JPH03174348A - Hydraulic calcium phosphate cement - Google Patents
Hydraulic calcium phosphate cementInfo
- Publication number
- JPH03174348A JPH03174348A JP1309041A JP30904189A JPH03174348A JP H03174348 A JPH03174348 A JP H03174348A JP 1309041 A JP1309041 A JP 1309041A JP 30904189 A JP30904189 A JP 30904189A JP H03174348 A JPH03174348 A JP H03174348A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- cement
- hydroxyapatite
- bone
- weight
- 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
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 35
- 239000004568 cement Substances 0.000 title claims abstract description 35
- 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 28
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 26
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 25
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 24
- 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 abstract description 23
- 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 12
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 28
- 239000000203 mixture Substances 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000003479 dental cement Substances 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 2
- 229910052791 calcium Inorganic materials 0.000 abstract 2
- 230000007547 defect Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 150000004804 polysaccharides Chemical class 0.000 description 6
- 238000001356 surgical procedure Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 3
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 3
- 229920002527 Glycogen Polymers 0.000 description 3
- 229920000084 Gum arabic Polymers 0.000 description 3
- 241000978776 Senegalia senegal Species 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000000205 acacia gum Substances 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 229960001126 alginic acid Drugs 0.000 description 3
- 150000004781 alginic acids Chemical class 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229940096919 glycogen Drugs 0.000 description 3
- 229920002674 hyaluronan Polymers 0.000 description 3
- 229960003160 hyaluronic acid Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920001287 Chondroitin sulfate Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 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
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- KXKPYJOVDUMHGS-OSRGNVMNSA-N chondroitin sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](OS(O)(=O)=O)[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](C(O)=O)O1 KXKPYJOVDUMHGS-OSRGNVMNSA-N 0.000 description 2
- 229940059329 chondroitin sulfate Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 208000006386 Bone Resorption Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-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
- 229920002567 Chondroitin Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002385 Sodium hyaluronate Polymers 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000024279 bone resorption Effects 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
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- -1 fluoroapatite Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000011164 ossification Effects 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、骨欠損部及び骨空隙部を充填する医科用セメ
ント及び歯牙様管部充填材等の歯科用セメントとして利
用可能な水硬性リン酸カルシウムセメントに関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides a hydraulic calcium phosphate that can be used as a medical cement for filling bone defects and bone voids, and a dental cement such as a filling material for a tooth-like canal. Regarding cement.
〈従来の技術〉
水硬性リン酸カルシウムセメントは、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。<Prior art> Hydraulic calcium phosphate cement 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 setting and hardening, and is also useful as a material for restoring teeth and bones. It is known to be useful as an adsorbent for harmful organic substances or inorganic ions in living organisms.
従来、このような水硬性リン酸カルシウムセメントは、
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）、また不飽
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）、シか
しながら、このような従来の水硬性リン酸カルシウムセ
メントにおいては、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。Conventionally, such hydraulic calcium phosphate cement is
As a curing liquid, use a combination of salts and dilute acids (
For example, Japanese Patent Application Laid-Open No. 59-88351) and acidic solutions containing unsaturated carboxylic acid polymers were used (for example, Japanese Patent Application Laid-Open No. 60-253454). In conventional hydraulic calcium phosphate cements, until the cement hardens,
The curing liquid was highly acidic and caused considerable irritation to living organisms. Furthermore, even after the cement has finished hardening, the pH decreases due to the elution of unreacted acids, resulting in the problem of irritation to living organisms.
一方、結晶子の大きさが、５０人〜１０μｍのヒドロキ
シアパタイトを骨欠損部及び骨空隙部充填剤に充填して
骨組織と一体化させる骨欠損部及び骨空隙部充填剤は公
知である（例えば、特開昭５６−５４８４１号公報）。On the other hand, a bone defect and bone void filling material is known in which the bone defect and bone void filling material is integrated with bone tissue by filling the bone defect and bone void filling material with hydroxyapatite having a crystallite size of 50 to 10 μm ( For example, Japanese Patent Application Laid-Open No. 56-54841).
更に、骨欠損部及び骨空隙部並びに骨吸収部に最短径が
０．１〜３．０ａｍ、且つ比表面積形状係数φが６．３
〜１５であるヒドロキシアパタイトを充填する充填剤も
公知である（特開昭６１−２０５５８号）。Furthermore, the shortest diameter of the bone defect part, bone void part, and bone resorption part is 0.1 to 3.0 am, and the specific surface area shape factor φ is 6.3.
A filler for filling hydroxyapatite with a molecular weight of 15 to 15 is also known (JP-A-61-20558).
これらの公知の骨欠損部及び骨空隙部充填材中で使用さ
れるヒドロキシアパタイトは生体親和性に優れており、
不定形上の骨欠損部及び骨空隙部への充填剤としては上
記のような粉状又は粒状のヒドロキシアパタイトが最適
である。Hydroxyapatite used in these known bone defect and bone cavity filling materials has excellent biocompatibility,
Powdered or granular hydroxyapatite as described above is most suitable as a filler for irregularly shaped bone defects and bone voids.
しかしながら、粉状又は粒状のヒドロキシアパタイトは
圧密を行った場合でも、圧密後に形状が保持されない場
合があり、手術後２〜３週間が経過して切開部位の周辺
に骨組織が生成して固定する以前に、切開した部位から
充填物の漏出が起こって、充填部位の治癒を遅らせる場
合がある。このように、充填した圧密ヒドロキシアパタ
イト粒子の形状を初期の形状に保持することは、治癒の
促進上極めて重要である。However, even if powdered or granular hydroxyapatite is compacted, it may not retain its shape after compaction, and bone tissue will form around the incision site two to three weeks after surgery and fix it. Previously, leakage of filling material from the incision site may occur, slowing healing of the filling site. Thus, maintaining the initial shape of the filled compacted hydroxyapatite particles is extremely important for promoting healing.
〈発明が解決し゛ようとする課題〉
従って１本発明の目的は、生体に対する刺激がなく、生
体親和性に優れた新規な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> Accordingly, an object of the present invention is to provide a novel hydraulic calcium phosphate cement that is not irritating to living organisms and has excellent biocompatibility.
本発明の別の目的は１手術後の初期における形状保持性
が優れた新規な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。Another object of the present invention is to provide a new hydraulic calcium phosphate cement that exhibits excellent shape retention in the early stages after one operation.
本発明の更に別な目的は、手術後の充填物の漏出を防止
し得る新規な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。Still another object of the present invention is to provide a new hydraulic calcium phosphate cement that can prevent leakage of the filling after surgery.
く課題を解決するための手段〉
本発明によれば、ヒドロキシアパタイトと、第１リン酸
カルシウムとの混合粉体を主成分として含有する水硬性
リン酸カルシウムセメントが提供される。Means for Solving the Problems> According to the present invention, a hydraulic calcium phosphate cement containing a mixed powder of hydroxyapatite and monobasic calcium phosphate as a main component is provided.
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.
本発明の水硬性リン酸カルシウムセメントは、ヒドロキ
シアパタイトと、第１リン酸カルシウムとを必須の構成
成分として含むことを特徴とする。The hydraulic calcium phosphate cement of the present invention is characterized by containing hydroxyapatite and monobasic calcium phosphate as essential components.
本発明において使用するヒドロキシアパタイト（Ｃａ
ｓ （Ｐ Ｏ４） ＝ ＯＨ）は７００℃以上で熱処理
して得られるヒドロキシアパタイト粒子が特に新生骨の
生成が早く好ましい、熱処理の上限温度は特に限定され
るものではないが、ヒドロキシアパタイトが分解を開始
するので１分解温度以下とするのが好ましい１本発明に
て使用し得るヒドロキシアパタイトは、湿式法、乾式法
又は水熱法等の公知の製造方法により人工的に合成され
たものであっても、又、骨等から得られる天然のものを
用いてもよい０本発明において使用するヒドロキシアパ
タイト粉体の粒径は１００μｍ以下であることが望まし
い。１００μｍを超える場合には、硬化液との練和操作
が難しくなり、且つ均一な充填物の製造が困難であって
、更には硬化物の強度を高くすることができないので好
ましくない。本発明の水硬性リン酸カルシウムセメン１
−に用いる第１リン酸カルシウムは、硬化液中の水と反
応して、第２リン酸カルシウムに変化し、セメント粉体
を硬化させる成分である。この際前記ヒドロキシアパタ
イトは骨材としてセメント硬化体の強度を増大させるた
めに作用する。前記第１リン酸カルシウムとしては、市
販品を好ましく用いることができる。一般に市販品は水
和物であるが、無水物であっても使用することができる
。Hydroxyapatite (Ca
s (P O4) = OH), hydroxyapatite particles obtained by heat treatment at 700°C or higher are particularly preferable because new bone formation is fast.The upper limit temperature of heat treatment is not particularly limited, but hydroxyapatite particles are preferable because they are heat-treated at 700°C or higher. 1. Hydroxyapatite that can be used in the present invention is preferably synthesized by a known production method such as a wet method, a dry method, or a hydrothermal method. Alternatively, a natural material obtained from bones or the like may be used. The particle size of the hydroxyapatite powder used in the present invention is preferably 100 μm or less. If it exceeds 100 μm, it is not preferable because the kneading operation with the curing liquid becomes difficult, it is difficult to produce a uniform filler, and furthermore, the strength of the cured product cannot be increased. Hydraulic calcium phosphate cement of the present invention 1
The monobasic calcium phosphate used in - is a component that reacts with water in the curing liquid to change to dibasic calcium phosphate, thereby curing the cement powder. At this time, the hydroxyapatite acts as an aggregate to increase the strength of the hardened cement body. As the primary calcium phosphate, commercially available products can be preferably used. Generally, commercially available products are hydrated, but anhydrous forms can also be used.
本発明において、前記ヒドロキシアパタイト及び第１リ
ン酸カルシウムの含有割合は、水硬性リン酸カルシウム
セメント全体に対して、ヒドロキシアパタイトが９７〜
５０重量％、第１リン酸カルシウムが３〜５０重量％、
特に１０〜３０重量％の範囲であるのが好ましい、この
際第ニリン酸カルシウムの含有割合が３重量％未満の場
合には、得られる硬化体の強度が低下し、また５０重量
％を超える場合には、第１リン酸カルシウムが水溶性で
あるため練和時の操作が困難となり、しかもヒドロキシ
アパタイトの量が減少し、生体親和性が失われるので好
ましくない。In the present invention, the content ratio of hydroxyapatite and monobasic calcium phosphate is such that hydroxyapatite is 97 to 97% of the total hydraulic calcium phosphate cement.
50% by weight, 3 to 50% by weight of monobasic calcium phosphate,
In particular, it is preferably in the range of 10 to 30% by weight; in this case, if the content of calcium diphosphate is less than 3% by weight, the strength of the resulting cured product will decrease, and if it exceeds 50% by weight, is not preferable because monocalcium phosphate is water-soluble, making it difficult to operate during kneading, and furthermore, the amount of hydroxyapatite decreases and biocompatibility is lost.
本発明の水硬性リン酸カルシウムは、前記ヒドロキシア
パタイトと、第１リン酸カルシウムとを含む成分を混合
させることにより得ることができ。The hydraulic calcium phosphate of the present invention can be obtained by mixing components containing the hydroxyapatite and monobasic calcium phosphate.
また硬化させるには、単に水と混和することにより、約
１５〜６０分間で硬化させることができる。For curing, it can be cured in about 15 to 60 minutes by simply mixing with water.
更に本発明の水硬性リン酸カルシウムセメントは、ｐＨ
が中性付近であるため、生体を刺激することがなく、シ
かも骨欠損部又は骨空隙部に充填する場合、充填物自体
が硬化するので、術直後の形状を保持することができ、
切開箇所からの漏出を防止し、ヒドロキシアパタイトの
有する生体親和性を最大限に活かすことができる。Furthermore, the hydraulic calcium phosphate cement of the present invention has a pH of
Since it is near neutral, it does not stimulate the living body, and when filling bone defects or bone voids, the filling itself hardens, so it can maintain its shape immediately after surgery.
It is possible to prevent leakage from the incision site and make the most of the biocompatibility of hydroxyapatite.
また本発明の水硬性リン酸カルシウムを硬化させるため
の硬化液としては、前述のとおり水で十分であるが、練
和時又は生体へ充填する際の操作性を向上させるために
、粘稠剤を含有させるのが好ましい。該粘稠剤としては
、例えばポリエチレングリコール、ポリビニルアルコー
ル等の合成高分子等を挙げることができるが、生体との
親和性を鑑みると、多糖類を含有させるのが最も好まし
い。一般的に多糖類は、生物により生成される高分子物
質であり、植物、海藻類、昆虫、甲殻類等の主成分であ
って、当然人体中にも含まれる物質であるので、生体に
対する親和性には何等問題のないものである。具体的に
は例えばキチン、キトサン、溶性デンプン、グリコーゲ
ン、アラビアゴム、アルギン酸、コンドロイチンＭ酸、
ヒアルロン酸及びこれらの混合物から成る群より選択さ
れる化合物等を好ましく挙げることができる。使用に際
しては、例えばキチン、キトサンの場合、クエン酸、リ
ンゴ酸、乳酸等の有機酸を含む水溶液に溶解させ、また
他の多糖類は、単に水に溶解させることにより用いるこ
とができる。一方前記アルギン酸、コンドロイチン硫酸
及びヒアルロン酸の水溶液は、強酸性を示すが、例えば
カリウム塩、カルシウム塩、ナトリウム塩等の塩にして
使用することにより、はぼ中世の状態で用いることがで
き、しかも該コンドロイチン硫酸の塩は、練和時の操作
性が非常に良く、且つセメント泥が歯や骨の主要構成成
分であるヒドロキシアパタイトと良好な接着性を示すの
で特に好ましい、前記水溶性の多糖類の硬化液中の濃度
は、多糖類の種類により異なるが、例えばキチン、キト
サンの場合１〜１０重量％、溶性デンプン、グリコーゲ
ン、アラビアゴム、アルギン酸、コンドロイチン硫酸及
びその塩の場合、１〜３０重量％、ヒアルロン酸及びそ
の塩の場合０．５〜２重量％であるのが好ましい、多糖
類の濃度が前記範囲未満の場合には、十分な効果が期待
できず、また前記範囲を超える場合には粘度が高くなり
、操作性に問題が生ずるので好ましくない。In addition, water is sufficient as the curing liquid for curing the hydraulic calcium phosphate of the present invention, as described above, but in order to improve the operability during kneading or filling into a living body, a thickening agent may be added. It is preferable to let Examples of the thickening agent include synthetic polymers such as polyethylene glycol and polyvinyl alcohol, but in view of compatibility with living organisms, it is most preferable to include polysaccharides. In general, polysaccharides are polymeric substances produced by living organisms, and are the main components of plants, seaweed, insects, crustaceans, etc., and are naturally found in the human body, so they have an affinity for living organisms. There is nothing wrong with gender. Specifically, for example, chitin, chitosan, soluble starch, glycogen, gum arabic, alginic acid, chondroitin M acid,
Preferred examples include compounds selected from the group consisting of hyaluronic acid and mixtures thereof. When used, for example, chitin and chitosan can be dissolved in an aqueous solution containing an organic acid such as citric acid, malic acid, or lactic acid, and other polysaccharides can be used by simply dissolving them in water. On the other hand, the aqueous solutions of alginic acid, chondroitin sulfate, and hyaluronic acid exhibit strong acidity, but by using them in the form of salts such as potassium salts, calcium salts, and sodium salts, they can be used in modern conditions. The chondroitin sulfate salt is particularly preferred as the water-soluble polysaccharide because it has very good operability during kneading and the cement mud exhibits good adhesion to hydroxyapatite, which is a main constituent of teeth and bones. The concentration in the hardening solution varies depending on the type of polysaccharide, but for example, 1 to 10% by weight for chitin and chitosan, and 1 to 30% by weight for soluble starch, glycogen, gum arabic, alginic acid, chondroitin sulfate and its salts. %, and in the case of hyaluronic acid and its salts, it is preferably 0.5 to 2% by weight. If the concentration of the polysaccharide is less than the above range, sufficient effects cannot be expected, and if it exceeds the above range, is not preferable because it increases the viscosity and causes problems in operability.
本発明の水硬性リン酸カルシウムセメントは、生体親和
性を損ねることがない限り、前記必須の構成成分のほか
に、セラミックス粉体等を含有させて、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。該セラミックス粉体としては、例えば、
フッ素アパタイト、第３リン酸カルシウム、ビロリン酸
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。The hydraulic calcium phosphate cement of the present invention can contain ceramic powder, etc. in addition to the above-mentioned essential components, as long as it does not impair biocompatibility, so as to improve the mechanical strength when the composition is cured. Biocompatibility etc. can also be improved. As the ceramic powder, for example,
Examples include calcium phosphate compounds such as fluoroapatite, tertiary calcium phosphate, birocalcium phosphate, and quaternary calcium phosphate, which can be used alone or as a mixture.
また本発明の水硬性リン酸カルシウムセメントでは、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
ては、硫酸バリウム、塩基性炭酸ビスマス、ヨードホル
ム及びこれらの混合物から成る群より選択することがで
きる。また好ましい抗菌剤としては、ヨードホルム又は
クロルヘキシジン等がある。該Ｘｓ造影剤又は抗菌剤の
使用量は、特に限定されるものではないが、水硬性リン
酸カルシウムセメント組成物１００重量部に対して０〜
３０重量部であるのが好ましい。Furthermore, the hydraulic calcium phosphate cement of the present invention can optionally contain an X-ray contrast agent, an antibacterial agent, etc., if necessary. For example, preferred X-ray contrast agents may be selected from the group consisting of barium sulfate, bismuth basic carbonate, iodoform, and mixtures thereof. Preferred antibacterial agents include iodoform and chlorhexidine. The amount of the Xs contrast agent or antibacterial agent used is not particularly limited, but is from 0 to 100 parts by weight of the hydraulic calcium phosphate cement composition.
Preferably it is 30 parts by weight.
〈発明の効果〉
本発明の水硬性リン酸カルシウムセメントは、ヒドロキ
シアバイトと、第１リン酸カルシウムとを必須の構成成
分として含有するので、生体親和性に優れており、また
骨欠損部及び骨空隙部等に充填した際の初期の形状を保
持することができるので、手術後等における充填物の漏
出を防止することができる。<Effects of the Invention> The hydraulic calcium phosphate cement of the present invention contains hydroxyabite and monobasic calcium phosphate as essential constituents, so it has excellent biocompatibility and is effective against bone defects, bone voids, etc. Since the initial shape when filled can be maintained, leakage of the filling after surgery can be prevented.
く実ｍ例〉
以下本発明を実施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 with reference to Examples below, but the present invention is not limited thereto.
失に量上
ヒドロキシアバイト粉末（１００μｍ以下）と第１リン
酸カルシウムと（和光補薬工業社製）を、第１リン酸カ
ルシウムが重量比で３．１０，３０゜５０％となるよう
に混合し、水硬性リン酸カルシウムセメント粉体を夫々
調製した。次いで、得られたセメント粉体１００重量部
に対して６０重量部の水を添加して、練和して硬化させ
た。その結果いずれの配合割合であっても硬化体が製造
でき、しかも生体親和性に富んだ生体用セメントであっ
た。Mix hydroxyavite powder (100 μm or less) and monobasic calcium phosphate (manufactured by Wako Saiyaku Kogyo Co., Ltd.) so that the monobasic calcium phosphate becomes 3.10.30°50% by weight, and add water. Hard calcium phosphate cement powders were prepared respectively. Next, 60 parts by weight of water was added to 100 parts by weight of the obtained cement powder, and the mixture was kneaded and hardened. As a result, it was possible to produce a cured product regardless of the blending ratio, and it was a living body cement that was highly biocompatible.
去ＪｆＬｆＬ尖
ヒドロキシアパタイト（１００μｍ以下）８０重量部と
、第１リン酸カルシウム（和光補薬工業社製）２０重量
部とを混合し、水硬性リン酸カルシウムセメント粉体を
ｉｓした。80 parts by weight of JfLfL pointed hydroxyapatite (100 μm or less) and 20 parts by weight of dibasic calcium phosphate (manufactured by Wako Saiyaku Kogyo Co., Ltd.) were mixed to form a hydraulic calcium phosphate cement powder.
一方硬化液として、溶性デンプン、グリコーゲン、アラ
ビアゴム（以上和光補薬工業社製）夫々を２０重量％水
溶液となるように水に溶解した溶液、アルギン酸ナトリ
ウム（和光補薬工業社製）を５重量％水溶液となるよう
に水に溶解した溶液。On the other hand, as a curing liquid, soluble starch, glycogen, and gum arabic (manufactured by Wako Hyakuyaku Kogyo Co., Ltd.) were each dissolved in water to make a 20% aqueous solution, and 5 weight of sodium alginate (manufactured by Wako Hoyaku Kogyo Co., Ltd.) was used. % aqueous solution.
ヒアルロン酸ナトリウム（チッソ社１１）を１重量％溶
液となるように水に溶解した溶液、コンドロイチン硫酸
ナトリウム（和光補薬工業社ＩＩ）を１０重量％水溶液
となるように水に溶解した溶液を夫々ｍ製した。得られ
たセメント粉末と硬化液とを夫々１００：６０の重量割
合で練和したところすべての組合せにおいて良好な稠度
が得られ、また硬化時間も６０分間と短時間であった。A solution of sodium hyaluronate (Chisso Co., Ltd. 11) dissolved in water to make a 1% by weight solution, and a solution of sodium chondroitin sulfate (Wako Hyakuyaku Kogyo Co., Ltd. II) dissolved in water to make a 10% by weight solution, respectively. Made by M. When the obtained cement powder and hardening liquid were kneaded in a weight ratio of 100:60, good consistency was obtained in all combinations, and the hardening time was as short as 60 minutes.
失旌班立
クエン酸の１重量％水溶液に、キトサン（片倉チッカリ
ン社製）０．５重量％を溶解した硬化液を用いた以外は
、実施例２と同様に、セメント粉末と硬化液とを混合練
和したところ、良好な稠度が得られ、硬化時間も１５分
程度と短時間であった。Cement powder and hardening liquid were prepared in the same manner as in Example 2, except that a hardening liquid was used in which 0.5% by weight of chitosan (manufactured by Katakura Chikkarin Co., Ltd.) was dissolved in a 1% by weight aqueous solution of citric acid. When mixed and kneaded, a good consistency was obtained, and the curing time was as short as about 15 minutes.
天動Ｄ４髪
実施例２で調製したセメント粉末を、コンドロイチン硫
酸ナトリウム（和光補薬工業社製）の１０重量％水溶液
で流動状態とし、家兎大腿骨に作製した骨欠損部に充填
した６手術において、セメント粉末を流動状態にする操
作は容易であり。Tendo D4 hair The cement powder prepared in Example 2 was made fluid with a 10% by weight aqueous solution of sodium chondroitin sulfate (manufactured by Wako Hyakuyaku Kogyo Co., Ltd.), and was filled into a bone defect created in a rabbit femur in 6 surgeries. In this case, it is easy to make the cement powder into a fluid state.
且つ充填物の流動性が良く、骨欠損部の隅々まで完全に
充填することができた。また充填物は、充填時の形状が
保持されており、術後の漏出は認められなかった。In addition, the filling material had good fluidity and was able to completely fill every corner of the bone defect. In addition, the filling material maintained its original shape, and no leakage was observed after the surgery.
Claims (1)
合粉体を主成分として含有する水硬性リン酸カルシウム
セメント。A hydraulic calcium phosphate cement containing as a main component a mixed powder of hydroxyapatite and monobasic calcium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1309041A JPH03174348A (en) | 1989-11-30 | 1989-11-30 | Hydraulic calcium phosphate cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1309041A JPH03174348A (en) | 1989-11-30 | 1989-11-30 | Hydraulic calcium phosphate cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03174348A true JPH03174348A (en) | 1991-07-29 |
| JPH0528628B2 JPH0528628B2 (en) | 1993-04-26 |
Family
ID=17988166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1309041A Granted JPH03174348A (en) | 1989-11-30 | 1989-11-30 | Hydraulic calcium phosphate cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03174348A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07289627A (en) * | 1994-04-26 | 1995-11-07 | Kunio Ishikawa | Hardening composition and treatment agent therefor |
| EP0715802A1 (en) * | 1993-08-25 | 1996-06-12 | Audiodontics, Inc. | Method and apparatus imparting vibrations to bone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59217666A (en) * | 1983-05-26 | 1984-12-07 | 株式会社未来化学研究所 | Apatite hydroxide sintered body and manufacture |
| JPS61242968A (en) * | 1985-04-01 | 1986-10-29 | ティーディーケイ株式会社 | Forming material |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
-
1989
- 1989-11-30 JP JP1309041A patent/JPH03174348A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59217666A (en) * | 1983-05-26 | 1984-12-07 | 株式会社未来化学研究所 | Apatite hydroxide sintered body and manufacture |
| JPS61242968A (en) * | 1985-04-01 | 1986-10-29 | ティーディーケイ株式会社 | Forming material |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0715802A1 (en) * | 1993-08-25 | 1996-06-12 | Audiodontics, Inc. | Method and apparatus imparting vibrations to bone |
| EP0715802A4 (en) * | 1993-08-25 | 2000-05-17 | Audiodontics Inc | Method and apparatus imparting vibrations to bone |
| JPH07289627A (en) * | 1994-04-26 | 1995-11-07 | Kunio Ishikawa | Hardening composition and treatment agent therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0528628B2 (en) | 1993-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9883923B2 (en) | Dental and endodontic filing materials and methods | |
| US9668825B2 (en) | Dental and endodontic filling materials and methods | |
| EP2266634B1 (en) | Rapid-hardening calcium phosphate cement compositions | |
| US5238491A (en) | Hardening material for medical and dental use | |
| JP5307547B2 (en) | Two-phase cement precursor system for bone repair | |
| US6425949B1 (en) | Hydraulic surgical cement | |
| GB2248232A (en) | Cement compositions | |
| EP1002513A1 (en) | Calcium phosphate cements containing polyalkene acids | |
| JPH05168692A (en) | Curable material for restoration of hard biotissue | |
| JPS6219508A (en) | Root canal filling material for dental use | |
| US10561583B2 (en) | Dental cement composition | |
| JPH03174349A (en) | Hydraulic calcium phosphate cement | |
| JPH03174348A (en) | Hydraulic calcium phosphate cement | |
| JP3965249B2 (en) | Calcium phosphate cement and calcium phosphate cement composition | |
| JPS62153204A (en) | Root canal filling material for dental use | |
| JPH0534300B2 (en) | ||
| JPH06172008A (en) | Hardenable composition | |
| JP2626811B2 (en) | Curable glue root canal filling material | |
| JPH03141955A (en) | Hydraulic calcium phosphate cement setting fluid | |
| JPS62270164A (en) | Substitute material for repairing living body hard tissue | |
| JPH0763502B2 (en) | Human hard tissue replacement composition | |
| JP4319280B2 (en) | Calcium phosphate cement powder and calcium phosphate cement composition | |
| JPH03128062A (en) | Water-curable type calcium phosphate cement composition | |
| JPH03128061A (en) | Water-curable type calcium phosphate cement composition | |
| JPH04348755A (en) | Hydraulic calcium phosphate cement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090426 Year of fee payment: 16 |
|
| LAPS | Cancellation because of no payment of annual fees |