JPH0333670B2 - - Google Patents
Info
- Publication number
- JPH0333670B2 JPH0333670B2 JP62193482A JP19348287A JPH0333670B2 JP H0333670 B2 JPH0333670 B2 JP H0333670B2 JP 62193482 A JP62193482 A JP 62193482A JP 19348287 A JP19348287 A JP 19348287A JP H0333670 B2 JPH0333670 B2 JP H0333670B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- hydraulic cement
- molar ratio
- cement composition
- hardening
- 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
- 239000011575 calcium Substances 0.000 claims description 25
- 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 20
- 239000000203 mixture Substances 0.000 claims description 17
- 239000001506 calcium phosphate Substances 0.000 claims description 12
- 239000011396 hydraulic cement Substances 0.000 claims description 11
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 10
- 235000011010 calcium phosphates Nutrition 0.000 claims description 10
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 235000019731 tricalcium phosphate Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 4
- 235000019700 dicalcium phosphate Nutrition 0.000 description 4
- 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 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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
- 230000002378 acidificating effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- -1 Dicalcium phosphate-calcium carbonate-water Chemical compound 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940078495 calcium phosphate dibasic Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 239000000243 solution Substances 0.000 description 1
- ZGYZFXSEIYZCNV-UHFFFAOYSA-H tricalcium hydrogen phosphate Chemical compound [Ca++].[Ca++].[Ca++].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O ZGYZFXSEIYZCNV-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
Description
産業上の利用分野
本発明はリン酸カルシウム水硬性セメント組成
物に関する。
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、骨の主成分に近似した
化合物に転化するゆえに、歯、骨修復材料とし
て、また生体高分子や生体有害機物または無機質
イオンの吸着剤として有用なものである。
従来技術
従来のリン酸カルシウム水硬性セメント組成物
には、(1)第３リン酸カルシウム−硬化液剤系（門
間、上野、特許第1103653号；門間、後藤、特許
第1343300号；楠ら、特開昭62−83348）、(2)第４
リン酸カルシウム−第２リン酸カルシウム−リン
酸水溶液系（土井ら、歯科材料・器機、６、53
（1987））、(3)第２リン酸カルシウム−炭酸カルシ
ウム−水系（門間、窯業協会誌、95、284（1987））
が知られている。
しかし、これらの水硬性セメント組成物は、(1)
においてはセメント基材の硬化を有効に発現させ
るために各種の硬化液剤が使用され、その選択に
よつて硬化体の物性が変動するので、安定した性
状のものが得られにくい、(2)では硬化速度および
物性は良いが、基材の第４リン酸カルシウムは非
常に高価であり、また緩和液に水ではなく希リン
酸を使用する必要があり高価となる。(3)では原料
基材は安価であるが、炭酸カルシウムを使用する
必要があり、凝結時間も比較的長い、などの欠点
があつた。
発明の目的
本発明は従来法のような高価な原料、繁雑な硬
化剤の選択などをすることなく、単に水と練和す
るだけで容易に安定した物性を与える安価なリン
酸カルシウム水硬性セメント組成物を提供するに
ある。
発明の構成
本発明者は、前記目的を達成すべく鋭意研究の
結果、α型第３リン酸カルシウムと第２リン酸カ
ルシウム２水和物のそれぞれ単体では凝結性の低
いあるいは無い両物質を混合した組成物が、単に
水と練和するだけで、容易にアパタイト（Ca10-z
（HPO4）z（PO4）6-z（OH）2・nH2O）あるいはそ
の類似化合物であるオクタルカルシウムホスフエ
ート（Ca8H2（PO4）6・5H2O、以下はOCPと略記
する）を生じながら凝結硬化する新しい知見を得
た。この知見に基づいて本発明を完成した。
本発明の要旨は、α型第３リン酸カルシウムに
第２リン酸カルシウム２水和物をCa／Ｐモル比
で1.20〜1.47になる割合で混合した粉末から成る
ことを特徴とするリン酸カルシウム水硬性セメン
ト組成物にある。α型第３リン酸カルシウム
（Ca3（PO4）2は次のように水中でアパタイトおよ
びOCPへ変化させることができる。
（Ca3（PO4）2→Ca10-z（HPO4）z（PO4）6-z
（OH）2・nH2O＋２（１−ｚ）／3H3PO4
→Ca8H2（PO4）6・5H2O＋Ca（OH）2
これらの反応は弱酸性の範囲（５＜PH＜８）で
よく進行する。従つて、塩基性物質である（Ca3
（PO4）2によつて上昇した反応系のPH値（９−10）
を引き下げなければ、反応は進行しにくい。その
ために、これまではPH調整能のある各種の無機系
および有機系の塩の中から硬化液剤を選択すると
いう繁雑な作業をしなければならなかつた。
一方、第２リン酸カルシウム２水和物
（CaHPO4・2H2O）は、次のような反応でアパタ
イトおよびOCPへ変化させることができる。
CaHPO4・2H2O
→Ca10-z（HPO4）z（PO4）6-z
（OH）2・nH2O＋（４−ｚ）H3PO4
→Ca8H2（PO4）6・5H2O
＋2Ca（H2PO4）2・H2O
これらの反応は弱酸性から塩基性の範囲（６＜
PH＜９）でよく進行する。従つて、酸性物質であ
るCaHPO4・2H2Oによつて降下する反応系のPH
値（50℃で約5.0）を引き上げなければ、反応は
進行しない。そのために、これまでは、炭酸カル
シウムを添加してPHを上げていたが、凝結に時間
がかかつた。
本発明のように、α型第３リン酸カルシウムと
第２リン酸カルシウム２水和物を混合しておく
と、各々の水和反応の進行に必要とされるPH条件
が相補し合つて、両方とも継続的に水和反応して
硬化していく。第１図にこのPH効果を示した。
α型第３リン酸カルシウムと第２リン酸カルシ
ウムとの混合割合はCa／モル比で1.20〜1.47であ
る。例えば、Ca／Ｐ＝1.33の混合物に水を加えて
ペースト化してから生体温度である37℃に放置す
るとOCPを生じて凝結硬化する。その反応を示
すと次の通りである。
2Ca3（PO4）2＋2CaHPO4・2H2O
→Ca8H2（PO4）6・5H2O
このように、OCP以外の副生成物はなく、非
常に優れた水硬性セメント組成物である。
本発明の水硬性セメント組成物におけるCa／
Ｐモル比が1.20〜1.47の範囲であり、第３リン酸
カルシウムはα型であることが必要である。
Ca／Ｐモル比（α型第３リン酸カルシウムの
Ca／Ｐは1.50、第２リン酸カルシウムのCa／Ｐ
は1.00）が1.20未満、1.47を越えると、凝固硬化
時間が160分以上と長くなり、また、β型第３リ
ン酸カルシウムを使用すると凝固硬化時間は120
分と長くなる。またCa／Ｐモル比が1.33未満の場
合は未反応のCaHPO4・2H2Oが残留する。なお、
本発明の水硬性セメント組成物は、これに、アル
ミナ、アパタイト、ジルコニア、窒化けい素、炭
化けい素などの骨材を１種または２種以上混合す
ることは任意である。これら骨材を混合すると、
硬化物の機械的性質を向上させることができる。
実施例 １
α−Ca3（PO4）2（3.10ｇ）にCaHPO4・2H2O
（1.72ｇ）を混合してCa／Ｐモル比を1.33とした。
この混合物を適量の水と練和してペーストを作製
し、37℃に保持した。凝固時間は約９分であつ
た。硬化物中にOCPの生成が確認された。
実施例 ２−５
実施例１の操作手順で、第１表に示した混合割
合で実験を行つた。その結果は第１表に示す通り
であつた。
FIELD OF INDUSTRIAL APPLICATION The present invention relates to calcium phosphate hydraulic cement compositions. Because the calcium phosphate hydraulic cement composition is converted into a compound similar to the main components of teeth and bones in living organisms through setting and hardening, it can be used as a tooth and bone repair material, and also as a material for removing biopolymers, biohazardous substances, and inorganic ions. It is useful as an adsorbent. Prior Art Conventional calcium phosphate hydraulic cement compositions include (1) tertiary calcium phosphate-curing liquid system (Monma, Ueno, Patent No. 1103653; Monma, Goto, Patent No. 1343300; Kusunoki et al., JP-A-62-1999); 83348), (2) 4th
Calcium phosphate-dibasic calcium phosphate-phosphoric acid aqueous solution system (Doi et al., Dental Materials and Equipment, 6, 53
(1987)), (3) Dicalcium phosphate-calcium carbonate-water system (Monma, Ceramics Association Journal, 95, 284 (1987))
It has been known. However, these hydraulic cement compositions (1)
In (2), various hardening liquid agents are used to effectively harden the cement base material, and the physical properties of the cured product vary depending on the selection, making it difficult to obtain stable properties. Although the curing speed and physical properties are good, the base material, quaternary calcium phosphate, is very expensive, and it is necessary to use dilute phosphoric acid instead of water as a relaxing solution, making it expensive. In (3), the raw material base material is inexpensive, but it has drawbacks such as the need to use calcium carbonate and the coagulation time is relatively long. Purpose of the Invention The present invention provides an inexpensive calcium phosphate hydraulic cement composition that easily provides stable physical properties simply by mixing with water, without requiring expensive raw materials or complicated selection of curing agents as required in conventional methods. is to provide. Composition of the Invention As a result of intensive research to achieve the above object, the present inventor has discovered a composition in which α-type tribasic calcium phosphate and dibasic calcium phosphate dihydrate are mixed together, each of which has low or no coagulability when used alone. , apatite (Ca 10-z
(HPO 4 ) z (PO 4 ) 6-z (OH) 2・nH 2 O) or its similar compound octal calcium phosphate (Ca 8 H 2 (PO 4 ) 6・5H 2 O, hereinafter referred to as OCP). We have obtained new knowledge that solidification and hardening occur while producing (abbreviated). The present invention was completed based on this knowledge. The gist of the present invention is to provide a calcium phosphate hydraulic cement composition comprising a powder in which α-type tribasic calcium phosphate is mixed with dibasic calcium phosphate dihydrate at a Ca/P molar ratio of 1.20 to 1.47. be. α-type tricalcium phosphate (Ca 3 (PO 4 ) 2 ) can be converted into apatite and OCP in water as follows: (Ca 3 (PO 4 ) 2 →Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2・nH 2 O+2(1-z)/3H 3 PO 4 →Ca 8 H 2 (PO 4 ) 6・5H 2 O+Ca(OH) 2These reactions occur in the weakly acidic range ( 5<PH<8). Therefore, it is a basic substance (Ca 3
PH value of the reaction system increased by (PO 4 ) 2 (9-10)
Unless the is lowered, the reaction will be difficult to proceed. To this end, until now it has been necessary to carry out the complicated task of selecting a curing agent from among various inorganic and organic salts that have the ability to adjust pH. On the other hand, dicalcium phosphate dihydrate (CaHPO 4 .2H 2 O) can be changed into apatite and OCP by the following reaction. CaHPO 4・2H 2 O →Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2・nH 2 O+(4-z)H 3 PO 4 →Ca 8 H 2 (PO 4 ) 6・5H 2 O +2Ca(H 2 PO 4 ) 2・H 2 O These reactions range from weak acidity to basicity (6<
It progresses well with pH<9). Therefore, the pH of the reaction system is lowered by the acidic substance CaHPO 4 2H 2 O.
The reaction will not proceed unless the value (approximately 5.0 at 50°C) is raised. To this end, calcium carbonate was previously added to raise the pH, but it took a long time for it to coagulate. As in the present invention, when α-type tribasic calcium phosphate and dibasic calcium phosphate dihydrate are mixed, the PH conditions required for each hydration reaction to proceed are complementary, and both can be continuously produced. It undergoes a hydration reaction and hardens. Figure 1 shows this PH effect. The mixing ratio of α-type tertiary calcium phosphate and dibasic calcium phosphate is 1.20 to 1.47 in terms of Ca/mole ratio. For example, if water is added to a mixture of Ca/P=1.33 to form a paste and then left at 37° C., which is the biological temperature, OCP will be generated and the paste will solidify and harden. The reaction is shown below. 2Ca 3 (PO 4 ) 2 + 2CaHPO 4・2H 2 O →Ca 8 H 2 (PO 4 ) 6・5H 2 O In this way, there are no by-products other than OCP, making it an excellent hydraulic cement composition. be. Ca/in the hydraulic cement composition of the present invention
It is necessary that the P molar ratio is in the range of 1.20 to 1.47, and that the tertiary calcium phosphate is α-type.
Ca/P molar ratio (α-type tertiary calcium phosphate
Ca/P is 1.50, Ca/P of dibasic calcium phosphate
1.00) is less than 1.20 or exceeds 1.47, the solidification and hardening time will be longer than 160 minutes, and if β-type tricalcium phosphate is used, the solidification and hardening time will be 120 minutes or more.
It will be a minute longer. Moreover, when the Ca/P molar ratio is less than 1.33, unreacted CaHPO 4 .2H 2 O remains. In addition,
The hydraulic cement composition of the present invention may optionally contain one or more aggregates such as alumina, apatite, zirconia, silicon nitride, and silicon carbide. When these aggregates are mixed,
The mechanical properties of the cured product can be improved. Example 1 α-Ca 3 (PO 4 ) 2 (3.10g) and CaHPO 4 2H 2 O
(1.72 g) was mixed to give a Ca/P molar ratio of 1.33.
This mixture was kneaded with an appropriate amount of water to prepare a paste, which was maintained at 37°C. The solidification time was approximately 9 minutes. Formation of OCP was confirmed in the cured product. Example 2-5 An experiment was conducted using the operating procedure of Example 1 and the mixing ratios shown in Table 1. The results were as shown in Table 1.
【表】【table】
【表】
発明の効果
本発明の組成物は、従来のような高価な第４リ
ン酸カルシウムを使用することなく、単体では凝
結性の遅いα型第３リン酸カルシウムと単体では
凝結性の無い第２リン酸カルシウムの両物質を組
み合わせるだけで、凝結硬化性の良いリン酸カル
シウム水硬性セメント組成物が得られる優れた硬
化を奏し得られる。[Table] Effects of the Invention The composition of the present invention does not use expensive quaternary calcium phosphate as in the past, but instead combines α-type tribasic calcium phosphate, which is slow to set when used alone, and dibasic calcium phosphate, which does not set when used alone. By simply combining both substances, a calcium phosphate hydraulic cement composition with good setting and hardening properties can be obtained, resulting in excellent hardening.
第１図はα−Ca3（PO4）2または（CaHPO4・
2H2O、もしくはその混合物（Ca／Ｐモル比＝
1.25−1.45）の1.0ｇを37℃の水50ml中に分散させ
たときのPHの時間変化を示す。
Figure 1 shows α−Ca 3 (PO 4 ) 2 or (CaHPO4・
2H 2 O or mixture thereof (Ca/P molar ratio =
1.25-1.45) is dispersed in 50 ml of water at 37°C.
Claims (1)
シウム２水和物をCa／Ｐモル比で1.20〜1.47の割
合で混合した粉末から成ることを特徴とするリン
酸カルシウム水硬性セメント組成物。1. A calcium phosphate hydraulic cement composition comprising a powder obtained by mixing α-type tertiary calcium phosphate and dicalcium phosphate dihydrate at a Ca/P molar ratio of 1.20 to 1.47.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62193482A JPS6437445A (en) | 1987-07-31 | 1987-07-31 | Calcium phosphate hydraulic cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62193482A JPS6437445A (en) | 1987-07-31 | 1987-07-31 | Calcium phosphate hydraulic cement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6437445A JPS6437445A (en) | 1989-02-08 |
| JPH0333670B2 true JPH0333670B2 (en) | 1991-05-17 |
Family
ID=16308763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62193482A Granted JPS6437445A (en) | 1987-07-31 | 1987-07-31 | Calcium phosphate hydraulic cement composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6437445A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345266A (en) * | 1989-07-12 | 1991-02-26 | Mitsubishi Materials Corp | Filling material for bone-defective part and bone-vacant part |
| JPH0360451A (en) * | 1989-07-25 | 1991-03-15 | Natl Inst For Res In Inorg Mater | Calcium phosphate hydraulic cement composition |
| JPH03112843A (en) * | 1989-09-25 | 1991-05-14 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement composition |
| JPH03122855A (en) * | 1989-10-06 | 1991-05-24 | Fuji Xerox Co Ltd | Floating head for magneto-optical recording type recorder |
| JPH03128061A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Hydraulic calcium phosphate cement composition |
| JPH03128063A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Hydraulic calcium phosphate cement composition |
| JPH03128062A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Hydraulic 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 |
| JPH0645494B2 (en) * | 1990-05-09 | 1994-06-15 | 三菱マテリアル株式会社 | Hydraulic calcium phosphate cement composition |
| JPH0645493B2 (en) * | 1990-05-09 | 1994-06-15 | 三菱マテリアル株式会社 | Hydraulic calcium phosphate cement composition |
| 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 |
| ATE425129T1 (en) * | 2000-07-19 | 2009-03-15 | Hoya Corp | CALCIUM PHOSPHATE CEMENT |
| WO2002068358A1 (en) * | 2001-02-28 | 2002-09-06 | Mitsubishi Materials Corporation | Calcium phosphate cement |
| WO2002068357A1 (en) * | 2001-02-28 | 2002-09-06 | Mitsubishi Materials Corporation | Calcium phosphate cement |
-
1987
- 1987-07-31 JP JP62193482A patent/JPS6437445A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6437445A (en) | 1989-02-08 |
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Legal Events
| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |