水酸アパタイト含有率が
低下し、多孔質水酸アパタイトのもつ望ましい性質であ
る、各種タンパク質に対する吸着率や人工骨における生
体内同化性などが劣化する傾向がある。Samples containing more than 50% by weight of tricalcium phosphate have reduced porosity and stoichiometric ratio of hydroxyapatite, which is a desirable property of porous hydroxyapatite. The adsorption rate and in vivo assimilation in artificial bone tend to deteriorate.
また、実施例３及び４で添加されている塩化アンモニウ
ムは単に硬化速度を促進するだけで、得られた成形材料
の硬度にはほとんど影響を与えていない。Further, ammonium chloride added in Examples 3 and 4 merely accelerates the curing rate, and hardly affects the hardness of the obtained molding material.
Claims (1)
酸三カルシウム１０〜１００重量部との混合物の加圧水
硬化物から成る成形材料。1. A molding material comprising a cured product under pressure of a mixture of 100 parts by weight of porous hydroxyapatite and 10 to 100 parts by weight of tricalcium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60066693A JPH0665635B2 (en) | 1985-04-01 | 1985-04-01 | Molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60066693A JPH0665635B2 (en) | 1985-04-01 | 1985-04-01 | Molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61242968A JPS61242968A (en) | 1986-10-29 |
| JPH0665635B2 true JPH0665635B2 (en) | 1994-08-24 |
Family
ID=13323270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60066693A Expired - Lifetime JPH0665635B2 (en) | 1985-04-01 | 1985-04-01 | Molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665635B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062153B2 (en) * | 1987-09-18 | 1994-01-12 | 三菱マテリアル株式会社 | Filling material for bone defect and bone void |
| JPH0360451A (en) * | 1989-07-25 | 1991-03-15 | Natl Inst For Res In Inorg Mater | Calcium phosphate hydraulic cement composition |
| JPH03128061A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| JPH03128063A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| JPH03174348A (en) * | 1989-11-30 | 1991-07-29 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement |
| JPH03174349A (en) * | 1989-12-01 | 1991-07-29 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59219B2 (en) * | 1976-06-07 | 1984-01-05 | 旭光学工業株式会社 | Artificial teeth, artificial bones and their manufacturing method |
| JPS54158099A (en) * | 1977-05-25 | 1979-12-13 | Tokyo Ika Shika Daigakuchiyou | Preparation of artificial bone and artificial fang by means of apatite sintering body |
-
1985
- 1985-04-01 JP JP60066693A patent/JPH0665635B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61242968A (en) | 1986-10-29 |
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