JPH059383B2 - - Google Patents
Info
- Publication number
- JPH059383B2 JPH059383B2 JP1203801A JP20380189A JPH059383B2 JP H059383 B2 JPH059383 B2 JP H059383B2 JP 1203801 A JP1203801 A JP 1203801A JP 20380189 A JP20380189 A JP 20380189A JP H059383 B2 JPH059383 B2 JP H059383B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- hydraulic
- present
- cement composition
- molar ratio
- 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 - Fee Related
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- 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 39
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 29
- 239000001506 calcium phosphate Substances 0.000 claims description 24
- 235000011010 calcium phosphates Nutrition 0.000 claims description 23
- 239000004568 cement Substances 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 15
- 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 13
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 239000011396 hydraulic cement Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- 210000000988 bone and bone Anatomy 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007794 irritation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229910052586 apatite Inorganic materials 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
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 2
- ZBZJARSYCHAEND-UHFFFAOYSA-L calcium;dihydrogen phosphate;hydrate Chemical compound O.[Ca+2].OP(O)([O-])=O.OP(O)([O-])=O ZBZJARSYCHAEND-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 monocalcium phosphate anhydride Chemical class 0.000 description 2
- 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 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 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
- 239000011324 bead Substances 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
- 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
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium phosphate dihydrate Substances O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 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 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002631 root canal filling material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Dental Preparations (AREA)
Description
＜産業上の利用分野＞
本発明は、骨欠損部及び骨空〓部を充填するこ
とができる医科用セメント、歯牙根管部充填剤等
に利用可能な水硬性リン酸カルシウムセメント組
成物に関する。
＜従来の技術＞
リン酸カルシウム水硬性セメント組成物は凝結
硬化によつ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。
従来は、このようなリン酸カルシウム水硬性セ
メント組成物は、硬化液として、塩類及び希薄酸
を組合せて使用したり（例えば、特開昭第59−
88351号公報）、又は不飽和カルボン酸重合体を含
有する酸性溶液を使用していた（例えば、特開昭
第60−253454号公報）。しかしながら、このよう
な従来のリン酸カルシウム水硬性セメント組成物
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
していた。更に、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。
かかる問題の解決のために、水により硬化する
リン酸カルシウム水硬性セメント組成物が開発さ
れている（例えば、FC REPORT、vol.6
（1988）、p.475〜480「バイオセラミツクスとして
の水硬化アパタイト」）。このような水により硬化
するリン酸カルシウム水硬性セメント組成物は現
在までに数種類開発されており、例えば単に水と
練和するのみで37℃において10分程度で硬化する
リン酸カルシウム水硬性セメント組成物（特開昭
64−37445号）が知られている。このリン酸カル
シウム水硬性セメント組成物はPHもほぼ中性程度
であり、生体に体する刺激も少なく、従来公知の
リン酸カルシウム水硬性セメント組成物の問題点
を解消するものである。
しかしながら、前記リン酸カルシウム水硬性セ
メント組成物は、α型第３リン酸カルシウムと、
第２リン酸カルシウム２水和物とをCa／Ｐモル
比で、1.20〜1.47の割合で混合することを特徴と
するものであつて、実用的な硬化時間を得るため
には、本来単独では硬化することがない前記第２
リン酸カルシウム２水和物を、Ca／Ｐモル比が
1.47である場合、最低でも6.6重量％程度含有さ
せなければならないという欠点がある。
＜発明が解決しようとする課題＞
従つて、本発明の主要な目的は、単に水と練和
するのみで、実用的な時間内に硬化し、空〓率が
低く、しかも初期強度が高い新規な水硬性リン酸
カルシウム水硬性セメント組成物を提供すること
にある。
また本発明の別の目的は、PHを中性付近に保持
することができ、生体親和性に優れた新規な水硬
性リン酸カルシウム水硬性セメント組成物を提供
することにある。
＜課題を解決するための手段＞
本発明によれば、α型第３リン酸カルシウム
と、第１リン酸カルシウムとをCa／Ｐモル比で、
1.400〜1.497の割合で混合して成る粉末を主成分
として含むことを特徴とする水硬性リン酸カルシ
ウムセメント組成物が提供される。
以下本発明を更に詳細に説明する。
本発明の水硬性リン酸カルシウムセメント組成
物は、α型第３リン酸カルシウムと、第１リン酸
カルシウムとを必須の構成成分として含有する。
本発明に用いる前記第１リン酸カルシウムは、
α型第３リン酸カルシウムの硬化促進剤として作
用する化合物であつて、例えば第１リン酸カルシ
ウム１水和物、第１リン酸カルシウム無水物等を
挙げることができ、更には、市販品を使用するこ
ともできる。前記第１リン酸カルシウムの組成物
全体に対する配合割合は、α型第３リン酸カルシ
ウムとのCa／Ｐモル比で決定することができ、
好ましくは0.2〜8.3重量％の微量な配合で十分で
ある。このように第１リン酸カルシウムの配合割
合が微量で良いのは、第１リン酸カルシウムが水
溶性であること及びα型第３リン酸カルシウム
と、第１リン酸カルシウムとの反応、具体的には
例えば、下記反応式で表わされる第１リン酸カル
シウム１水和物と、α型第３リン酸カルシウムと
の反応
2Ca3（PO4）2＋2Ca（H2PO4）2・H2O＋3H2O
→Ca8H2（PO4）6・5H2O＋2H3PO4
Ca3（PO4）2＋Ca（H2PO4）2・H2O＋7H2O
→4CaHPO4・2H2O
に関連があり、またα型第３リン酸カルシウムが
自己硬化能力を有するからである。従つて、本発
明の水硬性リン酸カルシウムセメント組成物は、
例えば、組成物全体に対して好ましくは90重量％
以上、特に好ましくは95重量％以上という多量の
塩基性物質であるα型第３リン酸カルシウムと、
微量の第１リン酸カルシウムとを含有するば良い
ので、PHを中性から弱アルカリ性に保持すること
ができ、生体への刺激は全く心配する必要がない
ものである。
本発明において、α型第３リン酸カルシウム
と、第１リン酸カルシウムとのCa／Ｐモル比は、
1.400〜1.497、好ましくは1.450〜1.495の範囲で
ある。前記Ca／Ｐモル比が1.400〜1.497の範囲外
である場合には、硬化時間が100分以上となり、
実用的でない。またCa／Ｐモル比が1.450〜1.495
の場合には、水と練和することにより溶解、反応
して玉を容易に生成する第１リン酸カルシウムの
配合割合を少量とすることができるので、操作性
の点で特に好ましく、更には硬化時間を10〜30分
の範囲とすることができるので好ましい。
本発明の水硬性リン酸カルシウムセメント組成
物では、前記必須の構成成分のほかに、生体親和
性を損ねることがないセラミツク粉体を含有させ
て、組成物を硬化させた際の機械的強度及び更に
生体親和性等を向上させることもできる。該セラ
ミツク粉体としては、例えばヒドロキシアパタイ
ト、フツ素アパタイト、β型第３リン酸カルシウ
ム、ピロリン酸カルシウム、第４リン酸カルシウ
ム等のリン酸カルシウム化合物；アルミナ、ジル
コニア、窒化珪素、炭化珪素等を挙げることがで
き、使用に際しては単独若しくは混合物として用
いることができる。
また本発明の水硬性リン酸カルシウムセメント
組成物では、更に必要に応じて、Ｘ線造影剤及び
抗菌剤等を任意に含有させることができる。例え
ば、好ましいＸ線造影剤としての硫酸バリウム、
次炭酸ビスマス、ヨードホルム等があり、好まし
い抗菌剤としてはヨードホルム及びクロルヘキシ
ジン等がある。
本発明の水硬性リン酸カルシウムセメント組成
物は、通常水と練和することにより使用すること
ができるが、操作性の向上及びセメント泥の濡れ
性を向上させるために、組成物及び／又は水の中
に例えば、高分子表面活性剤を添加することもで
きる。該高分子表面活性剤としては、合成高分子
化合物であるポリエチレングリコール、ポリビニ
ルアルコール等、生体高分子であるメチルセルロ
ース、カルボキシメチルセルロース、ヒドロキシ
プロピルメチルセルロース等及びこれらの化合物
の誘導体等が挙げられるが、生体に対する毒性が
ない限りは任意の化合物及びその誘導体が使用で
きる。
＜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。
実施例 １〜６
α型第３リン酸カルシウムと、市販の第１リン
酸カルシウム（和光純薬工業株式会社製）とを、
Ca／Ｐモル比で1.400、1.450、1.475、1.485、
1.495、1.497となるように、ボールミルによつて
混合し、水硬性リン酸カルシウムセメント組成物
を調製した。得られた夫々の組成物を水で練和硬
化させ、水中に24時間浸漬させた後、インストロ
ン社製1125型万能試験機により圧縮強度を測定し
た。この際硬化時間及びPHも同時に測定した。尚
PHの測定は、PH7.5の蒸留水50ml中に得られた
夫々の組成物１ｇを撹拌しながら分散させて、３
時間後に測定した値を示す。測定結果を表１に示
す。
比較例１及び２
Ca／Ｐモル比を1.333及び1.498とした以外は、
実施例１〜６と同様に水硬性リン酸カルシウムセ
メント組成物を調製し、各測定を行なつた。その
結果を表１に示す。
比較例 ３
水硬性リン酸カルシウムセメント組成物成分を
α型第３リン酸カルシウムのみにした以外は、実
施例１〜６と同様に各測定を行なつた。その結果
を表１に示す。
<Industrial Application Field> The present invention relates to a hydraulic calcium phosphate cement composition that can be used as a medical cement capable of filling bone defects and bone cavities, a tooth root canal filling agent, and the like. <Prior art> Calcium phosphate hydraulic cement compositions are useful as tooth and bone repair materials because they are converted into compounds that resemble the main components of teeth and bones in living organisms through setting and hardening, and are also useful as materials for restoring teeth and bones. It is known to be useful as an adsorbent for harmful organic substances or inorganic ions in macromolecules and living organisms. Conventionally, such calcium phosphate hydraulic cement compositions have been prepared by using a combination of salts and dilute acids as a curing liquid (for example, as disclosed in Japanese Patent Application Laid-open No. 59-1989).
88351), or an acidic solution containing an unsaturated carboxylic acid polymer (for example, JP-A-60-253454). However, in such conventional calcium phosphate hydraulic cement compositions, until the hardening of the cement is completed,
The curing liquid was highly acidic and caused considerable irritation to living organisms. Furthermore, even after the cement has hardened, the pH decreases due to the elution of unreacted acids, resulting in the problem of irritation to living organisms. To solve this problem, calcium phosphate hydraulic cement compositions that harden with water have been developed (for example, FC REPORT, vol.6
(1988), p. 475-480 “Hydraulic apatite as bioceramics”). To date, several types of calcium phosphate hydraulic cement compositions that harden with water have been developed. Akira
No. 64-37445) is known. The pH of this calcium phosphate hydraulic cement composition is approximately neutral, and it is less irritating to living organisms, thus solving the problems of conventionally known calcium phosphate hydraulic cement compositions. However, the calcium phosphate hydraulic cement composition contains α-type tertiary calcium phosphate;
It is characterized by being mixed with dibasic calcium phosphate dihydrate at a Ca/P molar ratio of 1.20 to 1.47. There is no such thing as the second
Calcium phosphate dihydrate has a Ca/P molar ratio of
If it is 1.47, there is a drawback that the content must be at least 6.6% by weight. <Problems to be Solved by the Invention> Therefore, the main object of the present invention is to create a new material that cures within a practical time by simply mixing with water, has a low porosity, and has high initial strength. An object of the present invention is to provide a hydraulic calcium phosphate hydraulic cement composition. Another object of the present invention is to provide a novel hydraulic calcium phosphate hydraulic cement composition that can maintain pH near neutrality and has excellent biocompatibility. <Means for Solving the Problems> According to the present invention, α-type tertiary calcium phosphate and monobasic calcium phosphate are mixed at a Ca/P molar ratio,
A hydraulic calcium phosphate cement composition is provided, which contains as a main component a powder mixed in a ratio of 1.400 to 1.497. The present invention will be explained in more detail below. The hydraulic calcium phosphate cement composition of the present invention contains α-type tertiary calcium phosphate and monobasic calcium phosphate as essential components. The primary calcium phosphate used in the present invention is
Compounds that act as hardening accelerators for α-type tertiary calcium phosphate include monocalcium phosphate monohydrate, monocalcium phosphate anhydride, and commercially available products. The blending ratio of the monobasic calcium phosphate to the entire composition can be determined by the Ca/P molar ratio with α-type tribasic calcium phosphate,
Preferably, a trace amount of 0.2 to 8.3% by weight is sufficient. The reason why the mixing ratio of monobasic calcium phosphate can be small is that monobasic calcium phosphate is water-soluble, and the reaction between alpha-type tribasic calcium phosphate and monobasic calcium phosphate can be carried out, for example, by the following reaction formula. Reaction between monocalcium phosphate monohydrate and α-type tertiary calcium phosphate 2Ca 3 (PO 4 ) 2 + 2Ca (H 2 PO 4 ) 2・H 2 O + 3H 2 O →Ca 8 H 2 (PO 4 ) 6・5H 2 O＋2H 3 PO 4 Ca 3 (PO 4 ) 2 +Ca(H 2 PO 4 ) 2・H 2 O＋7H 2 O →4CaHPO 4・2H 2 O is related, and α-type tribasic calcium phosphate has self-hardening ability. This is because it has Therefore, the hydraulic calcium phosphate cement composition of the present invention is
For example, preferably 90% by weight based on the total composition
As mentioned above, α-type tribasic calcium phosphate, which is a basic substance, preferably has a large amount of 95% by weight or more,
Since it is sufficient to contain a trace amount of monobasic calcium phosphate, the pH can be maintained from neutral to weakly alkaline, and there is no need to worry about irritation to living organisms. In the present invention, the Ca/P molar ratio of α-type tertiary calcium phosphate and monobasic calcium phosphate is:
It ranges from 1.400 to 1.497, preferably from 1.450 to 1.495. When the Ca/P molar ratio is outside the range of 1.400 to 1.497, the curing time is 100 minutes or more,
Not practical. Also, the Ca/P molar ratio is 1.450 to 1.495.
In this case, the proportion of monobasic calcium phosphate, which dissolves and reacts to easily form beads when mixed with water, can be reduced to a small amount, which is particularly preferable from the viewpoint of operability, and furthermore, the curing time can be reduced. This is preferable because it can range from 10 to 30 minutes. In addition to the above-mentioned essential components, the hydraulic calcium phosphate cement composition of the present invention contains ceramic powder that does not impair biocompatibility, thereby improving mechanical strength and biocompatibility when the composition is cured. It is also possible to improve affinity and the like. Examples of the ceramic powder include calcium phosphate compounds such as hydroxyapatite, fluoroapatite, β-type tertiary calcium phosphate, calcium pyrophosphate, and quaternary calcium phosphate; alumina, zirconia, silicon nitride, and silicon carbide. can be used alone or as a mixture. Furthermore, the hydraulic calcium phosphate cement composition of the present invention may optionally contain an X-ray contrast agent, an antibacterial agent, etc., if necessary. For example, barium sulfate as a preferred X-ray contrast agent,
Examples include bismuth subcarbonate and iodoform, and preferred antibacterial agents include iodoform and chlorhexidine. The hydraulic calcium phosphate cement composition of the present invention can be used by mixing with water, but in order to improve operability and wettability of cement mud, it is possible to use the composition and/or water. For example, a polymeric surfactant can also be added. Examples of the polymeric surfactants include synthetic polymers such as polyethylene glycol and polyvinyl alcohol, biopolymers such as methylcellulose, carboxymethylcellulose, and hydroxypropylmethylcellulose, and derivatives of these compounds. Any compound or derivative thereof can be used as long as it is not toxic. <Examples> The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 6 α-type tertiary calcium phosphate and commercially available monobasic calcium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) were
Ca/P molar ratio: 1.400, 1.450, 1.475, 1.485,
1.495 and 1.497, and mixed in a ball mill to prepare a hydraulic calcium phosphate cement composition. After kneading and hardening each of the obtained compositions with water and immersing them in water for 24 hours, the compressive strength was measured using a universal testing machine model 1125 manufactured by Instron. At this time, curing time and pH were also measured at the same time. still
To measure PH, 1 g of each composition was dispersed in 50 ml of distilled water with a pH of 7.5 with stirring.
Shows the value measured after hours. The measurement results are shown in Table 1. Comparative Examples 1 and 2 Except that the Ca/P molar ratio was 1.333 and 1.498,
Hydraulic calcium phosphate cement compositions were prepared in the same manner as Examples 1 to 6, and each measurement was performed. The results are shown in Table 1. Comparative Example 3 Each measurement was carried out in the same manner as in Examples 1 to 6, except that the only component of the hydraulic calcium phosphate cement composition was α-type tertiary calcium phosphate. The results are shown in Table 1.
【表】
＜発明の効果＞
本発明の水硬性リン酸カルシウムセメント組成
物は、塩基性のα型第３リン酸カルシウムと、弱
酸性の微量第１リン酸カルシウムとを、特定の
Ca／Ｐモル比で混合しているので、PHを中性程
度に保持することができ、単に水と練和すること
により、アパタイト、オクタカルシウムホスフエ
ート（Ca8H2（PO4）6・5H2O）、第２リン酸カル
シウム２水和物（CaHPO4・2H2O）を生成しな
がら水和させることができる。また生体親和性に
優れており、短時間で硬化させることができ、更
には得られる硬化体の空〓率が低く、初期強度に
優れるので、骨欠損部及び骨空〓部を充填するこ
とができる医科用セメント、歯牙根管部充填剤等
として極めて有用である。[Table] <Effects of the Invention> The hydraulic calcium phosphate cement composition of the present invention combines basic α-type tertiary calcium phosphate and weakly acidic trace amount monobasic calcium phosphate in a specific manner.
Since the Ca/P molar ratio is mixed, the pH can be maintained at a neutral level, and by simply mixing with water, apatite and octacalcium phosphate (Ca 8 H 2 (PO 4 ) 6 . 5H 2 O) and dicalcium phosphate dihydrate (CaHPO 4 .2H 2 O). In addition, it has excellent biocompatibility and can be cured in a short time, and the resulting cured product has a low porosity and excellent initial strength, making it suitable for filling bone defects and bone voids. It is extremely useful as medical cement, tooth root canal filling material, etc.
Claims (1)
ルシウムとをCa／Ｐモル比で、1.400〜1.497の割
合で混合して成る粉末を主成分として含むことを
特徴とする水硬性リン酸カルシウムセメント組成
物。1. A hydraulic calcium phosphate cement composition comprising as a main component a powder obtained by mixing α-type tertiary calcium phosphate and monobasic calcium phosphate at a Ca/P molar ratio of 1.400 to 1.497.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1203801A JPH0369536A (en) | 1989-08-08 | 1989-08-08 | Hydraulic calcium phosphate cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1203801A JPH0369536A (en) | 1989-08-08 | 1989-08-08 | Hydraulic calcium phosphate cement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0369536A JPH0369536A (en) | 1991-03-25 |
| JPH059383B2 true JPH059383B2 (en) | 1993-02-04 |
Family
ID=16479964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1203801A Granted JPH0369536A (en) | 1989-08-08 | 1989-08-08 | Hydraulic calcium phosphate cement composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0369536A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2621622B2 (en) * | 1990-09-27 | 1997-06-18 | 三菱マテリアル株式会社 | Hydraulic calcium phosphate cement |
| JP2776049B2 (en) * | 1991-04-23 | 1998-07-16 | 三菱マテリアル株式会社 | Method for producing tertiary calcium phosphate and hydraulic calcium phosphate cement |
| JP2626358B2 (en) * | 1991-10-29 | 1997-07-02 | 三菱マテリアル株式会社 | Calcium phosphate granule cement and method for producing the same |
| FR2693716B1 (en) * | 1992-07-20 | 1994-10-21 | Toulouse Inst Nat Polytech | Process for obtaining phosphocalcic hydroxyapatite, applications for bone or dental filling, or molding of parts, and products used. |
| JP5781265B2 (en) | 2009-07-31 | 2015-09-16 | 三菱重工業株式会社 | Transport container for fuel assembly |
-
1989
- 1989-08-08 JP JP1203801A patent/JPH0369536A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0369536A (en) | 1991-03-25 |
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