JPH0459911B2 - - Google Patents
Info
- Publication number
- JPH0459911B2 JPH0459911B2 JP63057890A JP5789088A JPH0459911B2 JP H0459911 B2 JPH0459911 B2 JP H0459911B2 JP 63057890 A JP63057890 A JP 63057890A JP 5789088 A JP5789088 A JP 5789088A JP H0459911 B2 JPH0459911 B2 JP H0459911B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- paa
- molecular weight
- acids
- medical
- 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
- 229920002125 Sokalan® Polymers 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 150000007513 acids Chemical class 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 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 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000004898 kneading Methods 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 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 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- 239000011575 calcium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004568 cement Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- RRAFCDWBNXTKKO-UHFFFAOYSA-N Eugenol Natural products COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 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 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- -1 citric acid Chemical class 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003178 glass ionomer cement Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 239000002631 root canal filling material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000243 solution Substances 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
Landscapes
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
産業上の利用分野
本発明は医科用として、骨欠損部充填剤、骨接
合剤、人工骨および人工関節と生体との合着充填
剤等、歯科用として、合着セメント、充填セメン
ト、仮封セメント、根管充填剤等に用いられる医
療用硬化組成物に関する。
従来の技術および発明が解決しようとする課題
従来使用されている医療用硬化組成物にはZnO
−正リン酸水溶液系のリン酸亜鉛セメント、ZnO
−ポリカルボン酸水溶液系のカルボキシレートセ
メント、SiO2、Al2O3−ポリカルボン酸水溶液系
のグラスイオノマーセメント、ZnO−ユージノー
ル系のユージノールセメント、SiO2−BISGMA
樹脂系のレジンセメント、ポリメタアクリル酸メ
チル粉末−メチルメタアクリル酸系のボーンセメ
ント等があるが、近年、これらに比べて生体親和
性の優れたハイドロキシアパタイト（以下HAP
と略す）、α−リン酸三カルシウム（以下α−
TCPと略す）、リン酸四カルシウム（以下4CPと
略す）が医療用材料として普及してきている。こ
の中でも4CPは、HAP、α−TCPに比べて骨誘
導性が優れており、特に注目されている材料であ
る。
生体材料として用いる際には、耐圧強度に優
れ、崩壊率が低い事が要求されるが、上記の材料
を用いた硬化組成物は、クエン酸等の酸と混合練
和すると、高い耐圧強度を示すが、崩壊率が高
く、またポリアクリル酸（以下PAAと略す）等
のポリマーと混合練和すると、低崩壊率を示す
が、耐圧強度が低く、現実には、この両者の良い
特性を満たす事が出来ていない。
課題を解決するための手段
上記の現状を鑑み、本発明者等は、鋭意研究の
結果、特定分子量のPAA等のポリマーとクエン
酸等の酸とを一定比率で混合して水溶液とし、こ
の水溶液中のPAA等を特定の濃度にしたものを
硬化剤として使用し、これに4CPを混合すること
により、従来にない高耐圧強度、低崩壊率の医療
用硬化組成物が得られることを知見し本発明に至
つた。
すなわち、本発明は、
(A) 分子量5000〜70000のPAA、または、同一分
量のPAAとイタコン酸との共重合体と
(B) クエン酸またはリンゴ酸、マレイン酸、酒石
酸、グリコール酸の１種以上の酸または混合酸
とを
(A)：(B)＝2.0〜4.5：１の比率で混合し、混合物
中の(A)成分の濃度を25〜55wt.％の水溶液とした
ものを硬化剤として使用し、この硬化剤と4CPを
主成分とする粉末を混練してなる医療用硬化組成
物に関する。
以後発明の詳細について説明する。
本発明に於ける4CPは、カルシウム源として
CaCO3、CaO、Ca（OH）2、リン源としてP2O5、
H3PO4、（NH4）H2PO4、（NH4）2HPO4、Caと
Ｐの両者を含有するCaHPO4、Ca（H2PO4）2、
Ca2P2O7等が考えられ、公知の方法で造られる。
CaCO3とCa2P2O7を1300℃以上で２時間前後保持
する乾式製造法で化学反応式、
2CaCO3＋Ca2P2O7→
Ca4（PO4）2O＋2CO2
により合成される4CPを粉砕して微粉末として用
いる。好ましくは、24μｍ以下の微粉末にする。
この際、粗粒が混在していると練和時にざらつき
があり、粒径分布幅が大きいと硬化反応速度が均
一に進行しないため良好な硬化組成物が得られな
い。この様な方法で製造された4CPの粉末は有機
酸水溶液と練和すれば、硬化作用を示し、医療用
硬化組成物の粉末基剤として極めて有用である。
硬化剤として分子量5000〜70000のPAAまたは
PAAとイタコン酸との共重合体のみを使用した
場合、低崩壊率を示すが、耐圧強度は700Kg／cm2
未満となる。また、クエン酸またはリンゴ酸、マ
レイン酸、酒石酸、グリコール酸の一種類の酸あ
るいは二種類以上の混合酸のみを硬化剤として使
用した場合、高耐圧強度硬化組成物を形成する
が、崩壊率が1.5％を越えて好ましくない。以上
の様に単独の場合、耐圧強度と低崩壊率の両特性
を維持することが出来ない。
分子量5000〜70000のPAAまたは同一分子量の
PAAとイタコン酸との共重合体を(A)とし、クエ
ン酸またはリンゴ酸、マレイン酸、酒石酸、グリ
コール酸の１種以上の酸または混合酸を(B)とした
場合、(A)：(B)＝2.0〜4.5：１の一定比率で混合
し、(A)成分濃度が25〜55wt.％である水溶液を硬
化剤として、初めて、耐圧強度と低崩壊率を両立
できる。PAAにイタコン酸を共重合させるのは、
有効カルボキシル基を増やし特性を増すためであ
る。
分子量5000未満および70000を越えるPAAを使
用した場合や(A)：(B)＝2.0：１の比率を越えて(B)
である酸を過剰に入れた場合は崩壊率が1.5％を
越え、一方(A)：(B)＝4.5：１の比率より(B)である
酸を少なく添加した場合は、耐圧強度が700Kg／
cm2未満となる。また、硬化剤中のPAAの濃度が
55wt.％を越えると、硬化剤の粘度が高く練和が
困難となり、25wt.％未満になると硬化時間が長
くなり気泡を巻き込むため、低崩壊率、耐圧強度
共に悪影響を及ぼし、良好な硬化組成物が得られ
ず、硬化剤として25〜55wt.％の範囲のPAAの濃
度が必要となる。また、硬化剤１重量部に対し
4CPを混練する割合は、0.7〜1.7重量部の範囲で
行なわれるのが好ましい。
この様に上記の条件を全て満たさなければ生体
材料として用いるのに十分な特性を示さず硬化組
成物が得られない。条件を全て満して調製された
硬化剤と4CPを混合練和して得られる硬化体は耐
圧温度が700Kg／cm2以上、崩壊率が1.5％以下の優
れた特性を持つ医療用組成物として使用される。
実施例
以下、本発明を実施例をもつて説明する。
実施例 １
乾式製造法で合成した4CPを微粉砕して24μｍ
以下の微粉末とした。この4CP粉末を分子量
29000のPAAとクエン酸を用いた硬化剤とを4CP
と硬化剤との混合比率を1.3：１にして均一に混
合練和し、パテ状物を得て、歯科用リン酸亜鉛セ
メント試験法（JIST6602−1979）に準じて硬化
時間、圧壊強度、崩壊率を測定した。その結果を
表１に示す。
比較例 １
実施例１と同様に微粉砕化した4CPに対し、分
子量29000のPAAのみを使用した場合とPAAと
クエン酸との混合比率が2.0〜4.5：１の範囲外の
場合につき、実施例１と同様の測定をした結果を
表２に示す。
Industrial Application Fields The present invention is applicable to medical applications such as bone defect fillers, bone bonding agents, artificial bones and artificial joints, and adhesive fillers for living bodies, and dental applications such as luting cements, filling cements, temporary sealants, etc. This invention relates to medical hardening compositions used in cement, root canal filling materials, etc. Problems to be solved by the conventional technology and the invention Conventionally used medical curing compositions include ZnO.
- Orthophosphoric acid aqueous solution based zinc phosphate cement, ZnO
- Carboxylate cement based on polycarboxylic acid aqueous solution, SiO 2 , Al 2 O 3 - Glass ionomer cement based on polycarboxylic acid aqueous solution, ZnO - Eugenol cement based on eugenol, SiO 2 - BISGMA
There are resin-based resin cements, polymethyl methacrylate powder-methyl methacrylic acid-based bone cements, etc., but in recent years, hydroxyapatite (hereinafter referred to as HAP), which has better biocompatibility than these, has been developed.
), α-tricalcium phosphate (hereinafter α-
Tetracalcium phosphate (abbreviated as TCP) and tetracalcium phosphate (hereinafter abbreviated as 4CP) are becoming popular as medical materials. Among these, 4CP is a material that is attracting particular attention because it has superior osteoinductivity compared to HAP and α-TCP. When used as a biomaterial, it is required to have excellent pressure resistance and a low rate of disintegration, but when cured compositions using the above materials are mixed and kneaded with acids such as citric acid, they exhibit high pressure resistance. However, when mixed with a polymer such as polyacrylic acid (hereinafter abbreviated as PAA), it shows a low disintegration rate, but the pressure resistance is low, and in reality, it satisfies both of these favorable characteristics. I haven't been able to do anything. Means for Solving the Problems In view of the above-mentioned current situation, as a result of intensive research, the present inventors prepared an aqueous solution by mixing a polymer such as PAA of a specific molecular weight and an acid such as citric acid at a certain ratio, and created an aqueous solution. We found that by using a specific concentration of PAA, etc. in the material as a hardening agent and mixing it with 4CP, a medical hardening composition with unprecedented high pressure resistance and low disintegration rate could be obtained. This led to the present invention. That is, the present invention comprises (A) PAA having a molecular weight of 5,000 to 70,000, or a copolymer of PAA and itaconic acid in the same amount, and (B) citric acid or one of malic acid, maleic acid, tartaric acid, and glycolic acid. A curing agent is prepared by mixing the above acids or mixed acids at a ratio of (A):(B)=2.0 to 4.5:1, and making an aqueous solution with a concentration of component (A) in the mixture of 25 to 55 wt.%. This invention relates to a medical curing composition prepared by kneading this curing agent and a powder containing 4CP as a main component. The details of the invention will be explained below. 4CP in the present invention is used as a calcium source.
CaCO 3 , CaO, Ca(OH) 2 , P 2 O 5 as a phosphorus source,
H 3 PO 4 , (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , CaHPO 4 containing both Ca and P, Ca(H 2 PO 4 ) 2 ,
Possible examples include Ca 2 P 2 O 7 , which can be produced using known methods.
4CP is synthesized by the chemical reaction formula: 2CaCO 3 + Ca 2 P 2 O 7 → Ca 4 (PO 4 ) 2 O + 2CO 2 using a dry manufacturing method in which CaCO 3 and Ca 2 P 2 O 7 are held at 1300°C or higher for about 2 hours. It is crushed and used as a fine powder. Preferably, it is made into a fine powder of 24 μm or less.
At this time, if coarse particles are mixed, it will be rough during kneading, and if the width of the particle size distribution is large, the curing reaction rate will not proceed uniformly, making it impossible to obtain a good cured composition. The 4CP powder produced by this method exhibits a curing action when mixed with an aqueous organic acid solution, and is extremely useful as a powder base for medical curing compositions. PAA with a molecular weight of 5000-70000 as a curing agent or
When only a copolymer of PAA and itaconic acid is used, the disintegration rate is low, but the compressive strength is 700Kg/cm 2
less than Furthermore, when only one type of acid or a mixture of two or more types of acids such as citric acid, malic acid, maleic acid, tartaric acid, or glycolic acid is used as a curing agent, a cured composition with high pressure resistance is formed, but the disintegration rate is low. Exceeding 1.5% is unfavorable. As described above, when used alone, it is not possible to maintain both properties of pressure resistance and low collapse rate. PAA with a molecular weight of 5000-70000 or the same molecular weight
When (A) is a copolymer of PAA and itaconic acid, and (B) is one or more acids or mixed acids of citric acid, malic acid, maleic acid, tartaric acid, and glycolic acid, (A): ( Only by mixing at a constant ratio of B) = 2.0 to 4.5:1 and using an aqueous solution having a concentration of component (A) of 25 to 55 wt.% as a hardening agent can both compressive strength and low disintegration rate be achieved. Copolymerizing itaconic acid with PAA is
This is to increase the number of effective carboxyl groups and improve properties. When using PAA with a molecular weight of less than 5,000 or more than 70,000, or when the ratio of (A):(B)=2.0:1 is exceeded (B)
If too much acid is added, the disintegration rate will exceed 1.5%, while if less acid (B) is added than the ratio of (A):(B) = 4.5:1, the compressive strength will be 700 kg. /
less than cm2 . In addition, the concentration of PAA in the curing agent
If it exceeds 55wt.%, the viscosity of the curing agent will be high and it will be difficult to mix it, and if it is less than 25wt.%, the curing time will be longer and air bubbles will be involved, which will have a negative effect on both low disintegration rate and pressure resistance, making it difficult to obtain a good curing composition. A concentration of PAA in the range of 25-55 wt.% is required as a curing agent. Also, for 1 part by weight of curing agent
The proportion of 4CP to be kneaded is preferably in the range of 0.7 to 1.7 parts by weight. As described above, unless all of the above conditions are satisfied, a cured composition cannot be obtained because it does not exhibit sufficient properties to be used as a biomaterial. The cured product obtained by mixing and kneading 4CP with a curing agent prepared in accordance with all the conditions is a medical composition with excellent properties such as a pressure resistance of 700 kg/cm 2 or more and a disintegration rate of 1.5% or less. used. Examples Hereinafter, the present invention will be explained with examples. Example 1 4CP synthesized by dry manufacturing method is finely pulverized to 24 μm
The following fine powder was prepared. This 4CP powder has a molecular weight of
4CP with 29000 PAA and hardening agent using citric acid
and curing agent at a mixing ratio of 1.3:1 to obtain a putty. The rate was measured. The results are shown in Table 1. Comparative Example 1 For 4CP finely pulverized in the same manner as in Example 1, Example Table 2 shows the results of measurements similar to those in 1.
【表】【table】
【表】
実施例 ２
分子量29000のPAAと15wt.％のイタコン酸の
共重合体を用いて実施例１と同様の測定をした結
果を表３に示す。
比較例 ２
分子量29000のPAAと15wt.％のイタコン酸の
共重合体のみを使用した場合と、共重合体と酸と
の混合率が2.0〜4.5：１の範囲外の場合、共重合
濃度が20wt.％の場合につき実施例１と同様の測
定をした結果を表４に示す。[Table] Example 2 Table 3 shows the results of the same measurements as in Example 1 using a copolymer of PAA with a molecular weight of 29,000 and itaconic acid with a weight of 15 wt.%. Comparative Example 2 When only a copolymer of PAA with a molecular weight of 29,000 and 15 wt.% itaconic acid was used, and when the mixing ratio of the copolymer and acid was outside the range of 2.0 to 4.5:1, the copolymer concentration was Table 4 shows the results of the same measurements as in Example 1 for the case of 20 wt.%.
【表】【table】
【表】 比較例 ３ 酸のみを用いた場合の例を表５に示す。【table】 Comparative example 3 Table 5 shows an example in which only acid was used.
【表】
実施例 ３
分子量65000のPAAを用いた場合につき実施例
１と同様な測定の結果を表６に示す。[Table] Example 3 Table 6 shows the results of the same measurements as in Example 1 when PAA with a molecular weight of 65,000 was used.
【表】
比較例 ４
分子量65000のPAAを用いた請求範囲外の比較
例を表７に示す。[Table] Comparative Example 4 Table 7 shows a comparative example using PAA with a molecular weight of 65,000, which is outside the scope of the claims.
【表】
実施例 ４
分子量5000のPAAを用いた場合につき、実施
例１と同様な測定の結果を表８に示す。[Table] Example 4 Table 8 shows the results of the same measurements as in Example 1 when PAA with a molecular weight of 5000 was used.
【表】
比較例 ５
分子量5000のPAAを用いた請求範囲外の比較
例を表９に示す。[Table] Comparative Example 5 Table 9 shows a comparative example using PAA with a molecular weight of 5000, which is outside the scope of the claims.
【表】
比較例 ６
PAAの分子量が2000の場合、90000の場合につ
きそれぞれ表10、表11に示す。[Table] Comparative Example 6 Tables 10 and 11 show cases in which the molecular weight of PAA was 2000 and 90000, respectively.
【表】【table】
【表】
発明の効果
本発明は、上記の様に4CPに対し、分子量5000
〜70000のPAAまたは同一分子量のPAAとイタ
コン酸との共重合体とクエン酸またはリンゴ酸等
の１種以上の酸または混合酸とを一定比率にて混
合した硬化剤を使用することにより初めて、高耐
圧強度と低崩壊率の両特性を両立させることがで
き、医科および歯科の医療用硬化組成物として使
用され従来にない優れた特性を示すものが得られ
る。[Table] Effects of the invention As mentioned above, the present invention has a molecular weight of 5000 for 4CP.
For the first time, by using a curing agent that is a mixture of ~70,000 PAA or a copolymer of PAA and itaconic acid with the same molecular weight and one or more acids such as citric acid or malic acid or mixed acids at a certain ratio, It is possible to achieve both high compressive strength and low disintegration rate, and it is possible to obtain a composition that is used as a cured composition for medical and dental applications and exhibits unprecedented properties.
Claims (1)
または、同一分子量のポリアクリル酸とイタコ
ン酸との共重合体と (B) クエン酸またはリンゴ酸、マレイン酸、酒石
酸、グリコール酸の１種以上の酸または混合酸
とを (A)：(B)＝2.0〜4.5：１の比率で混合し、混合物
中の(A)成分の濃度を25〜55wt.％の水溶液とした
ものを硬化剤として使用し、この硬化剤とリン酸
四カルシウムを主成分とする粉末を混練してなる
医療用硬化組成物。[Claims] 1 (A) polyacrylic acid with a molecular weight of 5,000 to 70,000;
Alternatively, a copolymer of polyacrylic acid and itaconic acid with the same molecular weight and (B) one or more acids or mixed acids of citric acid, malic acid, maleic acid, tartaric acid, and glycolic acid (A): (B) ) = 2.0 to 4.5:1, an aqueous solution with a concentration of component (A) in the mixture of 25 to 55 wt.% is used as a hardening agent, and this hardening agent and tetracalcium phosphate are used as main components. A medical cured composition made by kneading powders as ingredients.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057890A JPH01230367A (en) | 1988-03-10 | 1988-03-10 | Medical hardening composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057890A JPH01230367A (en) | 1988-03-10 | 1988-03-10 | Medical hardening composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230367A JPH01230367A (en) | 1989-09-13 |
| JPH0459911B2 true JPH0459911B2 (en) | 1992-09-24 |
Family
ID=13068582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63057890A Granted JPH01230367A (en) | 1988-03-10 | 1988-03-10 | Medical hardening composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01230367A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6642285B1 (en) * | 1999-02-02 | 2003-11-04 | Robert Mathys Stiftung | Implant comprising calcium cement and hydrophobic liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52101893A (en) * | 1976-02-24 | 1977-08-26 | Nippon Kayaku Kk | Liquid hardener for dental glass ionomer cement |
| JPS6168054A (en) * | 1984-09-10 | 1986-04-08 | 増原 英一 | Artificial bone and tooth |
| JPS61270249A (en) * | 1985-05-25 | 1986-11-29 | 株式会社はいる | Tetracalcium phosphate settable composition |
| JPS6272363A (en) * | 1985-09-25 | 1987-04-02 | 名神株式会社 | Medical or dental cement composition |
| JPS6283348A (en) * | 1985-10-08 | 1987-04-16 | 株式会社アドバンス | Curable composition for medical use |
-
1988
- 1988-03-10 JP JP63057890A patent/JPH01230367A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52101893A (en) * | 1976-02-24 | 1977-08-26 | Nippon Kayaku Kk | Liquid hardener for dental glass ionomer cement |
| JPS6168054A (en) * | 1984-09-10 | 1986-04-08 | 増原 英一 | Artificial bone and tooth |
| JPS61270249A (en) * | 1985-05-25 | 1986-11-29 | 株式会社はいる | Tetracalcium phosphate settable composition |
| JPS6272363A (en) * | 1985-09-25 | 1987-04-02 | 名神株式会社 | Medical or dental cement composition |
| JPS6283348A (en) * | 1985-10-08 | 1987-04-16 | 株式会社アドバンス | Curable composition for medical use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01230367A (en) | 1989-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4668295A (en) | Surgical cements | |
| AU2005338323B2 (en) | Bone repair material | |
| US4677140A (en) | Surgical cement containing α-tricalcium phosphate, poly(carboxylic acid) and water | |
| JPH0645487B2 (en) | Curing material | |
| GB2197329A (en) | Hard tissue substitute composition | |
| JPS6272363A (en) | Medical or dental cement composition | |
| JPS6283348A (en) | Curable composition for medical use | |
| JPS59182263A (en) | Production of calcium phosphate cement set body | |
| JPH11335155A (en) | Calcium phosphate cement and calcium phosphate cement composition | |
| JP3987220B2 (en) | Fast-setting calcium phosphate cement | |
| JPH0459911B2 (en) | ||
| JPH01111762A (en) | Hardening composition | |
| JP2780120B2 (en) | Hardening calcium phosphate dental composition | |
| JPH0699181B2 (en) | Tetracalcium phosphate curable composition | |
| JPH0526503B2 (en) | ||
| JPS63153069A (en) | Medical or dental cement composition | |
| JPH11130491A (en) | Calcium phosphate cement and calcium phosphate cement composition | |
| JPS6323671A (en) | Medical curable composition | |
| JPH0585914A (en) | Curing type paste material | |
| JP2001170161A (en) | Calcium phosphate medical hardening composition | |
| JPH0763502B2 (en) | Human hard tissue replacement composition | |
| JPH05285214A (en) | Medical hardened composition | |
| JPS6368173A (en) | Composition for filling bone and tooth | |
| JPS61161206A (en) | Dental cement composition | |
| WO1990008530A1 (en) | Root canal filling material comprising hardenable paste |