JPH03128062A - Water-curable type calcium phosphate cement composition - Google Patents
Water-curable type calcium phosphate cement compositionInfo
- Publication number
- JPH03128062A JPH03128062A JP1266235A JP26623589A JPH03128062A JP H03128062 A JPH03128062 A JP H03128062A JP 1266235 A JP1266235 A JP 1266235A JP 26623589 A JP26623589 A JP 26623589A JP H03128062 A JPH03128062 A JP H03128062A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- cement
- cement composition
- molar ratio
- hydraulic
- 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 44
- 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 43
- 239000004568 cement Substances 0.000 title claims abstract description 27
- 239000001506 calcium phosphate Substances 0.000 title claims description 31
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims description 30
- 235000011010 calcium phosphates Nutrition 0.000 title claims description 30
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 14
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229940036348 bismuth carbonate Drugs 0.000 claims description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 210000000988 bone and bone Anatomy 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000003479 dental cement Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 238000004898 kneading Methods 0.000 abstract description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 abstract 2
- 230000002950 deficient Effects 0.000 abstract 1
- 229960001714 calcium phosphate Drugs 0.000 description 27
- 239000011396 hydraulic cement Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- -1 calcium phosphate compound Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000004262 dental pulp cavity Anatomy 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003462 bioceramic Substances 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
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002631 root canal filling material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CMJFWZAVQWOMKU-UHFFFAOYSA-H tricalcium diphosphate tetrahydrate Chemical compound O.O.O.O.[Ca++].[Ca++].[Ca++].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CMJFWZAVQWOMKU-UHFFFAOYSA-H 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 239000012137 tryptone Substances 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
ント及び歯牙根管熱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組成物に関す
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 as a dental cement such as a tooth root canal thermal filling material. Relating to cement compositions.
〈従来の技術〉
リン酸カルシウム水硬性セメント組成物は凝結硬化によ
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> Calcium phosphate hydraulic cement compositions are useful as tooth and bone repair materials because they are converted into compounds similar to the main components of teeth and bones in living organisms through setting and hardening, and are also useful as biopolymer materials. It is known to be useful as an adsorbent for harmful organic substances or inorganic ions in living organisms.
従来は、このようなリン酸カルシウム水硬性セメント組
成物は、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）、
又は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、このような従来のリン酸カルシウム
水硬性セメント組成物においては、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 calcium phosphate hydraulic cement compositions have been prepared by using a combination of salts and dilute acids as a curing liquid (for example, Japanese Patent Application Laid-open No. 59-88351),
However, in such conventional calcium phosphate hydraulic cement compositions, Until the cement hardens, the hardening liquid is highly acidic and causes 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.
かかる問題の解決のため、水により硬化するリン酸カル
シウム水硬性セメント組成物が開発されている（例えば
、ＦＣＲＥＰＯＲＴ、ｖｏ ｌ。To solve this problem, calcium phosphate hydraulic cement compositions that harden with water have been developed (for example, FCREPORT, vol.
６ （１９８８）、ｐ、４７５〜４８０「バイオセラミ
ックスとしての水硬性アパタイト」）。このような水に
より硬化するリン酸カルシウム水硬性セメント組成物は
現在までに数種類開発されており、例えば単に水と練和
するのみで３７℃において１０分程度で硬化するリン酸
カルシウム水硬性セメント組成物（特開昭６４−３７４
４５号）が知られている。このリン酸カルシウム水硬性
セメント組成物はＰＨもほぼ中性程度であり、生体に体
する刺激も少なく、従来公知のリン酸カルシウム水硬性
セメント組成物の問題点を解消するものである。6 (1988), p. 475-480 "Hydraulic apatite as bioceramics"). Several types of calcium phosphate hydraulic cement compositions that harden with water have been developed to date. For example, a calcium phosphate hydraulic cement composition that hardens in about 10 minutes at 37°C by simply kneading with water (Japanese Patent Application Laid-open No. Showa 64-374
No. 45) is known. This calcium phosphate hydraulic cement composition has a pH of approximately neutral and is less irritating to living organisms, thus solving the problems of conventionally known calcium phosphate hydraulic cement compositions.
しかしながら、前記リン酸カルシウム水硬性セメント組
成物は、α型第３リン酸カルシウムと、第２リン酸カル
シウム２水和物とをＣａ ／ Ｐモル比で、１．２０〜
１．４７の割合で混合することを特徴とするものであっ
て、実用的な硬化時間を得るためには１本来単独では硬
化することがない前記第２リン酸カルシウム２水和物を
、Ｃａ ／ Ｐモル比が１．４７である場合、最低でも
６．６重量％程度含有させなければならないので、強度
が低下するという欠点があり、しかも硬化時間が１０分
程度と、使用目的、特に歯科用セメントとして用いる場
合には、硬化時間が短かすぎるという問題もある。However, the calcium phosphate hydraulic cement composition contains α-type tertiary calcium phosphate and dibasic calcium phosphate dihydrate at a Ca/P molar ratio of 1.20 to 1.20.
It is characterized by mixing at a ratio of Ca/P of 1.47, and in order to obtain a practical curing time, 1. If the molar ratio is 1.47, the content must be at least 6.6% by weight, which has the disadvantage of decreasing strength.Moreover, the curing time is about 10 minutes, which is difficult to use, especially for dental cement. When used as such, there is also the problem that the curing time is too short.
〈発明が解決しようとする課題〉
従って１本発明の目的は、単に水と練和するのみで、実
用的な時間内に硬化し、空隙率が低く。<Problems to be Solved by the Invention> Therefore, one object of the present invention is to cure within a practical time by simply mixing with water, and to have a low porosity.
しかも高強度の水硬性リン酸カルシウムセメント組成物
を提供することにある。Moreover, it is an object of the present invention to provide a hydraulic calcium phosphate cement composition with high strength.
く課題を解決するための手段〉
本発明によれば、α型第３リン酸カルシウムと、第２リ
ン酸カルシウム２水和物とを混合して成るＣ ａ ／
Ｐモル比が、１．４７０より大きく、且つ１．４９８以
下の混合粉末を、主成分として含有することを特徴とす
る水硬性リン酸カルシウムセメント組成物が提供される
。Means for Solving the Problems According to the present invention, C a / formed by mixing α-type tertiary calcium phosphate and dibasic calcium phosphate dihydrate.
A hydraulic calcium phosphate cement composition is provided, which contains as a main component a mixed powder having a P molar ratio of greater than 1.470 and less than or equal to 1.498.
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組戊物は、α
型第３リン酸カルシウムと、第２リン酸カルシウム２水
和物とを必須の構成成分として含有する。The hydraulic calcium phosphate cement composition of the present invention has α
Contains type tertiary calcium phosphate and dibasic calcium phosphate dihydrate as essential components.
本発明に用いる前記第２リン酸カルシウム２水和物は、
α型第３リン酸カルシウムが水和を行なう際の始発剤と
して作用する化合物であって、微量の使用で充分である
。具体的には、前記第２リン酸カルシウム２水和物の組
成物全体に対する配合割合は、α型第３リン酸カルシウ
ムとのＣａ／４モル比で決定することができ、好ましく
は１．１〜４．４重量％の微量な配合で、α型第３リン
酸カルシウム単独で使用するよりも強度を増大させ、且
つ空隙率を減少させることができる。The second calcium phosphate dihydrate used in the present invention is
It is a compound that acts as an initiator when α-type tertiary calcium phosphate hydrates, and its use in a small amount is sufficient. Specifically, the blending ratio of the second calcium phosphate dihydrate to the entire composition can be determined by the Ca/4 molar ratio with α-type third calcium phosphate, preferably 1.1 to 4.4. By adding a small amount by weight, it is possible to increase the strength and reduce the porosity compared to using α-type tertiary calcium phosphate alone.
このように第２リン酸カルシウム２水和物の配合割合が
微量で良いのは、α型第３リン酸カルシウムが自己硬化
能力を有するからである。The reason why the blending ratio of dibasic calcium phosphate dihydrate may be small is that α-type dibasic calcium phosphate has a self-hardening ability.
本発明において、α型第３リン酸カルシウムと、第２リ
ン酸カルシウム２水和物とのＣａ ／ Ｐモル比は、１
．４７０より大きく、且つ１．４９８以下であり、好ま
しくは１．４８０〜１．４９５の範囲である。前記Ｃａ
／ Ｐモル比が１．４７０以下又は１．４９８を超え
る場合には、得られる硬化物の強度が低下する。In the present invention, the Ca/P molar ratio between α-type tertiary calcium phosphate and dihydrate calcium phosphate dihydrate is 1.
．． It is larger than 470 and 1.498 or less, preferably in the range of 1.480 to 1.495. Said Ca
/P molar ratio is 1.470 or less or exceeds 1.498, the strength of the obtained cured product decreases.
また本発明の水硬性リン酸カルシウムセメント組成物の
硬化時間は、前記Ｃａ ／ Ｐモル比及び反応温度によ
って決定するが、通常使用される３７℃においては、約
４０〜８０分で硬化させることができる。前記硬化時間
は、若干長いように思われるが、α型第３リン酸カルシ
ウムを単独で硬化させる場合、１６０分間を要すること
を鑑みると短く、しかも硬化時間が前記４０〜８０分と
いうのは、使用目的１例えば歯牙根管部充填材等に用い
る場合には、好ましい硬化時間である６尚、前記Ｃａ
／ Ｐモル比が１．４７０以下では、硬化時間が３０分
以下と短く、またＣ ａ ／ Ｐモル比が１、−４９８
を超えると、硬化時間が１００分以上と成るので好まし
くない。Further, the curing time of the hydraulic calcium phosphate cement composition of the present invention is determined by the Ca/P molar ratio and the reaction temperature, but it can be cured in about 40 to 80 minutes at the commonly used temperature of 37°C. The curing time may seem a little long, but considering that it takes 160 minutes to cure α-type tricalcium phosphate alone, it is short, and the curing time of 40 to 80 minutes is suitable for the intended use. 1. For example, when used as a tooth root canal filling material, the curing time is a preferable 6.
/P molar ratio of 1.470 or less, the curing time is short, 30 minutes or less, and C a /P molar ratio of 1.-498
If it exceeds this, the curing time will be 100 minutes or more, which is not preferable.
本発明の水硬性リン酸カルシウムセメント組成物は、生
体の骨や歯の主成分であるヒドロキシアパタイトと同系
のリン酸カルシウム化合物を用いているので、生体に対
する親和性が良好である。Since the hydraulic calcium phosphate cement composition of the present invention uses a calcium phosphate compound that is similar to hydroxyapatite, which is the main component of bones and teeth of living organisms, it has good affinity for living organisms.
従って本発明においては、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、例えばヒドロキシアパタイト、
フッ素アパタイト、β型第３リン酸カルシウム、ピロリ
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；アルミナ、ジルコニア、窒化珪素、炭化
珪素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。Therefore, in the present invention, in addition to the above-mentioned essential components, ceramic powder may be added to improve mechanical strength and biocompatibility when the composition is cured, as long as it does not impair biocompatibility. It can also be improved. Examples of the ceramic powder include hydroxyapatite,
Calcium phosphate compounds such as fluoroapatite, β-type tertiary calcium phosphate, calcium pyrophosphate, and quaternary calcium phosphate; examples include alumina, zirconia, silicon nitride, silicon carbide, etc., and 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組成物で
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ＸＭ造影
剤としては硫酸バリウム。Furthermore, the hydraulic calcium phosphate cement composition of the present invention may optionally contain an X-ray contrast agent, an antibacterial agent, etc., if necessary. For example, a preferred XM contrast agent is barium sulfate.
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。It can be selected from the group consisting of basic bismuth carbonate, iodoform and mixtures thereof. Preferred antibacterial agents include iodoform and chlorhexidine.
本発明の水硬性リン酸カルシウムセメント組成物は、通
常水と練和することにより使用することができるが、操
作性の向上及びセメント泥の濡れ性を向上させるために
、組成物及び／又は水の中に例えば、高分子表面活性剤
を添加することもできる。該高分子表面活性剤としては
、合成高分子化合物であるポリエチレングリコール、ポ
リビニルアルコール等、生体高分子であるメチルセルロ
ース、カルボキシメチルセルロース、ヒドロキシプロピ
ルメチルセルロース等及びこれらの化合物の誘導体等が
挙げられるが、生体に対する毒性がない限りは任意の化
合物及びその誘導体が使用できる。The hydraulic calcium phosphate cement composition of the present invention can be used by mixing with water, but in order to improve operability and wettability of cement mud, it is possible to use the composition and/or water. For example, a polymeric surfactant can also be added. Examples of the polymeric surfactants include synthetic polymers such as polyethylene glycol and polyvinyl alcohol, biopolymers such as methylcellulose, carboxymethylcellulose, and hydroxypropylmethylcellulose, and derivatives of these compounds. Any compound or derivative thereof can be used as long as it is not toxic.
〈実施例〉
以下本発明を実施例及び比較例により更に詳細に説明す
るが１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 described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
失あ」リニニｉ
α型第３リン酸カルシウムと、第２リン酸カルシウム２
水和物とを、Ｃａ／Ｐモル比で１．４７１゜１．４８０
，１．４９０．１．４９５．１．４９８となるように、
ボールミルによって混合し、水硬性リン酸カルシウムセ
メント組成物を調製した。得られた夫々の組成物を水で
練和硬化させ、水中に２４時間浸漬させた後、濡れたま
まインストロン社製１１２５型万能試験機により圧縮強
度を測定した。この際硬化時間も同時に測定した。測定
結果を表１に示す。Lininii α-type tertiary calcium phosphate and dibasic calcium phosphate 2
hydrate and Ca/P molar ratio of 1.471°1.480
, 1.490.1.495.1.498,
A hydraulic calcium phosphate cement composition was prepared by mixing using a ball mill. Each of the resulting compositions was kneaded and cured with water, immersed in water for 24 hours, and then compressive strength was measured while wet using a universal testing machine model 1125 manufactured by Instron. At this time, the curing time was also measured at the same time. The measurement results are shown in Table 1.
里笠銖よ二重
Ｃａ ／ Ｐモル比を１．４５０．１．４７０及び１．
４９９とした以外は、実施例１〜５と同様に水硬性リン
酸カルシウムセメント組成物を調製し、各測定を行なっ
た。その結果を表土に示す。The double Ca/P molar ratio was 1.450.1.470 and 1.470.
A hydraulic calcium phosphate cement composition was prepared in the same manner as in Examples 1 to 5, except that the composition was set to 499, and each measurement was performed. The results are shown on the topsoil.
生佼藍土
水硬性リン酸カルシウムセメント組成物成分をα型第３
リン酸カルシウムのみした以外は、実施例１〜５と同様
に各測定を行なった。その結果を去Ｌ０４【
実施例１で調製した水硬性リン酸カルシウムセメント組
成物のＸ線造影性を向上させるために、更に硫酸バリウ
ム、塩基性炭酸ビスマス及びヨードホルム（和光純薬株
式会社）を、前記組成物に対して夫々３０重量％含有さ
せた。次いで得られた組成物を水で練和してペースト状
とし、抜髄処理を行なったヒトの抜去歯牙の根管部に充
填した。Alpha-type 3
Each measurement was carried out in the same manner as in Examples 1 to 5, except that only calcium phosphate was used. The results were compared to L04 [In order to improve the X-ray contrast properties of the hydraulic calcium phosphate cement composition prepared in Example 1, barium sulfate, basic bismuth carbonate and iodoform (Wako Pure Chemical Industries, Ltd.) were added to the composition. Each was contained in an amount of 30% by weight based on the weight of the product. The resulting composition was then kneaded with water to form a paste, and the paste was filled into the root canal of a human tooth that had undergone pulp removal treatment.
該ペーストが硬化した後、レントゲン撮影を行なったと
ころ、セメントの充填箇所が明瞭に認められた。尚実施
例１で調製した水硬性リン酸カルシウムセメント組成物
についても同様に、レントゲン撮影を行なったところ、
セメントの充填箇所を特定することができなかった。After the paste had hardened, X-ray photography was performed, and the cement-filled areas were clearly seen. The hydraulic calcium phosphate cement composition prepared in Example 1 was also subjected to X-ray photography, and the results were as follows.
It was not possible to determine the location of cement filling.
失凰鼻ヱ
抗菌性を付与するために実施例１で調製した水硬性リン
酸カルシウムセメント組威物に、ヨードホルムを、組成
物に対して３０重量％含有させた。In order to impart antibacterial properties to the hydraulic calcium phosphate cement composition prepared in Example 1, iodoform was added to the composition in an amount of 30% by weight.
次いで得られた組成物を水で練和し、直径３ｍｍ、高さ
６ｍ＋の円柱状に成形し、硬化直後、１日、３日、７日
及び３０日後の硬化体について、以下に示す試験を行な
ったところ、ヨードホルムを含有させた硬化体は、明瞭
な抗菌性を示し、すべての細菌の発育を著しく阻害した
。また抗菌性は、硬化直後で最も強く、経時的に減少傾
向を示した。Next, the obtained composition was kneaded with water and formed into a cylindrical shape with a diameter of 3 mm and a height of 6 m+, and the following tests were conducted on the cured product immediately after curing, and after 1 day, 3 days, 7 days, and 30 days. When tested, the cured product containing iodoform showed clear antibacterial properties and significantly inhibited the growth of all bacteria. Furthermore, the antibacterial properties were strongest immediately after curing and showed a tendency to decrease over time.
抜且作芙秩
供試菌として、 Ｓｔｒ、ｆａｅｃａｌｉｓ、Ｓｔｒ、
５ａｌｉｖａｒｉｕｓ。Selected Fuchichi test bacteria include Str, faecalis, Str,
5alivarius.
５ｔａｐｈ、ｅｐｉｄｅｒｍｉｄｉｓ、Ｂ、５ｕｂｔｉ
ｌｉｓ、Ｅ、ｃｏｌｉの５種類の菌と、感染根管由来の
ｍ１ｘｅｄ ｃｕｌｔｕｒｅを使用した。細菌の濃度は
、ＭｃＦａｒｌａｎｄ法に従い１．２ Ｘ １０１２／
ｍＱに培地中で調製した。次に各培地から培養液を０．
１ｍＱずつ均等に、ｔｒｙｐｔｏｎｅ ５ｏｙａ ａｇ
ａｒのペトリ皿に分注し、室温で３０分間乾燥後、好気
的条件下、３７℃、４８時間培養し、セメント硬化体か
ら最も近いコロニーまでの細菌育成阻止帯を計測した。5taph, epidermidis, B, 5ubti
Five types of bacteria, Lis, E. and coli, and m1xed culture derived from infected root canals were used. The concentration of bacteria was 1.2 x 10/1 according to the McFarland method.
mQ was prepared in culture medium. Next, remove the culture solution from each medium by 0.
Tryptone 5oya ag equally in 1mQ each
The mixture was dispensed into Ar Petri dishes, dried at room temperature for 30 minutes, and then cultured under aerobic conditions at 37°C for 48 hours, and the bacterial growth inhibition zone from the hardened cement body to the nearest colony was measured.
〈発明の効果〉
本発明の水硬性リン酸カルシウムセメント組成物は、自
己硬化能力を有するα型第３リン酸カルシウムと、弱酸
性の微量第２リン酸カルシウム水和物とを、特定のＣａ
／ Ｐモル比で混合しているので、高強度で、空隙率
が小さく、骨欠損部及び骨空隙部を充填することができ
る医科用セメント等に有用であり、しかも硬化に要する
時間が４０〜８０分であるので、特に歯牙根管熱充填剤
等の歯科用セメントとしても極めて有用である。また所
望に応じて、本発明の組成物中に、更に硫酸バリウム、
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される化合物を含有させることによ
り、組成物を硬化させた際のＸ線造影性を向上させたり
、抗菌性を付与することもできる。<Effects of the Invention> The hydraulic calcium phosphate cement composition of the present invention combines α-type tertiary calcium phosphate having self-hardening ability and a weakly acidic trace amount of dibasic calcium phosphate hydrate with a specific Ca
/P molar ratio, it has high strength, low porosity, and is useful for medical cement, etc. that can fill bone defects and bone voids, and the curing time is 40 ~ Since it takes 80 minutes, it is extremely useful especially as a dental cement such as a tooth root canal hot filling agent. If desired, the composition of the present invention may further include barium sulfate,
By containing a compound selected from the group consisting of basic bismuth carbonate, iodoform, and mixtures thereof, it is possible to improve the X-ray contrast property when the composition is cured or to impart antibacterial properties.
Claims (1)
ム２水和物とを混合して成るＣａ／Ｐモル比が、１．４
７０より大きく、且つ１．４９８以下の混合粉末を、主
成分として含有することを特徴とする水硬性リン酸カル
シウムセメント組成物。 ２）更に硫酸バリウム、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される化合
物を含有させることを特徴とする請求項１記載の水硬性
リン酸カルシウムセメント組成物。[Claims] 1) A mixture of α-type tertiary calcium phosphate and dibasic calcium phosphate dihydrate with a Ca/P molar ratio of 1.4.
1. A hydraulic calcium phosphate cement composition comprising, as a main component, a mixed powder having a particle size of more than 70 and less than or equal to 1.498. 2) The hydraulic calcium phosphate cement composition according to claim 1, further comprising a compound selected from the group consisting of barium sulfate, basic bismuth carbonate, iodoform and mixtures thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1266235A JPH03128062A (en) | 1989-10-16 | 1989-10-16 | Water-curable type calcium phosphate cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1266235A JPH03128062A (en) | 1989-10-16 | 1989-10-16 | Water-curable type calcium phosphate cement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03128062A true JPH03128062A (en) | 1991-05-31 |
| JPH0528631B2 JPH0528631B2 (en) | 1993-04-26 |
Family
ID=17428149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1266235A Granted JPH03128062A (en) | 1989-10-16 | 1989-10-16 | Water-curable type calcium phosphate cement composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03128062A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2667309A1 (en) * | 1990-09-27 | 1992-04-03 | Mitsubishi Materials Corp | CALCIUM PHOSPHATE HYDRAULIC CEMENT COMPOSITION AND CEMENT COMPOSITION CONTAINING HARDENING LIQUID. |
| FR2682947A1 (en) * | 1991-10-29 | 1993-04-30 | Mitsubishi Materials Corp | CALCIUM PHOSPHATE GRANULAR CEMENT AND METHOD FOR ITS PRODUCTION. |
| JPH05116997A (en) * | 1991-10-29 | 1993-05-14 | Mitsubishi Materials Corp | Granular calcium phosphate cement and production thereof |
| JPH05116998A (en) * | 1991-10-29 | 1993-05-14 | Mitsubishi Materials Corp | Granular calcium phosphate cement and production thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6219508A (en) * | 1985-07-18 | 1987-01-28 | Sankin Kogyo Kk | Root canal filling material for dental use |
| JPS6269823A (en) * | 1986-09-12 | 1987-03-31 | Mitsubishi Mining & Cement Co Ltd | Calcium phosphate based fiber |
| JPS6330361A (en) * | 1986-07-22 | 1988-02-09 | 太平洋セメント株式会社 | Manufacture of calcium phosphate base ceramics |
| JPS63201054A (en) * | 1987-02-10 | 1988-08-19 | 科学技術庁無線材質研究所長 | Manufacture of apatite formed sintered body |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
| JPH01148812A (en) * | 1988-09-30 | 1989-06-12 | Mitsubishi Mining & Cement Co Ltd | Production of inorganic fiber |
| JPH01158965A (en) * | 1987-12-16 | 1989-06-22 | Tokuyama Soda Co Ltd | Curable composition |
| JPH01301543A (en) * | 1988-05-31 | 1989-12-05 | Tokuyama Soda Co Ltd | Curable composition |
-
1989
- 1989-10-16 JP JP1266235A patent/JPH03128062A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6219508A (en) * | 1985-07-18 | 1987-01-28 | Sankin Kogyo Kk | Root canal filling material for dental use |
| JPS6330361A (en) * | 1986-07-22 | 1988-02-09 | 太平洋セメント株式会社 | Manufacture of calcium phosphate base ceramics |
| JPS6269823A (en) * | 1986-09-12 | 1987-03-31 | Mitsubishi Mining & Cement Co Ltd | Calcium phosphate based fiber |
| JPS63201054A (en) * | 1987-02-10 | 1988-08-19 | 科学技術庁無線材質研究所長 | Manufacture of apatite formed sintered body |
| JPS6437445A (en) * | 1987-07-31 | 1989-02-08 | Nat Inst Res Inorganic Mat | Calcium phosphate hydraulic cement composition |
| JPH01158965A (en) * | 1987-12-16 | 1989-06-22 | Tokuyama Soda Co Ltd | Curable composition |
| JPH01301543A (en) * | 1988-05-31 | 1989-12-05 | Tokuyama Soda Co Ltd | Curable composition |
| JPH01148812A (en) * | 1988-09-30 | 1989-06-12 | Mitsubishi Mining & Cement Co Ltd | Production of inorganic fiber |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2667309A1 (en) * | 1990-09-27 | 1992-04-03 | Mitsubishi Materials Corp | CALCIUM PHOSPHATE HYDRAULIC CEMENT COMPOSITION AND CEMENT COMPOSITION CONTAINING HARDENING LIQUID. |
| JPH04135562A (en) * | 1990-09-27 | 1992-05-11 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement |
| FR2682947A1 (en) * | 1991-10-29 | 1993-04-30 | Mitsubishi Materials Corp | CALCIUM PHOSPHATE GRANULAR CEMENT AND METHOD FOR ITS PRODUCTION. |
| GB2260977A (en) * | 1991-10-29 | 1993-05-05 | Mitsubishi Materials Corp | Calcium phosphate cement compositions |
| JPH05116997A (en) * | 1991-10-29 | 1993-05-14 | Mitsubishi Materials Corp | Granular calcium phosphate cement and production thereof |
| JPH05116998A (en) * | 1991-10-29 | 1993-05-14 | Mitsubishi Materials Corp | Granular calcium phosphate cement and production thereof |
| GB2260977B (en) * | 1991-10-29 | 1995-08-23 | Mitsubishi Materials Corp | Calcium phospate cement compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0528631B2 (en) | 1993-04-26 |
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