JPH04321507A - Production of calcium tertiary phosphate and hydraulic calcium phosphate cement - Google Patents
Production of calcium tertiary phosphate and hydraulic calcium phosphate cementInfo
- Publication number
- JPH04321507A JPH04321507A JP3092117A JP9211791A JPH04321507A JP H04321507 A JPH04321507 A JP H04321507A JP 3092117 A JP3092117 A JP 3092117A JP 9211791 A JP9211791 A JP 9211791A JP H04321507 A JPH04321507 A JP H04321507A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- raw material
- calcium
- phosphate
- cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 title claims abstract description 99
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 39
- 239000004568 cement Substances 0.000 title claims abstract description 38
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 37
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002994 raw material Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims abstract 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 12
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 5
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract 1
- 239000012669 liquid formulation Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 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 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 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
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高水和活性を示す第３
リン酸カルシウムの製造方法及び骨欠損部及び骨空隙部
充填材若しくは歯牙根管部充填材等として利用可能な水
硬性リン酸カルシウムセメントに関する。[Industrial Application Field] The present invention is directed to
The present invention relates to a method for producing calcium phosphate and a hydraulic calcium phosphate cement that can be used as a filling material for bone defects and voids, a tooth root canal, and the like.
【０００２】0002
【従来の技術】水硬性リン酸カルシウムは、凝結硬化に
よって生体内の歯及び骨の主成分に近似した化合物に転
化するために、歯及び骨の修復材料として有用であり、
更には生体高分子や生体中の有害な有機物又は無機質イ
オンの吸着剤として有用なものであることが知られてい
る。BACKGROUND OF THE INVENTION Hydraulic calcium phosphate is useful as a tooth and bone repair material because it is converted into a compound similar to the main components of teeth and bones in living organisms through coagulation and hardening.
Furthermore, it is known to be useful as an adsorbent for biopolymers and harmful organic substances or inorganic ions in living organisms.
【０００３】従来、前記水硬性リン酸カルシウムとして
は、特開昭５９−８８３５１号公報において硬化液とし
て、塩類及び希薄酸を組合せて使用するリン酸カルシウ
ムセメントが、また特開昭６０−２５３４５４号公報に
おいて、不飽和カルボン酸重合体を含有する酸性溶液を
使用するリン酸カルシウムセメントが開示されている。
しかしながら、前記水硬性リン酸カルシウムにおいては
、セメントの硬化が終了するまでは、硬化液の酸性が強
く、生体にかなりの刺激を及ぼすという問題があり、更
には、セメントの硬化終了後も未反応の酸の溶出により
ｐＨが低下し、その結果として生体に刺激を与えるとい
う問題もある。Conventionally, as the above-mentioned hydraulic calcium phosphate, calcium phosphate cement which uses a combination of salts and dilute acid as a hardening liquid is disclosed in JP-A No. 59-88351, and calcium phosphate cement is disclosed in JP-A No. 60-253454. Calcium phosphate cements are disclosed that use acidic solutions containing saturated carboxylic acid polymers. However, with the above-mentioned hydraulic calcium phosphate, there is a problem in that the curing liquid is highly acidic and causes considerable irritation to living organisms until the cement has finished hardening. Furthermore, even after the cement has finished hardening, unreacted acid There is also the problem that the pH decreases due to the elution of , which results in irritation to living organisms.
【０００４】そこでかかる問題の解決のため、水により
硬化する水硬性リン酸カルシウムセメントが開発されて
いる（例えば、ＦＣ ＲＥＰＯＲＴ，ｖｏｌ．６（１
９８８），ｐ．４７５〜４８０「バイオセラミックスと
しての水硬性アパタイト」）。前記水により硬化する水
硬性リン酸カルシウムとしては、特開昭６４−３７４４
５号公報において、単に水と練和するのみで３７℃にて
、１０分程度で硬化する水硬性リン酸カルシウムセメン
トが提案されている。前記水硬性リン酸カルシウムはｐ
Ｈがほぼ中性であり、生体に対する刺激も少なく、従来
の水硬性リン酸カルシウムセメントの問題点を解消する
ものである。In order to solve this problem, hydraulic calcium phosphate cement that hardens with water has been developed (for example, FC REPORT, vol. 6 (1)).
988), p. 475-480 "Hydraulic apatite as bioceramics"). The hydraulic calcium phosphate that hardens with water is disclosed in Japanese Patent Application Laid-Open No. 64-3744.
No. 5 proposes a hydraulic calcium phosphate cement that hardens in about 10 minutes at 37° C. simply by mixing with water. The hydraulic calcium phosphate is p
Since H is almost neutral, it is less irritating to living organisms and solves the problems of conventional hydraulic calcium phosphate cement.
【０００５】しかしながら、前記水硬性リン酸カルシウ
ムは、実用上十分な強度を発揮せず、また長期間水中に
放置すると強度の劣化が見られるため、生体内において
劣化し、破壊する危険性が極めて高いという問題がある
。[0005] However, the above-mentioned hydraulic calcium phosphate does not exhibit sufficient strength for practical use, and its strength deteriorates when left in water for a long period of time, so it is said that there is an extremely high risk of deterioration and destruction in vivo. There's a problem.
【０００６】[0006]
【発明が解決しようとする課題】従って本発明の目的は
、生体に対する刺激がなく、生体親和性に優れ、且つ実
用上十分な強度を有し、しかも長期間にわたり強度が劣
化することのない水硬性リン酸カルシウムセメントを提
供することにある。[Problems to be Solved by the Invention] Therefore, the object of the present invention is to provide water that is not irritating to living organisms, has excellent biocompatibility, has sufficient strength for practical use, and does not deteriorate in strength over a long period of time. The purpose of the present invention is to provide a hard calcium phosphate cement.
【０００７】本発明の別の目的は、前記水硬性リン酸カ
ルシウムセメントの主成分の１つとして用いることがで
き、且つ高水和活性を示す第３リン酸カルシウムの製造
方法を提供することにある。Another object of the present invention is to provide a method for producing tertiary calcium phosphate that can be used as one of the main components of the hydraulic calcium phosphate cement and exhibits high hydration activity.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、水温３
０℃以下の水溶液中において、カルシウム供給原料及び
リン供給原料を含む原料成分を湿式合成した原料スラリ
−を、乾燥後、７００℃以上で焼成することを特徴とす
る第３リン酸カルシウムの製造方法が提供される。[Means for Solving the Problems] According to the present invention, water temperature 3
Provided is a method for producing tertiary calcium phosphate, characterized in that a raw material slurry obtained by wet-synthesizing raw material components including a calcium supply raw material and a phosphorus supply raw material in an aqueous solution at 0 °C or lower is dried and then calcined at 700 °C or higher. be done.
【０００９】また本発明によれば、水温３０℃以下の水
溶液中において、カルシウム供給原料及びリン供給原料
を含む原料成分を湿式合成した原料スラリ−を、乾燥後
、７００℃以上で焼成して得られる第３リン酸カルシウ
ムと、第２リン酸カルシウム及び／又は第１リン酸カル
シウムとの混合物を主成分とする粉剤及び液剤を含む水
硬性リン酸カルシウムセメントが提供される。Further, according to the present invention, a raw material slurry obtained by wet-synthesizing raw material components including a calcium feedstock and a phosphorus feedstock in an aqueous solution with a water temperature of 30°C or lower is dried and then calcined at a temperature of 700°C or higher. Hydraulic calcium phosphate cement is provided, which includes powders and liquids containing a mixture of tertiary calcium phosphate, dibasic calcium phosphate, and/or dibasic calcium phosphate as a main component.
【００１０】以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
【００１１】本発明の第３リン酸カルシウムセメントの
製造方法においては、特定の温度にて湿式合成した原料
スラリ−を、乾燥後、焼成することを特徴とする。The method for producing tertiary calcium phosphate cement of the present invention is characterized in that a raw material slurry wet-synthesized at a specific temperature is dried and then fired.
【００１２】本発明の第３リン酸カルシウムセメントの
製造方法において、湿式合成する際に用いる原料成分は
、第３リン酸カルシウムを構成するカルシウム供給原料
及びリン供給原料を含有しておれば良く、具体的には、
カルシウム供給原料としてＣａＣｌ２、Ｃａ（ＮＯ３）
２、Ｃａ（ＯＨ）２等を、またリン供給原料としてＨ３
ＰＯ４、ＫＨ２ＰＯ４、（ＮＨ４）２ＨＰＯ４、ＮＨ４
Ｈ２ＰＯ４等を好ましく挙げることができる。[0012] In the method for producing tertiary calcium phosphate cement of the present invention, the raw material components used in the wet synthesis only need to contain the calcium feedstock and phosphorus feedstock constituting the tertiary calcium phosphate. ,
CaCl2, Ca(NO3) as calcium feedstock
2, Ca(OH)2, etc., and H3 as a phosphorus feedstock.
PO4, KH2PO4, (NH4)2HPO4, NH4
Preferred examples include H2PO4 and the like.
【００１３】本発明の製造方法においては、まず前記原
料スラリ−を得るために、原料成分を湿式合成する。該
湿式合成を行なうには、例えば前記カルシウム供給原料
と、前記リン供給原料とを含む原料成分を水に溶解し、
水溶液とした後、該水溶液の水温を３０℃以下に制御し
ながら反応させるなどして容易に行なうことができる。
前記反応は、発熱反応であるため反応系の温度は反応の
進行に従い上昇するが、より水和活性の高い第３リン酸
カルシウムを得るために、反応系の温度を前記３０℃以
下に制御する必要があり、特に１５℃以下に制御するの
が好ましい。また前記反応温度の下限については、水溶
液が凍結しない程度であれば、特に限定されるものでは
ない。In the manufacturing method of the present invention, first, raw material components are wet-synthesized to obtain the raw material slurry. To carry out the wet synthesis, for example, raw material components including the calcium feedstock and the phosphorus feedstock are dissolved in water,
This can be easily carried out by making an aqueous solution and then reacting while controlling the water temperature of the aqueous solution to 30° C. or lower. Since the reaction is an exothermic reaction, the temperature of the reaction system increases as the reaction progresses, but in order to obtain tribasic calcium phosphate with higher hydration activity, it is necessary to control the temperature of the reaction system to below 30 ° C. It is particularly preferable to control the temperature to 15°C or lower. Further, the lower limit of the reaction temperature is not particularly limited as long as the aqueous solution does not freeze.
【００１４】また本発明の製造方法においては、次に前
記得られた原料スラリ−を、乾燥後、焼成することによ
り所望の第３リン酸カルシウムを得ることができ、該乾
燥は、例えばスプレ−ドライヤ−を用いた噴霧乾燥や乾
燥機による乾燥等の通常の乾燥方法により行なうことが
できる。また焼成は、所望の第３リン酸カルシウムを得
るために７００℃以上とする必要がある。具体的には例
えばα型第３リン酸カルウシムを得る場合には、焼成温
度を好ましくは１２００℃以上とし、またβ型第３リン
酸カルシウムを得る場合には、焼成温度を好ましくは７
００℃〜１０５０℃とし、α型第３リン酸カルウシムと
β型第３リン酸カルシウムの混合物を得る場合には、１
０５０〜１２００℃とするのが好ましい。この際焼成温
度が７００℃未満の場合には、ヒドロキシアパタイトが
得られるのみであって、第３リン酸カルシウムが得られ
ないので、７００℃以上で焼成する必要がある。また焼
成時間は、１〜１０時間の範囲とするのが好ましい。Further, in the production method of the present invention, the desired tertiary calcium phosphate can be obtained by drying and then firing the obtained raw material slurry, and the drying can be carried out using, for example, a spray dryer. This can be carried out by a conventional drying method such as spray drying using a dryer or drying using a dryer. Further, the firing must be performed at a temperature of 700° C. or higher in order to obtain the desired tertiary calcium phosphate. Specifically, for example, when obtaining α-type tertiary calcium phosphate, the calcination temperature is preferably 1200°C or higher, and when obtaining β-type tertiary calcium phosphate, the calcination temperature is preferably 70°C or higher.
00°C to 1050°C to obtain a mixture of α-type tertiary calcium phosphate and β-type tertiary calcium phosphate, 1
It is preferable to set it as 050-1200 degreeC. At this time, if the firing temperature is less than 700°C, only hydroxyapatite will be obtained and no tertiary calcium phosphate will be obtained, so it is necessary to perform the firing at 700°C or higher. Further, the firing time is preferably in the range of 1 to 10 hours.
【００１５】本発明の製造方法により得られる第３リン
酸カルシウムをリン酸カルシウムセメント原料として使
用する際には、粉砕して粒体とした後使用するのが好ま
しい。またこの際粒体の平均粒径は、５μｍ以下とする
のが好ましい。前記平均粒径が５μｍを超えるとセメン
トの硬化に長時間を要し、また初期強度が低下するので
好ましくない。When the tertiary calcium phosphate obtained by the production method of the present invention is used as a raw material for calcium phosphate cement, it is preferable to crush it into granules before use. Further, in this case, the average particle diameter of the particles is preferably 5 μm or less. If the average particle size exceeds 5 μm, it will take a long time for the cement to harden and the initial strength will decrease, which is not preferable.
【００１６】また前記原料スラリ−の乾燥物を焼成する
際において乾燥物を加圧成形した後焼成するとセメント
の強度がより向上するので特に好ましい。[0016] Furthermore, when firing the dry product of the raw material slurry, it is particularly preferable to pressure-form the dry product and then fire it, since this further improves the strength of the cement.
【００１７】本発明の水硬性リン酸カルシウムセメント
は、前記製造方法により得られる第３リン酸カルシウム
と、第２リン酸カルシウム及び／又は第１リン酸カルシ
ウムとを混合して得られる混合物を粉剤の主成分とする
ことを特徴とする。The hydraulic calcium phosphate cement of the present invention is characterized in that the main component of the powder is a mixture obtained by mixing the tertiary calcium phosphate obtained by the above manufacturing method with dibasic calcium phosphate and/or dibasic calcium phosphate. shall be.
【００１８】本発明の水硬性リン酸カルシウムセメント
において、粉剤成分として前記第３リン酸カルシウムと
混合して用いる、第２リン酸カルシウム及び／又は第１
リン酸カルシウムは、水の存在下にて、第３リン酸カル
シウムと反応してリン酸８カルシウムを生成して硬化す
る成分である。この際用いる第２リン酸カルシウム、第
１リン酸カルシウムとしては、各々市販の第２リン酸カ
ルシウム２水和物、第１リン酸カルシウム１水和物等を
好ましく挙げることができる。In the hydraulic calcium phosphate cement of the present invention, dibasic calcium phosphate and/or primary calcium phosphate, which is used as a powder component by mixing with the tertiary calcium phosphate,
Calcium phosphate is a component that reacts with tertiary calcium phosphate to produce octacalcium phosphate and harden in the presence of water. Preferred examples of the dibasic calcium phosphate and dibasic calcium phosphate used in this case include commercially available dibasic calcium phosphate dihydrate, dibasic calcium phosphate monohydrate, and the like.
【００１９】本発明の水硬性リン酸カルシウムセメント
に用いる前記第３リン酸カルシウムは、α型第３リン酸
カルシウムとβ型第３リン酸カルシウムとを各々単独で
用いることもできるが、特にセメント強度の長期劣化を
防止するために、α型第３リン酸カルシウムとβ型第３
リン酸カルシウムとの混合物を用いるのが好ましい。該
α型第３リン酸カルシウムとβ型第３リン酸カルシウム
との混合割合は、重量比で１００：０〜５０：５０の範
囲とするのが好ましい。前記α型第３リン酸カルシウム
の混合割合が５０重量％未満の場合には、十分な初期強
度が発現しないので好ましくない。また前記第３リン酸
カルシウムとして、α型第３リン酸カルシウムとβ型第
３リン酸カルシウムとの混合物を用いる場合には、各々
単独で得られるα型第３リン酸カルシウムとβ型第３リ
ン酸カルシウムを混合しても良く、また前記製造方法に
おいて、直接混合物として得られる第３リン酸カルシウ
ム混合物をそのまま用いても良い。なお、本発明の製造
方法により得られるα型第３リン酸カルシウムは、通常
の乾式法で合成したα型第３リン酸カルシウムに比べて
、水和活性が高く、セメントの硬化時間をより短くする
ことができ、更には強度も高くすることができる。As the tertiary calcium phosphate used in the hydraulic calcium phosphate cement of the present invention, α-type tertiary calcium phosphate and β-type tertiary calcium phosphate can be used alone, but in particular, in order to prevent long-term deterioration of cement strength, In, α-type tertiary calcium phosphate and β-type tertiary calcium phosphate
Preference is given to using a mixture with calcium phosphate. The mixing ratio of the α-type tertiary calcium phosphate and the β-type tertiary calcium phosphate is preferably in the range of 100:0 to 50:50 by weight. If the mixing ratio of the α-type tertiary calcium phosphate is less than 50% by weight, sufficient initial strength will not be developed, which is not preferable. In addition, when using a mixture of α-type tertiary calcium phosphate and β-type tertiary calcium phosphate as the tertiary calcium phosphate, α-type tertiary calcium phosphate and β-type tertiary calcium phosphate, which can be obtained individually, may be mixed, Further, in the above manufacturing method, the tertiary calcium phosphate mixture obtained as a direct mixture may be used as it is. In addition, the α-type tertiary calcium phosphate obtained by the production method of the present invention has higher hydration activity than the α-type tertiary calcium phosphate synthesized by a normal dry method, and can shorten the hardening time of cement. Furthermore, the strength can also be increased.
【００２０】また本発明において、前記粉剤成分として
用いる第３リン酸カルシウムと、第２リン酸カルシウム
及び／又は第１リン酸カルシウムとの混合割合は、Ｃａ
／Ｐモル比で、１．４００〜１．４９８とするのが好ま
しい。Ｃａ／Ｐモル比が前記範囲外の場合には、強度が
低下するので好ましくない。Further, in the present invention, the mixing ratio of the tertiary calcium phosphate used as the powder component and the dibasic calcium phosphate and/or the monobasic calcium phosphate is Ca
/P molar ratio is preferably 1.400 to 1.498. If the Ca/P molar ratio is outside the above range, the strength will decrease, which is not preferable.
【００２１】本発明において用いる液剤としては、水の
みでも十分であるが、操作性をより向上させるために、
水溶性高分子や水溶性多糖類等を添加して用いてもよい
。Although water alone is sufficient as the liquid agent used in the present invention, in order to further improve operability,
Water-soluble polymers, water-soluble polysaccharides, etc. may be added and used.
【００２２】前記粉材と液材との配合割合は、重量比で
３〜１：１の範囲とするのが好ましい。前記粉材の配合
割合が１未満の場合には、硬化体の強度が低下し、３を
超えると練和時の操作性が低下するので好ましくない。[0022] The mixing ratio of the powder material and the liquid material is preferably in the range of 3 to 1:1 in terms of weight ratio. When the blending ratio of the powder material is less than 1, the strength of the cured product decreases, and when it exceeds 3, the operability during kneading decreases, which is not preferable.
【００２３】また本発明の水硬性リン酸カルシウムセメ
ントには、必要に応じて、硫酸バリウム、次炭酸ビスマ
ス、ヨ−ドホルム等のＸ線造影剤、ヨ−ドホルム、クロ
ルヘキシジン等の坑菌剤、ヒドロキシアパタイト、アル
ミナ、ジルコニア等生体親和性に優れるその他のセラミ
ックス粉等を更に含有させることもできる。In addition, the hydraulic calcium phosphate cement of the present invention may optionally contain X-ray contrast agents such as barium sulfate, bismuth subcarbonate, and iodoform, antibacterial agents such as iodoform and chlorhexidine, hydroxyapatite, It is also possible to further contain other ceramic powders having excellent biocompatibility such as alumina and zirconia.
【００２４】[0024]
【発明の効果】本発明の第３リン酸カルシウムの製造方
法は、３０℃以下に温度制御して湿式合成して得られる
原料スラリ−を乾燥した後焼成するので、通常の乾式法
により得られる第３リン酸カルシウムに比して、より水
和活性の高い第３リン酸カルシウムを得ることができる
。Effects of the Invention The method for producing tertiary calcium phosphate of the present invention involves drying and then firing the raw material slurry obtained by wet synthesis at a temperature controlled below 30°C. Tertiary calcium phosphate having higher hydration activity than calcium phosphate can be obtained.
【００２５】また本発明の水硬性リン酸カルシウムセメ
ントは、粉剤の主成分として、前記特定方法により得ら
れる第３リン酸カルシウムを用いるので、生体親和性に
優れ、長期間強度が劣化しない。従って骨欠損部及び骨
空隙部充填材若しくは歯牙根管部充填材として有用であ
る。Furthermore, since the hydraulic calcium phosphate cement of the present invention uses tertiary calcium phosphate obtained by the above specified method as the main component of the powder, it has excellent biocompatibility and does not deteriorate in strength over a long period of time. Therefore, it is useful as a filling material for bone defects and bone voids or for tooth root canals.
【００２６】[0026]
【実施例】以下本発明を実施例及び比較例により、更に
詳細に説明するが、本発明はこれらに限定されるもので
はない。EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００２７】[0027]
【実施例１〜４】２ｌビ−カ−に１．５ｌ水を投入し、
それぞれ表１に示すカルシウム化合物を３モル投入して
十分に撹拌した。次いでそれぞれ表１に示すリン化合物
２モルを水２００ｍｌに溶解した後、得られた水溶液を
撹拌しながら徐々に２時間かけて滴下した。この際ビ−
カ−内の水溶液の温度は、反応終了まで２０℃に制御し
た。反応終了後、１日放置し、全量を乾燥機で乾燥した
後、得られた乾燥物を３等分して、それぞれ１２５０℃
、１１５０℃、１０００℃にて３時間焼成し、第３リン
酸カルシウムを調製した。次いでボ−ルミルを用いて得
られた第３リン酸カルシウムを平均粒径４μｍまで粉砕
し、Ｘ線解析装置（商品名「ＲＵ−２００型」、理学電
気社製）を用いて同定を行なったところ、１２５０℃で
焼成したものはα型第３リン酸カルシウムであり、１１
５０℃で焼成したものはα型第３リン酸カルシウムとβ
型第３リン酸カルシウムとの混合物であり、１０００℃
で焼成したものはβ型第３リン酸カルシウムであった。[Examples 1 to 4] Pour 1.5 liters of water into a 2 liter beaker,
Three moles of each of the calcium compounds shown in Table 1 were added and thoroughly stirred. Next, 2 moles of each of the phosphorus compounds shown in Table 1 were dissolved in 200 ml of water, and the resulting aqueous solution was gradually added dropwise over 2 hours while stirring. At this time, Bee
The temperature of the aqueous solution in the car was controlled at 20°C until the end of the reaction. After the reaction was completed, it was left to stand for one day, and the whole amount was dried in a dryer.The obtained dried product was divided into three equal parts and each was heated at 1250°C.
, 1150°C and 1000°C for 3 hours to prepare tertiary calcium phosphate. Next, the obtained tertiary calcium phosphate was ground using a ball mill to an average particle size of 4 μm, and identified using an X-ray analyzer (trade name "RU-200 model", manufactured by Rigaku Denki Co., Ltd.). The one calcined at 1250°C is α-type tertiary calcium phosphate, and 11
The one calcined at 50℃ contains α-type tribasic calcium phosphate and β
It is a mixture with type tertiary calcium phosphate and heated at 1000℃.
The calcined product was β-type tertiary calcium phosphate.
【００２８】[0028]
【表１】[Table 1]
【００２９】[0029]
【実施例５】実施例３において、１２５０℃で焼成して
得られた第３リン酸カルシウムを用いて、表２に示す組
成にて水硬性リン酸カルシウムセメントを調製した。次
いで得られた水硬性リン酸カルシウムセメント１７５重
量部に対して、硬化液として水１００重量部を加えて練
和し、硬化時間及び硬化したセメントの圧縮強度を測定
した。この際硬化時間は、ＪＩＳ Ｔ６６０４に準じ
て測定し、圧縮強度は、人工体液中に１日放置した後取
り出したセメント（直径７ｍｍ，長さ１４ｍｍ）を濡れ
たまま毎分１ｍｍ／分の加重速度で加圧して測定した。
なお測定に際しては、インストロン社製万能試験機「１
１２５型」を用いた。結果を表２に示す。Example 5 Using the tertiary calcium phosphate obtained by firing at 1250° C. in Example 3, hydraulic calcium phosphate cement was prepared with the composition shown in Table 2. Next, 100 parts by weight of water as a hardening liquid was added to 175 parts by weight of the obtained hydraulic calcium phosphate cement and kneaded, and the hardening time and compressive strength of the hardened cement were measured. At this time, the hardening time was measured according to JIS T6604, and the compressive strength was measured by applying the cement (diameter 7 mm, length 14 mm), which was taken out after leaving it in an artificial body fluid for one day, at a loading rate of 1 mm/min while still wet. Measurement was carried out by applying pressure. For measurement, use Instron's universal testing machine "1".
125 type" was used. The results are shown in Table 2.
【００３０】[0030]
【比較例１】水硬性リン酸カルシウムセメントの粉剤成
分を、第３リン酸カルシウムのみとした以外は、実施例
５と同様にして硬化時間及び圧縮強度を測定した。結果
を表２に示す。[Comparative Example 1] The curing time and compressive strength were measured in the same manner as in Example 5, except that the powder component of the hydraulic calcium phosphate cement was only tertiary calcium phosphate. The results are shown in Table 2.
【００３１】[0031]
【参考例１】第２リン酸カルシウム２水和物（和光純薬
工業（株）社製，特級）３４４ｇを５５０℃にて３時間
焼成してピロリン酸カルシウム２５４ｇを得た。次いで
得られたピロリン酸カルシウムと炭酸カルシウムとを等
モルにて混合し、１２５０℃にて焼成してα型第３リン
酸カルシウムを得た。得られたα型第３リン酸カルシウ
ムをボ−ルミルを用いて平均粒径４μｍまで粉砕した。[Reference Example 1] 344 g of dicalcium phosphate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was calcined at 550° C. for 3 hours to obtain 254 g of calcium pyrophosphate. Next, the obtained calcium pyrophosphate and calcium carbonate were mixed in equimolar amounts and fired at 1250°C to obtain α-type tertiary calcium phosphate. The obtained α-type tertiary calcium phosphate was ground to an average particle size of 4 μm using a ball mill.
【００３２】[0032]
【比較例２】参考例１で調製したα型第３リン酸カルシ
ウムを用いた以外は実施例５と同様にして硬化時間及び
圧縮強度を測定した。結果を表２に示す。Comparative Example 2 The curing time and compressive strength were measured in the same manner as in Example 5, except that the α-type tertiary calcium phosphate prepared in Reference Example 1 was used. The results are shown in Table 2.
【００３３】[0033]
【表２】[Table 2]
【００３４】[0034]
【実施例６】Ｃａ（ＯＨ）２とＨ３ＰＯ４とを用いて、
反応温度をそれぞれ１℃、１０℃、２０℃、３０℃とし
、焼成温度を１２５０℃として３時間焼成した。得られ
たα型第３リン酸カルシウムと第２リン酸カルシウム２
水和物をＣａ／Ｐモル比１．４８となるように混合して
、水硬性リン酸カルシウムセメントを調製した。得られ
たセメントを用いて、実施例５と同様にして硬化時間及
び圧縮強度を測定した。結果を表３に示す。[Example 6] Using Ca(OH)2 and H3PO4,
The reaction temperatures were 1°C, 10°C, 20°C, and 30°C, respectively, and the firing temperature was 1250°C for 3 hours. The obtained α-type tertiary calcium phosphate and dibasic calcium phosphate 2
A hydraulic calcium phosphate cement was prepared by mixing the hydrates at a Ca/P molar ratio of 1.48. Using the obtained cement, the curing time and compressive strength were measured in the same manner as in Example 5. The results are shown in Table 3.
【００３５】[0035]
【比較例３】反応系の温度制御を行なわない以外は、実
施例６と同様にして、α型第３リン酸カルシウムを調製
し、次いで水硬性リン酸カルシウムセメントを調製して
、硬化時間及び圧縮強度を測定した。結果を表３に示す
。尚、この際反応系の温度は、３５〜４０℃であった。[Comparative Example 3] α-type tertiary calcium phosphate was prepared in the same manner as in Example 6, except that the temperature of the reaction system was not controlled. Then, hydraulic calcium phosphate cement was prepared, and the curing time and compressive strength were measured. did. The results are shown in Table 3. In this case, the temperature of the reaction system was 35 to 40°C.
【００３６】[0036]
【比較例４】参考例１で得られた第３リン酸カルシウム
を用いた以外は、実施例６と同様にして硬化時間及び圧
縮強度を測定した。結果を表３に示す。Comparative Example 4 The curing time and compressive strength were measured in the same manner as in Example 6, except that the tertiary calcium phosphate obtained in Reference Example 1 was used. The results are shown in Table 3.
【００３７】[0037]
【実施例７】原料スラリ−をスプレ−ドライヤ−で噴霧
乾燥した後、１０００Ｋｇ／ｃｍ２の圧力で加圧成形し
て焼成した以外は、実施例６と同様にして湿式合成及び
セメントの調製を行ない、硬化時間及び圧縮強度を測定
した。結果を表３に示す。[Example 7] Wet synthesis and cement preparation were carried out in the same manner as in Example 6, except that the raw material slurry was spray-dried with a spray dryer, then pressure-molded and fired at a pressure of 1000 kg/cm2. , curing time and compressive strength were measured. The results are shown in Table 3.
【００３８】[0038]
【表３】[Table 3]
【００３９】[0039]
【実施例８〜１０】Ｃａ（ＯＨ）２とＨ３ＰＯ４とを用
いて、反応温度を１０℃とし、焼成温度をそれぞれ１０
００℃（実施例８）、１１５０℃（実施例９）、１２５
０℃（実施例１０）として３時間焼成した以外は、実施
例３と同様にして第３リン酸カルシウムを調製した。結
果を表４に示す。[Examples 8 to 10] Using Ca(OH)2 and H3PO4, the reaction temperature was 10°C, and the calcination temperature was 10°C.
00°C (Example 8), 1150°C (Example 9), 125
Tertiary calcium phosphate was prepared in the same manner as in Example 3, except that the temperature was 0° C. (Example 10) for 3 hours. The results are shown in Table 4.
【００４０】[0040]
【表４】[Table 4]
【００４１】[0041]
【実施例１１〜１２】実施例８及び１０で得られた第３
リン酸カルシウムを表３に示す混合割合にて混合し、得
られた第３リン酸カルシウムと第２リン酸カルシウム２
水和物とをＣａ／Ｐモル比１．４８となるように混合し
て、水硬性リン酸カルシウムセメントを調製した（実施
例１１）。また実施例９で得られた第３リン酸カルシウ
ムをそのまま用いて、同様に水硬性リン酸カルシウムセ
メントを調製した（実施例１２）。実施例５と同様にし
て硬化時間及び圧縮強度を測定した。結果を表５に示す
。[Examples 11-12] The third product obtained in Examples 8 and 10
Calcium phosphate was mixed at the mixing ratio shown in Table 3, and the obtained tertiary calcium phosphate and dibasic calcium phosphate 2
Hydraulic calcium phosphate cement was prepared by mixing with Ca/P hydrate at a molar ratio of 1.48 (Example 11). Further, a hydraulic calcium phosphate cement was prepared in the same manner using the tertiary calcium phosphate obtained in Example 9 (Example 12). The curing time and compressive strength were measured in the same manner as in Example 5. The results are shown in Table 5.
【００４２】[0042]
【比較例５】反応系の温度制御を行なわない以外は、実
施例６と同様にして、α型第３リン酸カルシウムを調製
し、硬化時間及び圧縮強度を測定した。結果を表５に示
す。尚、この際反応系の温度は、３５℃であった。Comparative Example 5 α-type tertiary calcium phosphate was prepared in the same manner as in Example 6, except that the temperature of the reaction system was not controlled, and the curing time and compressive strength were measured. The results are shown in Table 5. Note that the temperature of the reaction system at this time was 35°C.
【００４３】[0043]
【比較例６】参考例１で得られたα型第３リン酸カルシ
ウムを用いた以外は、実施例６と同様にして硬化時間及
び圧縮強度を測定した。結果を表５に示す。Comparative Example 6 The curing time and compressive strength were measured in the same manner as in Example 6, except that the α-type tertiary calcium phosphate obtained in Reference Example 1 was used. The results are shown in Table 5.
【００４４】[0044]
【表５】[Table 5]
Claims (2)
カルシウム供給原料及びリン供給原料を含む原料成分を
湿式合成した原料スラリ−を、乾燥後、７００℃以上で
焼成することを特徴とする第３リン酸カルシウムの製造
方法。Claim 1: In an aqueous solution at a water temperature of 30°C or less,
A method for producing tertiary calcium phosphate, which comprises drying a raw material slurry obtained by wet-synthesizing raw material components including a calcium supply raw material and a phosphorus supply raw material, and then calcining it at 700°C or higher.
カルシウム供給原料及びリン供給原料を含む原料成分を
湿式合成した原料スラリ−を、乾燥後、７００℃以上で
焼成して得られる第３リン酸カルシウムと、第２リン酸
カルシウム及び／又は第１リン酸カルシウムとの混合物
を主成分とする粉剤及び液剤を含む水硬性リン酸カルシ
ウムセメント。Claim 2: In an aqueous solution at a water temperature of 30°C or less,
A mixture of tertiary calcium phosphate, dibasic calcium phosphate and/or monobasic calcium phosphate obtained by drying a raw material slurry obtained by wet-synthesizing raw material components including a calcium supply raw material and a phosphorus supply raw material, and then calcining it at 700°C or higher. Hydraulic calcium phosphate cement containing powder and liquid as main ingredients.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3092117A JP2776049B2 (en) | 1991-04-23 | 1991-04-23 | Method for producing tertiary calcium phosphate and hydraulic calcium phosphate cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3092117A JP2776049B2 (en) | 1991-04-23 | 1991-04-23 | Method for producing tertiary calcium phosphate and hydraulic calcium phosphate cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04321507A true JPH04321507A (en) | 1992-11-11 |
| JP2776049B2 JP2776049B2 (en) | 1998-07-16 |
Family
ID=14045495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3092117A Expired - Fee Related JP2776049B2 (en) | 1991-04-23 | 1991-04-23 | Method for producing tertiary calcium phosphate and hydraulic calcium phosphate cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2776049B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9487443B2 (en) | 2014-03-14 | 2016-11-08 | Ricoh Company, Ltd. | Layer stack formation powder material, powder layer stack formation hardening liquid, layer stack formation material set, and layer stack object formation method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211037B (en) * | 2014-08-07 | 2016-06-01 | 华中农业大学 | Phosvitin and polypeptide thereof is utilized to catalyze and synthesize the method for biomimetic material hydroxyapatite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58161911A (en) * | 1982-03-19 | 1983-09-26 | Taihei Kagaku Sangyo Kk | Manufacture of beta-form calcium tertiary phosphate |
| JPS63100008A (en) * | 1986-10-16 | 1988-05-02 | Hisao Sugihara | Preparation of tricalcium phosphate |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
| JPH0369536A (en) * | 1989-08-08 | 1991-03-25 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement composition |
-
1991
- 1991-04-23 JP JP3092117A patent/JP2776049B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58161911A (en) * | 1982-03-19 | 1983-09-26 | Taihei Kagaku Sangyo Kk | Manufacture of beta-form calcium tertiary phosphate |
| JPS63100008A (en) * | 1986-10-16 | 1988-05-02 | Hisao Sugihara | Preparation of tricalcium phosphate |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
| JPH0369536A (en) * | 1989-08-08 | 1991-03-25 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9487443B2 (en) | 2014-03-14 | 2016-11-08 | Ricoh Company, Ltd. | Layer stack formation powder material, powder layer stack formation hardening liquid, layer stack formation material set, and layer stack object formation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2776049B2 (en) | 1998-07-16 |
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