JPH01230367A - Medical hardening composition - Google Patents
Medical hardening compositionInfo
- Publication number
- JPH01230367A JPH01230367A JP63057890A JP5789088A JPH01230367A JP H01230367 A JPH01230367 A JP H01230367A JP 63057890 A JP63057890 A JP 63057890A JP 5789088 A JP5789088 A JP 5789088A JP H01230367 A JPH01230367 A JP H01230367A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- paa
- molecular weight
- medical
- hardener
- 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 abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 19
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 abstract description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 5
- 239000011976 maleic acid Substances 0.000 claims abstract description 5
- 239000011975 tartaric acid Substances 0.000 claims abstract description 5
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 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
- 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 1
- 239000011575 calcium Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 238000004898 kneading Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004568 cement Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 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 2
- 239000002672 zinc phosphate cement Substances 0.000 description 2
- 229910019670 (NH4)H2PO4 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
- 230000002411 adverse Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 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
- 210000004262 dental pulp cavity Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003178 glass ionomer cement Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 238000007789 sealing Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 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 1
Landscapes
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は医科用として、刊欠損部充填剤、骨接合剤、入
玉側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。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applicable to medical applications such as defect filling materials, bone bonding agents, filling materials for bonding between artificial joints and living bodies, and dental applications. The present invention relates to medical hardening compositions used as adhesive cements, filling cements, temporary sealing cements, root canal filling agents, etc.
従来の技術および発明か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−ポリカルホン酸水
溶液系のカルボキシレートセメント、Ｓ １０２ 、Ａ
ｇ２Ｏ３−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−ニーシノール系のニーシノールセメ
ント、Ｓ ｉｏ ２− Ｂ Ｉ Ｓ Ｇ Ｍ Ａ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かあるか、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
バタイ］・（以下ＨＡ Ｐ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）か医療用）」料として普及してき
ている。この中でも４ＣＰは、ＨＡＰ、 α−ＴＣＰ
に比べて骨誘導性か優れており、特に注目されている斗
」料である。BACKGROUND ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Conventionally used medical curing compositions include zinc phosphate cement based on ZnO-orthophosphoric acid aqueous solution, carboxylate cement based on ZnO-polycarphonic acid aqueous solution, S102, A
g2O3-Polycarboxylic acid aqueous solution-based glass ionomer cement, ZnO-Nissinol-based Nisinol cement, Sio2-BISGMA resin-based resin cement, polymethyl methacrylate powder-methyl methacrylic acid system In recent years, bone cement, etc., have been developed that have superior biocompatibility compared to these. Tetracalcium (hereinafter abbreviated as 4CP) is becoming popular as a medical ingredient. Among these, 4CP are HAP, α-TCP
It is a material that is attracting particular attention because of its superior osteoinductivity compared to other materials.
生体材料として用いる際には、耐圧強度に優れ、崩壊率
か低い事か要求されるが、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
を示すか、崩壊率が高く、またポリアクリル酸（以下Ｆ
ＡＡと略す）テ５′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か出来ていない。When used as a biomaterial, it is required to have excellent pressure resistance and low disintegration rate, but when cured compositions using the above materials are mixed and kneaded with acids such as citric acid, they exhibit high pressure resistance. The disintegration rate is high, and polyacrylic acid (hereinafter referred to as F
When mixed and kneaded with the polymer of Te5' (abbreviated as AA), it shows a low disintegration rate, but the compressive strength is low, and in reality, it has not been possible to satisfy both of these good characteristics.
課題を解決するだめの手段
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ＦＡＡ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
発明に至った。Means to Solve the Problem In view of the above-mentioned current situation, the inventors of the present invention, as a result of intensive research, 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. By using a specific concentration of FAA etc. as a hardening agent and mixing it with 4CP, we have achieved unprecedented high pressure resistance,
The inventors have discovered that a cured medical composition with a low disintegration rate can be obtained, leading to the present invention.
すなわぢ、本発明は、
（Ａ）分子量５．０００〜７０，０００のＦＡＡ、また
は、同一分子量のＦＡＡ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秤量」−の酸または混合酸とを
（Ａ）：（Ｂ） ＝ ２．０〜４．５：Ｉの比率で混合
し、混合物中の（Ａ）成分の濃度を２５〜５５Ｗ１％の
水溶液としたものを硬化剤とｌ、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。In other words, the present invention provides (A) FAA having a molecular weight of 5.000 to 70,000, or a copolymer of FAA and itaconic acid having the same molecular weight;
B) 1 weighed amount of citric acid or malic acid, maleic acid, tartaric acid, glycolic acid or mixed acids in a ratio of (A):(B) = 2.0 to 4.5:I, A medical curing composition prepared by using an aqueous solution of component (A) in the mixture with a concentration of 25 to 55W1% as a curing agent, and kneading this curing agent with a powder containing 4CP as a main component. Regarding.
以後発明の詳細について説明する。The details of the invention will be explained below.
本発明に於ける４ＣＰは、カルシウム源としてＣａＣ０
Ｃａｂ、Ｃａ（ＯＨ） リン源とし３°
２ゝ
てＰ ＯＨＰＯ（ＮＨ４）Ｈ２ＰＯ４゜２５’３４″
（Ｎ Ｈ） ＨＰ Ｏｉ、 、ＣａとＰの両者を含有
するｃ ａ ｎ ｐ ｏ 、Ｃａ（Ｈ２ｐ ｏ４）、ｃ
ａ ２ Ｐ ２０７等が考えられ、公知の方法で造ら
れる。ＣａＣＯ３とＣａ２Ｐ２Ｏ７を１３００°Ｃ以−
１−で２時間前後保持する乾式製造法で化学反応式、
２ＣａＣＯ＋Ｃａ２Ｐ２Ｏ７→
Ｃａ （Ｐ Ｏ） Ｏ＋ ２ ＣＯ２により合成さ
れる４ＣＰを粉砕して微粉末とじて用いる。好ましくは
、２４庫以下の微粉末にする。4CP in the present invention is CaC0 as a calcium source.
Cab, Ca(OH) as phosphorus source 3°
2ゝP OHPO(NH4)H2PO4゜25'34'' (NH) HP Oi, , can containing both Ca and P, Ca(H2p o4), c
a 2 P 207 and the like are considered and can be produced by known methods. CaCO3 and Ca2P2O7 above 1300°C
4CP synthesized by the chemical reaction formula: 2CaCO+Ca2P2O7→Ca(PO)O+2CO2 is pulverized and used as a fine powder using a dry manufacturing method in which it is held at 1- for about 2 hours. Preferably, it is made into a fine powder of 24 or less.
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か均一に進行しな
いため良好な硬化組成物か得られない。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。At this time, if coarse particles are present, 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. When the 4CP powder produced in this way is kneaded with an organic acid aqueous solution,
It exhibits hardening action and is extremely useful as a powder base for medical hardening compositions.
硬化剤として分子量５．０００〜７０．０００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／ｃ♂
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か、崩壊率が１５％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か出来ない。PAA with a molecular weight of 5.000 to 70.000 as a curing agent
Alternatively, when only a copolymer of PAA and itaconic acid is used, the disintegration rate is low, but the compressive strength is 700 kg/c♂
less than In addition, 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 hardened composition with high pressure resistance strength may be formed, or the disintegration rate may be low. If it exceeds 15%, it is not preferable. As described above, when used alone, it is impossible to maintain both the properties of pressure resistance and low collapse rate.
分子量５．０００〜・７０．０００のＦＡＡまたは同一
分子量のＦＡＡとイタコン酸との共重合体を（八）とし
、クエン酸またはリンゴ酸、マレイン酸、酒石酸、−区
−
グリコール酸の１種以上の酸または混合酸を（Ｉ３）と
した場合、（Ａ）・（Ｂ） −２，０〜４．５：］の一
定比率で混合し、（Ａ）成分濃度か２５〜５５ ｗｔ、
％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。ＦＡＡにイタコン酸を共重合させ
るのは、有効カルホキシル基を増やし特性を増すためで
ある。(8) FAA with a molecular weight of 5.000 to 70.000 or a copolymer of FAA with the same molecular weight and itaconic acid, and one or more of citric acid, malic acid, maleic acid, tartaric acid, and glycolic acid. When the acid or mixed acid of (I3) is mixed at a constant ratio of (A) and (B) -2.0 to 4.5:], the concentration of (A) component is 25 to 55 wt,
% as a hardening agent, it is possible to achieve both compressive strength and low disintegration rate for the first time. The reason why itaconic acid is copolymerized with FAA is to increase the number of effective carboxyl groups and improve the properties.
分子量５，０００未満および７０，０００を越えるＦＡ
Ａを使用した場合や（Ａ）：（Ｂ）−２，０：］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（八）：（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／ｃＪ未満となる。また、硬化剤中の
ＦＡＡの濃度か５５ ｗｔ、％を越えると、硬化剤の粘
度か高く練和か困難となり、２５ ｗｔ％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２５〜５５ ｗｔ、％の範囲のＰＡＡ
の濃度か必要となる。また、硬化剤１重量部に対し４Ｃ
Ｐを混練する割合は、０，７〜１．７重量部の範囲で行
なイツれるのか好ま１．い。FA with molecular weight less than 5,000 and more than 70,000
When A is used, or when (B) is added in excess of the ratio (A):(B)-2,0:], the disintegration rate exceeds 1.5%; ):(B) If less acid (B) is added than the ratio of 4.5:1, the compressive strength will be less than 700 kg/cJ. In addition, if the concentration of FAA in the curing agent exceeds 55 wt%, the viscosity of the curing agent will be high and it will be difficult to mix it, and if it is less than 25 wt%, the curing time will be longer and air bubbles will be involved, resulting in a lower disintegration rate. PAA in the range of 25 to 55 wt% as a curing agent has an adverse effect on pressure resistance and strength, making it impossible to obtain a good cured composition.
concentration is required. Also, 4C per 1 part by weight of curing agent.
The proportion of P to be kneaded is preferably in the range of 0.7 to 1.7 parts by weight.1. stomach.
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強度か７００ｋｇ／ｃ♂
以上、崩壊率か１，５％以下の優れた特性を持つ医療用
硬化組成物として使用される。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 satisfying all the conditions has a compressive strength of 700 kg/c♂
As described above, it is used as a medical cured composition having excellent properties with a disintegration rate of 1.5% or less.
実施例 以下、本発明を実施例をもって説明する。Example The present invention will be explained below with reference to examples.
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２９．０００
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１３．１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］・試験法（ＪＩ
Ｓ Ｔ６６０２ ’）に準じて硬化時間、圧壊強
度、崩壊率を測定Ｉ−た。その結果を表１に示す。Example 1 4CP synthesized by a dry manufacturing method was finely pulverized into a fine powder of 24 μm or less. This 4CP powder has a molecular weight of 29.000.
PAA and a curing agent using citric acid were uniformly mixed and kneaded at a mixing ratio of 4CP and curing agent of 13.1 to obtain a putty-like product, which was then used as dental zinc phosphate cement] Test method (JI
The curing time, crushing strength, and disintegration rate were measured according to ST6602'). The results are shown in Table 1.
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２
９，０００のＦＡＡのみを使用した場合とＦＡＡとクエ
ン酸との混合比率か２０〜４５：１の範囲外の場合につ
き、実施例１と同様の４１す定をしまた結果を表２に示
す。Comparative Example 1 For 4CP finely pulverized in the same manner as in Example 1, a molecular weight of 2
For the case where only 9,000 FAA was used and the case where the mixing ratio of FAA and citric acid was outside the range of 20 to 45:1, 41 tests were carried out in the same manner as in Example 1, and the results are shown in Table 2. .
（以下余白）
−つ −
＝ ］ 〇 −
実施例 ２
分子量２９．０ｏ［］のＰＡＡと１５ｗｔ、％のイタコ
ン酸の共重合体を用いて実施例］と同様の測定をした結
果を表３に示す。(Leaving space below) 〇 - Example 2 Table 3 shows the results of the same measurements as in Example] using a copolymer of PAA with a molecular weight of 29.0o[] and 15 wt% itaconic acid. show.
比較例 ２
分子量２９，０００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
混合比率か２０〜４５：１の範囲外の場合、共重合体濃
度か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。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 20 to 45:1, Table 4 shows the results of the same measurements as in Example 1 for a combined concentration of 20 wt%.
（以下余白） 一 １３ 〜 比較例 ３ 酸のみを用いた場合の例を表５に示す。(Margin below) 1 13 ~ Comparative example 3 Table 5 shows an example in which only acid was used.
（以下余白）
実施例 ３
分子量Ｇ５．ＯＱＯ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。(Left below) Example 3 Molecular weight G5. Table 6 shows the results of measurements similar to those in Example 1 when OQO's PAA was used.
（以下余白）
一 １７ −
比較例 ４
分子量Ｂ５．ＤＯＯのＰＡＡを用いた請求範囲外の比較
例を表７に示す。(The following is a blank space) 1 17 - Comparative Example 4 Molecular weight B5. Table 7 shows a comparative example outside the scope of claims using DOO's PAA.
（以下余白）
実施例 ４
分子ｆｉｔ５．ＤＯＤ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。(Left below) Example 4 Molecule fit5. Table 8 shows the results of measurements similar to those in Example 1 when DOD's PAA was used.
（以下余白）
一 ２０ −−
比較例 ５
分子ｆｉｋ ５ 、 ＯＯＯのＰＡＡを用いた請求範囲
外の比較例を表９に示す。(The following is a blank space) 1 20 -- Comparative Example 5 Table 9 shows a comparative example using a PAA having the molecules fik 5 and OOO, which is outside the scope of the claims.
（以下余白）
比較例 ６
ＦＡＡの分子量か２，０００の場合、９０．０００の場
合につきそれぞれ表１０、表１１に示す。(The following is a blank space) Comparative Example 6 The molecular weight of FAA is shown in Tables 10 and 11 for cases of 2,000 and 90,000, respectively.
（以下余白）
一 ２５ −
発明の効果
本発明は、上記の様に４ＣＰに対し、分子量５．０００
〜７０．０００のＰＡＡまたは同一分子量のＦＡＡ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ｌ〜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。(The following is a blank space) 1 25 - Effects of the Invention The present invention has a molecular weight of 5.000 for 4CP as described above.
~70.000 PAA or a copolymer of FAA of the same molecular weight and itaconic acid and 1 such as citric acid or malic acid.
By using a curing agent mixed with more than one type of acid or mixed acid at a certain ratio, it is possible to achieve both high pressure resistance and low disintegration rate. A composition that can be used as a composition and exhibits unprecedented properties can be obtained.
Claims (1)
酸、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。Scope of Claims: (A) polyacrylic acid with a molecular weight of 5,000 to 70,000, or a copolymer of polyacrylic acid and itaconic acid with the same molecular weight, and (B) citric acid, malic acid, or maleic acid. , tartaric acid,
Mixing one or more acids or mixed acids of glycolic acid at a ratio of (A):(B) = 2.0 to 4.5:1,
The concentration of component (A) in the mixture is 25 to 55 wt. % aqueous solution is used as a hardening agent, and this hardening agent is kneaded with a powder containing tetracalcium phosphate as a main component.
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 true JPH01230367A (en) | 1989-09-13 |
| JPH0459911B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002536075A (en) * | 1999-02-02 | 2002-10-29 | ドクトル．ハー．ツェー．ロベルト マシーズ スティフツング | Implant containing 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002536075A (en) * | 1999-02-02 | 2002-10-29 | ドクトル．ハー．ツェー．ロベルト マシーズ スティフツング | Implant containing calcium cement and hydrophobic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0459911B2 (en) | 1992-09-24 |
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