JPS62277965A - Medical curable composition - Google Patents
Medical curable compositionInfo
- Publication number
- JPS62277965A JPS62277965A JP61120142A JP12014286A JPS62277965A JP S62277965 A JPS62277965 A JP S62277965A JP 61120142 A JP61120142 A JP 61120142A JP 12014286 A JP12014286 A JP 12014286A JP S62277965 A JPS62277965 A JP S62277965A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- powder
- calcium phosphate
- curable composition
- unsaturated carboxylic
- 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
- 239000000203 mixture Substances 0.000 title claims description 19
- 239000000843 powder Substances 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000001506 calcium phosphate Substances 0.000 claims description 13
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 11
- 235000011010 calcium phosphates Nutrition 0.000 claims description 10
- -1 Calcium phosphate compound Chemical class 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000002504 physiological saline solution Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 4
- 239000004310 lactic acid Substances 0.000 claims 2
- 235000014655 lactic acid Nutrition 0.000 claims 2
- 150000007524 organic acids Chemical class 0.000 claims 2
- 235000005985 organic acids Nutrition 0.000 claims 2
- 235000015165 citric acid Nutrition 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 2
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 2
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 2
- 229940038472 dicalcium phosphate Drugs 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 208000018084 Bone neoplasm Diseases 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004068 calcium phosphate ceramic Substances 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 239000002672 zinc phosphate cement Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
３、発明の詳細な説明
本発明は、医用材料、特に生体の骨腫瘍その他によって
生ずる骨欠損部に充填し、当該個所の新生骨の形成を促
進し、損傷個所の治療後に於いて、生体の骨組織と一体
化する黒磯質材料あるいは歯科領域における合着材のセ
メント、歯髄覆翠材あるいは裏装剤として用いられる硬
化性組成物に関する。Detailed Description of the Invention 3. Detailed Description of the Invention The present invention is directed to filling bone defects caused by bone tumors or other causes in living bodies with medical materials, promoting the formation of new bone at the site, and improving the effectiveness of the damaged site. The present invention relates to a curable composition that is used as a black rock material that integrates with the bone tissue of a living body after treatment, or as a cement for a luting material in the dental field, a pulp covering material, or a lining agent.
従来の技術による生体硬組織イ■復材料は、生体外にて
目的の形状に成型加工されたものをそのままあるいは多
少の修正を施して埋入する方法と、練和物を複雑な形状
をした欠損部へ゛充填し生体内にて硬化させる方法とが
ある。Conventional techniques for reproducing biological hard tissue include two methods: molding into the desired shape outside the body and implanting it as is or with some modification; There is a method of filling the defect and hardening it in vivo.
いずれの場合も素材となるものは、生体との親和性、無
刺激性及び無毒性が必要で、最近では、生体硬組織と類
臥の組成を有するリン酸カルシウム系セラミックス粉体
か注目を集めている。この粉体を使用に耐え得る凝結硬
化体とするには、上記のように生体外では高温高圧焼結
法等が採用されるが、一般的には生体内にて直接硬化さ
せる方法が望ましい。In either case, the material must be compatible with living organisms, non-irritating, and non-toxic.Recently, calcium phosphate ceramic powder, which has a composition similar to that of biological hard tissues, has been attracting attention. . In order to make this powder into a usable solidified and hardened body, a high-temperature, high-pressure sintering method or the like is employed in vitro, as described above, but it is generally preferable to use a method of directly curing it in vivo.
生体用リン酸カルシウム系化合物として公知のものは、
ハイドロキシアパタイト、α又はβ−リン酸三カルシウ
ム、リン酸四カルシウム、リン酸へカルシウム等がある
が、特にα−リン酸カルシウムが、水和反応もしくは酸
と反応し）疑結することが知られている。Known calcium phosphate compounds for biological use are:
Hydroxyapatite, α- or β-tricalcium phosphate, tetracalcium phosphate, calcium phosphate, etc. are known, but especially α-calcium phosphate is known to cause hydration reactions or reactions with acids). .
しかしながら、α−リン酸三カルシウムと酸類の水利反
応による硬化物は生体内での分解の進行が早く、酸性度
の高い溶出液を放出することが、問題点として指摘され
でいる。However, it has been pointed out as a problem that the cured product resulting from the water-use reaction between α-tricalcium phosphate and acids rapidly decomposes in vivo and releases a highly acidic eluate.
上記問題点に鑑み本発明者らは、生体親和性に秀れ、体
液中での分解が少なく、溶出液のρＩＩは６．８〜７．
２の範囲であり、生体用硬組織代替物として充分な機械
的強度を有する医療用硬化性組成物を提供することを目
的とする。In view of the above problems, the inventors of the present invention have excellent biocompatibility, little decomposition in body fluids, and the ρII of the eluate is 6.8 to 7.
The object of the present invention is to provide a medical curable composition having a mechanical strength in the range of 2 and sufficient mechanical strength as a biological hard tissue substitute.
本発明の特徴とするところは、ｎを２．１以上に設定し
得るＣａｎ・２（ＰＯ＋ ）ｚＯｎ−）、例えば、ｎが
６であるリン酸へカルシウム等に水、クエン酸等を混和
することにより、体液中での溶出度が少なく、しかも経
時的に硬化していく組成物を生成酸すること、更に、ｎ
を２．１以上に設定したＣａｎや２ （ＰＯ，ＬＯｎ−
＋を焼結せしめ、次にその焼結体を粉砕せしめて焼結粉
体を成した後、上記水、クエン酸等を混和すると、上記
と同様経時的に硬化していと、更に強度のすぐれた組成
物が生成されることにある。The feature of the present invention is that n can be set to 2.1 or more (Can・2(PO+)zOn-), for example, by mixing calcium, etc., water, citric acid, etc. into phosphoric acid where n is 6. By this, it is possible to produce a composition that has a low degree of dissolution in body fluids and hardens over time, and furthermore,
Can and 2 (PO,LOn-
After sintering + and then crushing the sintered body to form a sintered powder, if you mix the above water, citric acid, etc., it will harden over time as above, and will have even better strength. The objective is to produce a composition that is
次に、本発明医療用硬化性！ｆｌ成物の実施例につき、
材料組成及び製法等につき詳細に説明する。Next, the medical curable properties of the present invention! For examples of fl products,
The material composition, manufacturing method, etc. will be explained in detail.
本発明におけるリン酸カルシウム化合物、ｎが２゜１以
上に設定し得るＣａｎ＋２（ＰＯ，）２Ｏｎ−＋であり
、いいかえればＣａ／Ｐモル比が２．１以上のリン酸カ
ルシウム化合物を示し、好ましくはＣａ７Ｐモル比が６
以下に設定するものである。The calcium phosphate compound in the present invention is Can+2(PO,)2On-+ where n can be set to 2°1 or more, in other words, it is a calcium phosphate compound with a Ca/P molar ratio of 2.1 or more, preferably a Ca7P molar ratio. is 6
The settings are as follows.
地方、その製法は、リン酸二カルシウム（２Ｃａ１１
Ｐ Ｏイ）、あるいはγ−ピロリン酸カルシウム（γ−
Ｃａ２Ｐ２０７）等とＣａＣ０−を混合した後、１００
０°Ｃ−１３００°Ｃで焼成し、以下の化学式で例示さ
れ得る。In the region, the manufacturing method is dicalcium phosphate (2Ca11
PO), or γ-calcium pyrophosphate (γ-
After mixing Ca2P207) etc. and CaC0-, 100
It is calcined at 0°C to 1300°C and can be exemplified by the following chemical formula.
ｎｃａｃＯ３＋ ２ＣａｌｌＰＯｒ−＋Ｃａｎ−２（Ｐ
Ｌ）ｚＯｎ−１＋ Ｈ３Ｏ＋ ７ＣＯ２ｎｃａｃＯ，＋
γ −Ｃａ２Ｐ２Ｌ→Ｃａｎ＋ｚ （ＰＯ４）２Ｏ
ｎ−＋ ＋ ｎｃ０２尚、本発明におけるリン酸カル
シウム化合物は上記の製法によってのみ生成されるもの
ではない。ncacO3+ 2CallPOr-+Can-2(P
L)zOn-1+ H3O+ 7CO2ncacO,+
γ -Ca2P2L→Can+z (PO4)2O
n-+ + nc02 Note that the calcium phosphate compound in the present invention is not produced only by the above manufacturing method.
本発明の医療用硬化組成物を構成する液剤は、水、生理
的食塩水、そしてポリアクリル酸のみならず、メタクリ
ル酸、イタコン酸など他の不飽和カルボン酸の共重合体
であっても良く、又、こｈらカルボキシル基を有するポ
リマーの形態は、前述の水溶液の池粉末でも良い。又、
ＴＣ八へイクル系の有（幾酸でも良く、特にクエン酸、
リンゴ酸、酒石酸、グリコール酸の水溶液が良νゝ 。The liquid agent constituting the medical curable composition of the present invention may be water, physiological saline, and a copolymer of not only polyacrylic acid but also other unsaturated carboxylic acids such as methacrylic acid and itaconic acid. The form of the carboxyl group-containing polymer may be the aqueous solution powder described above. or,
Presence of TC 8hacle type (any acid may be used, especially citric acid,
Aqueous solutions of malic acid, tartaric acid, and glycolic acid are good choices.
以上材料組成から、太る該リン酸カルシウム化合物粉末
と該液剤とｆ、：混和し、所謂の形状に、成形あるいは
充填して適用される。更に、生体硬！１１ｍすなわち骨
、歯科用インブラント等、きわめて高い強度が必要とさ
れる部分に適用される場合、上記製法では充分な強度が
得られない場合がある。これは、リン酸カルシウム化合
物Ｃ以下軽質ｎｃｐ）粉末が、かさ密度が小さいので、
液剤と練和する際の粉液比（粉剤と液剤の混合比＝粉剤
重量／液削重量）の上限が低い為であり、より硬化組成
物が高い強度を発現するためには、粉液比の上限が大で
あるｎｃｐ粉末が必要となることから、軽質ｎｃｐを加
工して、かさ密度か大で、粉液比の上限が大であり、し
かも高強度を得るのに適した粒度分布を有するｎｃｐ粉
末の製造方法を、次に詳細に説明する。From the above material composition, the calcium phosphate compound powder and the liquid agent are mixed and applied by molding or filling into a so-called shape. Furthermore, biohardness! 11m, that is, when applied to parts that require extremely high strength, such as bones and dental implants, the above manufacturing method may not provide sufficient strength. This is because the bulk density of calcium phosphate compound C (light ncp) powder is small.
This is because the upper limit of the powder-liquid ratio (mixing ratio of powder and liquid = powder weight/liquid removal weight) when kneading with liquid is low. Since we need an NCP powder with a high upper limit of A method for producing the NCP powder having the following will be described in detail below.
高強度を供える為には、上記５！法で得られた軽質ｎｃ
ｐを焼結せしめ、焼結体を形成、これを粉砕することに
よ１）焼結粉末を生成した後、軽質ｎｃｐと同様の液剤
を用いて硬化組成物を生成するものである。焼結させる
場合、焼結体密度か１，０ｇ／ｃ＋ｎ’よりも小である
と、かかる焼結体を粉砕したｎｃｐ粉末は充分に重質な
ものとはなり得す、逆に過度の焼結によって焼結体密度
が２．８ｇ／ｃ＋ａ３よりら大となった場合は、かがる
焼結体を乾式ボールミルなどの通常の方法で粉砕した時
、硬化組成物用粉剤として適した粒度の粉末を得ること
が困難になるという弊害が生ずるからである。焼結密度
が２．８ｇ／ａｍ”より大の場合であっても、湿式ミル
やジェットミル等による粉砕と分級、ブレンディング繰
作を組合せることによって硬化組成物用粉剤として適し
た粒度の粉末を製造することは可能ではあるが、製造上
好ましくはない点を考慮すると、焼結体密度は１．．０
ｇ７ｃｍ３−２．８ｇ／ｃ＋ｎ’が好適である。In order to provide high strength, please do the above 5! Light nc obtained by
After 1) producing a sintered powder by sintering P to form a sintered body and pulverizing it, a cured composition is produced using the same liquid agent as the light NCP. When sintering, if the density of the sintered body is lower than 1.0 g/c+n', the NCP powder obtained by crushing such a sintered body may be sufficiently heavy; on the other hand, excessive sintering may occur. If the density of the sintered body becomes greater than 2.8g/c+a3 due to sintering, when the sintered body is crushed by a normal method such as a dry ball mill, it is necessary to grind the sintered body to a particle size suitable for use as a powder for hardening compositions. This is because the disadvantage arises that it becomes difficult to obtain powder. Even if the sintered density is greater than 2.8 g/am, it is possible to produce powder with a particle size suitable for use as a powder for hardening compositions by combining pulverization with a wet mill or jet mill, classification, and blending operations. Although it is possible to manufacture it, considering that it is not preferable in terms of manufacturing, the density of the sintered body is 1.0
g7cm3-2.8g/c+n' is suitable.
改良されなる重質なｎｃｐ粉末が硬化組成物用粉剤とし
て優れた物性を示す理由は、およそ次のように考えられ
る。炭酸カルシウムとリン酸二カルシウムの混合物を焼
成して得た軽質ｎｃｐを電子顕微鏡で観察すると、原料
粒子が固相反応して生成した米粒状の粒子が隣接粒子と
２〜４箇所程度の細いネックを介して三次元的に樹枝状
に連なっている様子が見られる。このｎｃｐを粉砕した
粉末は突起の多い形状の粒子から成るため、かさ密度が
０．６ｇ／ｃｍ３以下と低い。地方、軽質ｎｃｐを加圧
成形し焼結後の密度を１．０〜２．８ｇ７ａｍ ’とし
た焼結体の破断面を電子顕微鏡にて観察すると、圧縮に
よって隣接粒子間・の接点の数が増えるとともにネック
部が成長して太くなっていた。焼結したｎｃｐを粉砕し
た粉末は、突起のない多面体の一次粒子から成り、粒度
分布が平坦で、かさ密度は０．９〜１．２ｇ／ｃｍ１に
増大し、かかる重質ｎｃｐ粉末を液剤と練和する時には
ｎｃｐ粒子がマトリックス間に高密度に分散するために
硬化体の強度が向上するものと考えられる。The reason why the improved heavy NCP powder exhibits excellent physical properties as a powder for hardening compositions is considered to be approximately as follows. When light NCP obtained by calcining a mixture of calcium carbonate and dicalcium phosphate is observed with an electron microscope, the rice-grain-like particles produced by the solid-phase reaction of the raw material particles are found to have narrow necks in two to four places with adjacent particles. It can be seen that they are connected in a three-dimensional dendritic manner through the . Since the powder obtained by pulverizing this NCP consists of particles with many protrusions, the bulk density is as low as 0.6 g/cm 3 or less. When the fractured surface of a sintered body made of pressure-molded light NCP and sintered with a density of 1.0 to 2.8g7am' was observed using an electron microscope, it was found that the number of contact points between adjacent particles increased due to compression. As I grew older, my neck grew and became thicker. The powder obtained by pulverizing sintered NCP consists of polyhedral primary particles without protrusions, has a flat particle size distribution, and has a bulk density of 0.9 to 1.2 g/cm1, and the heavy NCP powder can be used as a liquid agent. It is thought that during kneading, the strength of the cured product is improved because the NCP particles are dispersed at high density between the matrices.
以上詳述した様に、本発明医療用硬化性組成物は、各々
の強度に応じた硬度を有し、かつ繰作性がよく、しかも
生体との親和性を供え、体液中での分解が少ない等の効
果を奏効するものである。As described in detail above, the medical curable composition of the present invention has hardness corresponding to each strength, has good repeatability, has compatibility with living organisms, and is resistant to decomposition in body fluids. It is effective in reducing the amount of water used.
次に、本発明を実験例を用いて詳細に説明する。Next, the present invention will be explained in detail using experimental examples.
実験例
ＣａＣＬ（カルサイト形）と７−Ｃａ２Ｐ２Ｏ７の粉末
と表−１のようなモル比で秤量混合し、空気中で各濃度
、各時間で焼成した。放冷後、該リン酸カルシウムを乾
式ボールミルにて粉砕した後、３５０メンシユのふるい
で分級し、ふるい通過粉を硬化組成物粉剤とした。該粉
剤と硬化液をガラス仮に採り、均一に混合練和し泥状と
なし、内径６ｍ＋ｎ、高さ１２ ＋ｎ ＋ｎの金型に流
し込み、以下ＪＩＳ Ｔ６６０２の、リン酸亜鉛セメン
ト試験方法に準じて硬化体の物性を測定した。その結果
を表−Ｈに示す。Experimental Example CaCL (calcite type) and 7-Ca2P2O7 powder were weighed and mixed at the molar ratio shown in Table 1, and fired in air at various concentrations and for various times. After cooling, the calcium phosphate was pulverized using a dry ball mill, and then classified using a 350-mesh sieve, and the powder that passed through the sieve was used as a hardened composition powder. The powder and curing liquid were taken on a glass plate, mixed and kneaded uniformly to form a slurry, poured into a mold with an inner diameter of 6 m + n and a height of 12 + n + n, and cured according to the zinc phosphate cement test method of JIS T6602. The physical properties of the body were measured. The results are shown in Table H.
尚、比較例としてＣａＣ０□とγ−Ｃａ、Ｐ２０．のモ
ル比を１：１及び１：２に設定したリン酸カルシウムに
ついて上記と同様の試験を行った。In addition, as comparative examples, CaC0□, γ-Ca, P20. The same test as above was conducted on calcium phosphate with the molar ratio of 1:1 and 1:2.
実験結果に見られるように、Ｃａ７Ｐを高くするに従っ
て、本発明になる医療用硬化組成物の崩壊率か低下し、
１〕１１は中性、弱アルカリに改善される。又、高密度
化することにより物性が改善されることを示すのが表−
■である。即ち表−Ｉの実施例３（粉剤Ｎｏ、Ｃ）を高
密度化し、各種の硬化液で練和してＪＩＳ Ｔ６６０２
試験法で測定したのが表−■である。As seen in the experimental results, as the Ca7P content increases, the disintegration rate of the medical cured composition of the present invention decreases.
1] 11 is improved to neutrality and weak alkalinity. In addition, the table shows that the physical properties are improved by increasing the density.
■It is. That is, Example 3 (powder No., C) in Table I was densified and kneaded with various hardening liquids to obtain JIS T6602.
Table -■ shows the results measured using the test method.
表−１ ト ［ ］− 表−■ 表−■Table-1 to [ ]− Table - ■ Table - ■
Claims (2)
Ｏ＿４）＿２Ｏ＿ｎ＿−＿１で表わされるリン酸カルシ
ウム化合物粉末と、水、生理的食塩水、又は、不飽和カ
ルボン酸の重合体、又は二種以上の不飽和カルボン酸の
共重合体、又はクエン酸、リンゴ酸、酒石酸、グリコー
ル酸、乳酸等の有機酸、のうちの一者以上の水溶液とか
ら成ることを特徴とする医療用硬化性組成物。(1) Ca_n_+_2(P
O_4) Calcium phosphate compound powder represented by_2O_n_-_1 and water, physiological saline, or a polymer of unsaturated carboxylic acids, or a copolymer of two or more unsaturated carboxylic acids, or citric acid or malic acid. , and an aqueous solution of one or more of organic acids such as tartaric acid, glycolic acid, and lactic acid.
Ｏ＿４）＿２Ｏ＿ｎ＿−＿１で表わされるリン酸カルシ
ウム化合物を焼結、粉砕した焼結粉末と、水、生理的食
塩水、又は、不飽和カルボン酸の重合体、又は二種以上
の不飽和カルボン酸の共重合体、又はクエン酸、リンゴ
酸、酒石酸、グリコール酸、乳酸等の有機酸、のうちの
一者以上の水溶液とから成ることを特徴とする医療用硬
化性組成物。(2) Ca_n_+_2(P
O_4) A sintered powder obtained by sintering and pulverizing a calcium phosphate compound represented by _2O_n_-_1, and water, physiological saline, or a polymer of unsaturated carboxylic acids, or a copolymer of two or more unsaturated carboxylic acids. 1. A medical curable composition comprising an aqueous solution of one or more of organic acids such as citric acid, malic acid, tartaric acid, glycolic acid, and lactic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61120142A JPH0755234B2 (en) | 1986-05-27 | 1986-05-27 | Medical curable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61120142A JPH0755234B2 (en) | 1986-05-27 | 1986-05-27 | Medical curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62277965A true JPS62277965A (en) | 1987-12-02 |
| JPH0755234B2 JPH0755234B2 (en) | 1995-06-14 |
Family
ID=14779003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61120142A Expired - Lifetime JPH0755234B2 (en) | 1986-05-27 | 1986-05-27 | Medical curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0755234B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63115568A (en) * | 1986-11-01 | 1988-05-20 | 昭和電工株式会社 | Hard tissue substitute composition of human body |
| JPH01121059A (en) * | 1987-11-06 | 1989-05-12 | Ube Ind Ltd | Substitute composition for human body hard tissue |
-
1986
- 1986-05-27 JP JP61120142A patent/JPH0755234B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63115568A (en) * | 1986-11-01 | 1988-05-20 | 昭和電工株式会社 | Hard tissue substitute composition of human body |
| JPH01121059A (en) * | 1987-11-06 | 1989-05-12 | Ube Ind Ltd | Substitute composition for human body hard tissue |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0755234B2 (en) | 1995-06-14 |
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