JPH01320251A - Pasty hardenable composition - Google Patents
Pasty hardenable compositionInfo
- Publication number
- JPH01320251A JPH01320251A JP63150248A JP15024888A JPH01320251A JP H01320251 A JPH01320251 A JP H01320251A JP 63150248 A JP63150248 A JP 63150248A JP 15024888 A JP15024888 A JP 15024888A JP H01320251 A JPH01320251 A JP H01320251A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene glycol
- powder
- phosphate
- paste
- liquid
- 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 25
- 235000011837 pasties Nutrition 0.000 title 1
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 39
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 30
- 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 claims abstract description 16
- 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 abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 8
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 30
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 abstract description 30
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 14
- 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 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 239000002631 root canal filling material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000005888 Periodontal Pocket Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 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
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Dental Prosthetics (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〕
本発明は新規なワンペーストタイプ硬化性組成物に関す
る。詳しくは、保存安全性が特に良好で、且つ水との接
触により、良好なヒドロキシアパタイト硬化体を生成す
るペースト状硬化性組成物である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel one-paste type curable composition. Specifically, it is a paste-like curable composition that has particularly good storage safety and produces a good hardened hydroxyapatite product upon contact with water.
一般に、根管充填材、裏層材、覆軍材等の歯科用修復材
は、歯との親和性が良好で且つ生体に対して為害作用が
少ない硬化性材料が求められている。In general, dental restorative materials such as root canal filling materials, backing materials, and covering materials are required to be hardenable materials that have good affinity with teeth and have little harmful effect on living organisms.
従来、かかる硬化性材料として、硬化後に骨や歯の主成
分であるヒドロキシアパタイト（ＨＡＰ）を生成する組
成物が提案されている。例えば、リン酸四カルシウム及
び／又はα−リン酸三カルシウムと水又は有機酸水溶液
の練和液とよりなる組成物が知られている。Conventionally, compositions that produce hydroxyapatite (HAP), which is the main component of bones and teeth, after hardening have been proposed as such hardenable materials. For example, a composition comprising a kneading solution of tetracalcium phosphate and/or α-tricalcium phosphate and water or an aqueous organic acid solution is known.
しかしながら、上記組成物は、保存中における硬化を避
けるため、リン酸四カルシウム及び／又はα−リン酸三
カルシウムの粉末と練和液との二剤に分けて取り扱われ
、使用直前にこれらを練和して使用されている。そのた
め、治療において好適な粘度のペーストを調製するため
に時間及び熟練を要する等の操作上の問題があった。However, in order to avoid hardening during storage, the above composition is handled in two parts: a powder of tetracalcium phosphate and/or α-tricalcium phosphate and a kneading liquid, and these are kneaded immediately before use. It is used in harmony. Therefore, there are operational problems such as the need for time and skill to prepare a paste with a suitable viscosity for treatment.
上記問題点を解決するための手段として、リン酸四カル
シウム、またはα−リン酸三カルシウムを含む前記組成
物をあらかじめ水と置換可能な可能な特定の有機化合物
と混合して、ワンペースト化することにより、ペースト
状で保存が可能で、必要なときに患部への充填を行うと
、該有機化合物が生体内の水分と置換、反応してヒドロ
キシアパタイト硬化体が生成することが見い出され、既
に提案されている（特願昭６２−２９６２２７号）。As a means to solve the above problems, the composition containing tetracalcium phosphate or α-tricalcium phosphate is mixed in advance with a specific organic compound capable of replacing water to form a one-paste. It has been found that when it is stored in the form of a paste and filled into the affected area when necessary, the organic compound replaces and reacts with moisture in the body, producing a hardened hydroxyapatite. It has been proposed (Japanese Patent Application No. 62-296227).
上記発明において、水と置換可能な有機化合物としては
、植物油、多価アルコール、ポリアルキレングリコール
、シリコンオイル及び流動パラフィン等が挙げられてい
るが、操作性、大気中水分に対する保存安定性、患部へ
充填したときの水分との置換速度及び生体に対する安全
性等を勘案すると液状ポリエチレングリコールが優れて
いる。In the above invention, organic compounds that can replace water include vegetable oil, polyhydric alcohol, polyalkylene glycol, silicone oil, and liquid paraffin. Liquid polyethylene glycol is superior in terms of the rate of water replacement during filling and safety for living organisms.
しかしながら、液状ポリエチレングリコールを用いたペ
ースト状硬化性組成物の場合は、保存時の温度が４０〜
５０℃の高温になったり、輸送時に振動が加わると、粉
末と液状ポリエチレングリコールが分離するという問題
点がある。However, in the case of a paste-like curable composition using liquid polyethylene glycol, the temperature during storage is 40-40°C.
There is a problem in that the powder and liquid polyethylene glycol separate when the temperature is as high as 50° C. or when vibrations are applied during transportation.
本発明者等は、水と置換可能な有機化合物として、液状
ポリエチレングリコールを用いた前記組成物の問題点を
解決すべく鋭意研究を重ねた。その結果、上記リン酸カ
ルシウム粉末と液状ポリエチレングリコールよりなる組
成物に、分子量１０００以上の多価分子量ポリエチレン
グリコールを特定量添加することにより、操作性、アパ
タイトの生成における反応性等を損なうことなく、液と
粉末の分離のないペーストが得られることを見いだし、
本発明を完成するに至った。−
本発明は（ｉ）α−リン酸’Ｗｈルシウム、リン酸四カ
ルシウム又はリン酸四カルシウムとＣａ／Ｐ原子比が１
．６７未満のリン酸カルシウムとの混合物、（以下、こ
れらを総称してｐｃ粉末という。）（ｉｉ ）室温で液
状のポリエチレングリコール（以下、単に液状ポリエチ
レングリコールともいう）及び（ｉｉｉ）該液状ポリエ
チレングリコールに対して１〜２０重量％の分子量１０
００以上の高分子量ポリエチレングリコールよりなるペ
ースト状硬化性組成物である。The present inventors have conducted extensive research to solve the problems of the above-mentioned compositions that use liquid polyethylene glycol as an organic compound that can replace water. As a result, by adding a specific amount of polyvalent molecular weight polyethylene glycol with a molecular weight of 1,000 or more to the above-mentioned composition consisting of calcium phosphate powder and liquid polyethylene glycol, it was possible to mix the composition with liquid without impairing operability, reactivity in apatite production, etc. It was discovered that a paste without powder separation could be obtained,
The present invention has now been completed. - The present invention provides (i) α-'Wh lucium phosphate, tetracalcium phosphate, or tetracalcium phosphate and a Ca/P atomic ratio of 1.
．． (hereinafter collectively referred to as PC powder), (ii) polyethylene glycol that is liquid at room temperature (hereinafter also simply referred to as liquid polyethylene glycol), and (iii) for the liquid polyethylene glycol. 1 to 20% by weight, molecular weight 10
This is a paste-like curable composition made of high molecular weight polyethylene glycol having a molecular weight of 0.00 or more.
本発明の硬性組成物に用いられるリン酸四カルシウム（
以下、Ｃ４Ｐと略す。）粉体は、いかなる方法で製造し
たものであっても良い。原料はＣａ源としてＣａＣ０，
、Ｃａｂｓ Ｃａ（ＯＨ）ｚ、Ｐ源としてＰ２Ｏ３、Ｈ
３ＰＯ４、ＮＨ４ＨｚＰＯ４、（Ｎ Ｈ４）２ＨＰ Ｏ
ａ 、ＣａとＰの両方を含有するＣａＨＰ Ｏｓ ・２
Ｈ２０、ＣａＨＰＯ４、Ｃａ（ＨｚＰ ０ａ）ｔ−。Tetracalcium phosphate (
Hereinafter, it will be abbreviated as C4P. ) The powder may be manufactured by any method. The raw material is CaC0 as a Ca source,
, Cabs Ca(OH)z, P2O3 as P source, H
3PO4, NH4HzPO4, (NH4)2HP O
a, CaHP Os ・2 containing both Ca and P
H20, CaHPO4, Ca(HzP 0a)t-.
Ｃａｚ Ｐ ｔ ０７等が考えられ、原料によって種々
の製造方法があるが、公知のＣａ ＨＰ Ｏａ・２Ｈｚ
Ｏを＋３１成して得たＴ Ｃａ２Ｐ２０ｔをＣａＣ０
，と混和焼成する乾式製造法が好適である。Caz P t 07 etc. are considered, and there are various manufacturing methods depending on the raw materials, but the well-known Ca HP Oa・2Hz
T Ca2P20t obtained by forming +31 O is CaC0
A dry manufacturing method of mixing and firing with , is suitable.
この反応は、
２ＣａＨＰＯ４・２ＨｚＯ−
Ｔ −ＣａｔＰｚＯｙ ＋ ５ ＨｚＯＣａ、ＰｚＯ，
＋２ＣａＣＯ，−＋
Ｃａ４ＰｚＯ＊ ＋２ ＣＯｚ
の反応式で示され、１２００℃以上で焼成後炉外で急冷
するか、窒素雰囲気中で１２００℃以上で焼成すれば、
ヒドロキシアパタイトに転移することなく純粋なＣ４Ｐ
が得られる。This reaction is as follows: 2CaHPO4.2HzO- T -CatPzOy + 5HzOCa, PzO,
It is shown by the reaction formula +2CaCO, -+ Ca4PzO* +2 COz, and if fired at 1200°C or higher and then rapidly cooled outside the furnace, or fired at 1200°C or higher in a nitrogen atmosphere,
Pure C4P without transfer to hydroxyapatite
is obtained.
また、α−リン酸三カルシウム（以下、Ｃ３Ｐと略す）
の製造法も前記した原料を用いる公知の方法がｗＩ限な
く採用される。In addition, α-tricalcium phosphate (hereinafter abbreviated as C3P)
As for the manufacturing method, any known method using the above-mentioned raw materials can be employed without limitation.
また本発明において、前記したＣ４Ｐと混合されるＣａ
／Ｐモル比が１．６７未満のリン酸カルシウム（以下、
ＨＰＣＰと略す。）は、種々のものが使用できる。例え
ば、Ｃａ（Ｈ２Ｐ Ｏａ）ｚ ・Ｈｚ ０１ＣａＨＰ
Ｏｓ ・２ ＨｚＯｌＣａ ＨＰ Ｏａ、Ｃａ、Ｈｚ（
Ｐ ０４）６・５ ＨｚＯ，Ｃａｚ（Ｐ ０ｍ１ｔ、Ｃ
ａｚ Ｐ ２０ ｑ等が挙げられるが、そのうちＣａＨ
Ｐ Ｏａ ・２ ＨｚＯ２ＣａＨＰＯ−は、硬化体の力
学的性質、操作性、保存安定性の点で、特に好適である
。例えばＨＰＣＰとしてＣａＨＰＯ４・２Ｈ２０を用い
た場合、反応式は次式のように表され、ハイドロキシア
パタイトが生成する。In addition, in the present invention, Ca mixed with the above-mentioned C4P
/P molar ratio of less than 1.67 calcium phosphate (hereinafter referred to as
It is abbreviated as HPCP. ) can be used in various ways. For example, Ca(H2P Oa)z Hz 01CaHP
Os ・2 HzOlCa HP Oa, Ca, Hz (
P 04) 6.5 HzO, Caz (P 0m1t, C
az P 20 q, etc., among which CaH
P Oa .2 HzO2CaHPO- is particularly suitable in terms of the mechanical properties, operability, and storage stability of the cured product. For example, when CaHPO4.2H20 is used as HPCP, the reaction formula is expressed as the following formula, and hydroxyapatite is produced.
２ＣａａＰｚＯｑ ＋２ＣａＨＰ０４ ・２Ｈ，０−Ｃ
ａ＋ｏ（Ｐ ０４）６（ＯＨ）ｚ ＋ ２ ＨｚＯ本発
明において、上記のＨＰＣＰ粉末とＣ４Ｐ粉末の混合物
の混合比はＣａ／Ｐモル比力月、３〜１．８の割合にな
るように調節することが、ヒドロキシアパタイトを効率
よく生成させ、得られる硬化体の強度を多価めるために
好ましい。2CaaPzOq +2CaHP04 ・2H,0-C
a + o (P 04) 6 (OH) z + 2 HzO In the present invention, the mixing ratio of the mixture of HPCP powder and C4P powder is adjusted to a Ca/P molar specific ratio of 3 to 1.8. This is preferable in order to efficiently generate hydroxyapatite and increase the strength of the resulting cured product.
また、上記のｐｃ粉末の粒径、形状は特に制限されない
が、硬化速度を速めるためと、粉液比を向上させるため
に、ＲＰＣＰ粉末は平均粒径５０μｍ未満、好ましくは
０．１〜１０μｍが、またＣ３Ｐ及びＣ４Ｐ粉末は平均
粒径０．１〜１００μｍ、好ましくは０．５〜５０μｍ
の粒径を有するものを、各々使用するのが好適である。Furthermore, the particle size and shape of the above-mentioned PC powder are not particularly limited, but in order to accelerate the curing speed and improve the powder-liquid ratio, the RPCP powder has an average particle size of less than 50 μm, preferably 0.1 to 10 μm. , and C3P and C4P powders have an average particle size of 0.1 to 100 μm, preferably 0.5 to 50 μm.
It is preferable to use particles having a particle size of .
本発明の液状ポリエチレングリコールは、室温で液状で
あれば制限なく使用できる。中でも、操作性、安全性等
の点より、平均分子量が２００〜４００のものが好適に
使用できる。The liquid polyethylene glycol of the present invention can be used without any restriction as long as it is liquid at room temperature. Among them, those having an average molecular weight of 200 to 400 can be preferably used from the viewpoint of operability, safety, etc.
又、本発明に用いる高分子量ポリエチレングリコールは
、平均分子量が１０００以上であれば制限なく使用でき
る。中でも、平均分子量が１００００〜２０００００の
ものが好適である。平均分子量が１０００未満の場合は
ｐｃ粉末と液状ポリエチレングリコールとの分離防止効
果が充分でなく 、２０００００以上のものは、液状ポ
リエチレングリコールに均一に混合するのが困難となる
場合がある。Further, the high molecular weight polyethylene glycol used in the present invention can be used without any restriction as long as it has an average molecular weight of 1000 or more. Among these, those having an average molecular weight of 10,000 to 200,000 are preferred. If the average molecular weight is less than 1,000, the effect of preventing separation between PC powder and liquid polyethylene glycol is insufficient, and if it is more than 200,000, it may be difficult to mix uniformly into liquid polyethylene glycol.
上記高分子量ポリエチレングリコールの添加量は、分子
量によって異なるが、低分子量ポリエチレングリコール
に対して１〜２０重量％、更に好ましくは２〜ＩＯ重景
％が好適である。添加量が上記範囲より少い場合は前記
した効果が充分でなく、また、該範囲より多い場合は、
粉液比を上げることができず、高い強度を有するヒドロ
キシアパタイト硬化体を得ることが困難となる。The amount of the high molecular weight polyethylene glycol added varies depending on the molecular weight, but is preferably 1 to 20% by weight, more preferably 2 to IO% by weight, based on the low molecular weight polyethylene glycol. If the amount added is less than the above range, the above effects will not be sufficient, and if it is more than the range,
It is not possible to increase the powder-liquid ratio, making it difficult to obtain a cured hydroxyapatite body with high strength.
本発明において、ｐｃ粉末、液状ポリエチレングリコー
ル及び高分子量ポリエチレングリコールとの混合方法は
特に制限されない。一般には、液状ポリエチレングリコ
ールと高分子量ポリエチレングリコールを予め混合した
後、ｐｃ粉末と混合する方法が推奨される。In the present invention, the method of mixing PC powder, liquid polyethylene glycol, and high molecular weight polyethylene glycol is not particularly limited. Generally, a method is recommended in which liquid polyethylene glycol and high molecular weight polyethylene glycol are mixed in advance and then mixed with PC powder.
上記液状ポリエチレングリコールと高分子量ポリエチレ
ングリコールの混合方法は、特に制限されないが、６０
〜１００ ’Ｃで加熱攪拌して均一にすることが望まし
い。以下、液状ポリエチレングリコールと高分子量ポリ
エチレングリコールの混合物を練和液という。The method of mixing the liquid polyethylene glycol and high molecular weight polyethylene glycol is not particularly limited, but
It is desirable to heat and stir at ~100'C to make it uniform. Hereinafter, the mixture of liquid polyethylene glycol and high molecular weight polyethylene glycol will be referred to as a kneading solution.
本発明に於て、ｐｃ粉末と練和液との粉液比は、用途に
応して好適な粘度となるように適宜決定すればよい。一
般には、得られるペーストの粘度がまた、ｐｃ粉末と練
和液との混合方法は特に限定されるものではなく、公知
の混合機を用いた混合方法が制限なく採用される。例え
ば、播潰機、ボールミル、ニーダ−、ミキサー等の混合
機を用いる方法が一般的である。In the present invention, the powder-liquid ratio of the PC powder and the kneading liquid may be determined as appropriate to obtain a suitable viscosity depending on the application. Generally, the viscosity of the resulting paste is determined by the method of mixing the PC powder and the kneading liquid, and there are no particular limitations on the mixing method, and any mixing method using a known mixer may be employed without any restriction. For example, a method using a mixer such as a crusher, ball mill, kneader, mixer, etc. is common.
また、本発明のペーストは必要に応じて、硬化性に著し
い悪影響を与えない範囲で、他の成分を添加することが
できる。例えば、Ｘ線造影性を持たせるために、ジルコ
ニア、硫酸バリウム、ストロンチウムガラス、酸化亜鉛
、ヨードホルム等をペースト１００重量部に対して５〜
３０重量部添加するのが好適である。特に、ジルコニア
は他の成分と比較してＸ線造影性が高く、安定性、均一
性が優れ、しかも粉液比が高くなるため最も好適に使用
できる。Furthermore, other components may be added to the paste of the present invention, if necessary, within a range that does not significantly adversely affect the curability. For example, in order to provide X-ray contrast properties, zirconia, barium sulfate, strontium glass, zinc oxide, iodoform, etc. are added to 100 parts by weight of the paste.
It is preferable to add 30 parts by weight. In particular, zirconia can be most preferably used because it has higher X-ray contrast properties than other components, excellent stability and uniformity, and a high powder-liquid ratio.
また、硬化時間及びペースト粘度を調節するために、ヒ
ドロキシアパタイト、シリカ、フッ化カルシウム、チタ
ニア、水酸化カルシウム、アルミナ、リン酸ナトリウム
、リン酸アンモニウム等を添加することができる。Furthermore, in order to adjust the curing time and paste viscosity, hydroxyapatite, silica, calcium fluoride, titania, calcium hydroxide, alumina, sodium phosphate, ammonium phosphate, etc. can be added.
本発明のペースト状硬化性組成物は、保存中あるいは輸
送時等において４０〜５０’Ｃの高温、振動等に曝され
ても粉末と練和液が分離することなく、非常に安定性に
優れ、常に安定した効果を発揮できる。The paste-like curable composition of the present invention has excellent stability, with the powder and kneading solution not separating even when exposed to high temperatures of 40 to 50'C, vibration, etc. during storage or transportation. , can always produce stable effects.
このように本発明のペースト状硬化性組成物は、ワンペ
ーストタイプで作業性が良いうえに、保存安定性が非常
に良く、使用に際しては、水分と反応してヒドロキシア
パタイト硬化体を生成するため、根管充填材、裏層材、
歯周ポケット充填材、抜歯窩充填材等の歯科用修復材と
してのみでなく、骨セメント、骨充填材などの整形外科
用修復材等の用途にも広く使用することができる。As described above, the paste-like curable composition of the present invention is a one-paste type, has good workability, and has very good storage stability. , root canal filling material, lining material,
It can be widely used not only as a dental restorative material such as a periodontal pocket filling material and a tooth extraction socket filling material, but also as an orthopedic restorative material such as a bone cement and a bone filling material.
また、本発明の硬化性組成物の包装形態は特に制限され
るものではないが、シリング、チューブ、その他の容器
に充填する態様が代表的である。Further, the packaging form of the curable composition of the present invention is not particularly limited, but is typically filled in a shilling, tube, or other container.
以下、本発明を更に具体的に説明するため、実施例を示
すが、本発明はこれらの実施例に限定されるものではな
い。尚以下の実施例における粘度測定はハイシェアーレ
オメータ−を用い２３℃で行った。EXAMPLES Hereinafter, in order to explain the present invention more specifically, Examples will be shown, but the present invention is not limited to these Examples. In addition, the viscosity measurement in the following examples was carried out at 23°C using a high shear rheometer.
実施例ｌ
ＣａＨＰＯ４・２ＨｚＯを５００℃で２時間焼成してＴ
ＣａｚＰｚＯｔを得た。この粉末とＣａＣＯ３粉末
を１：２ （モル比）で混合し、空気中１４００℃で２
時間焼成したのち炉外で放冷しＣ４Ｐを得た。このＣ４
ＰとＣａ ＨＰ ＯａをＣａ／Ｐ原子比が１．６７とな
るよう混合粉砕した後２００メツシユのふるいを通し、
リン酸カルシウム混合粉末を得た。Example 1 CaHPO4.2HzO was calcined at 500°C for 2 hours to
CazPzOt was obtained. This powder and CaCO3 powder were mixed at a ratio of 1:2 (molar ratio), and
After firing for an hour, the product was allowed to cool outside the furnace to obtain C4P. This C4
After mixing and pulverizing P and Ca HP Oa so that the Ca/P atomic ratio was 1.67, the mixture was passed through a 200 mesh sieve.
A calcium phosphate mixed powder was obtained.
一方、液状ポリエチレングリコールとして和光純薬製ポ
リエチレングリコール４００（平均分子量４００）を用
い、これに対して高分子量ポリエチレンとして和光純薬
製ポリエチレングリコール２０．０００（平均分子量２
０，０００）を１１％添加し、真空ポンプで引きながら
７０℃で２時間攪拌混合を行い、室温まで冷却してポリ
エチレングリコール混合物を得た。On the other hand, Wako Pure Chemical's polyethylene glycol 400 (average molecular weight 400) was used as the liquid polyethylene glycol, whereas Wako Pure Chemical's polyethylene glycol 20.000 (average molecular weight 2) was used as the high molecular weight polyethylene.
0,000) was added in an amount of 11%, stirring and mixing was performed at 70° C. for 2 hours while pulling with a vacuum pump, and the mixture was cooled to room temperature to obtain a polyethylene glycol mixture.
上記リン酸カルシウム混合物とポリエチレングリコール
混合物を粉液比２．５（重量比）の割合で混合練和し、
ペースト状とした。このペースト粘度は２８０ポイズで
あった。このペーストを内径２０ｍｍφ高さ３０ｍｍの
ポリエチレン製密閉容器の上まで入れ５０℃に保った恒
温器中に３ケ月間保存した。このペーストは液と粉の分
離は全く見られず容器上部と下部のペースト粘度はそれ
ぞれ２７９ポイズと２７８ポイズであり保存安定性は非
常に良好であった。Mixing and kneading the above calcium phosphate mixture and polyethylene glycol mixture at a powder/liquid ratio of 2.5 (weight ratio),
It was made into a paste. The viscosity of this paste was 280 poise. This paste was placed up to the top of a polyethylene airtight container with an inner diameter of 20 mm and a height of 30 mm and stored in a constant temperature oven maintained at 50° C. for 3 months. This paste showed no separation of liquid and powder at all, and the paste viscosities at the top and bottom of the container were 279 poise and 278 poise, respectively, and the storage stability was very good.
また上記密閉容器に入れたペーストとパイプレーク−（
６Ｌ社製 ジ−シーパイブレーク−Ｒ−■）で１時間振
動をかけたが、分離は全く見られず容器上部″と下部の
粘度はそれぞれ２８０ポイズと２７９ボイズであり、振
動に対する安定性も良好であった。In addition, the paste and pipe lake in the above airtight container (
Vibration was applied for 1 hour using a GC Pie Break-R-■ (manufactured by 6L), but no separation was observed, and the viscosity at the top and bottom of the container was 280 poise and 279 poise, respectively, indicating stability against vibration. It was good.
またこのペーストを直径６ｍｍ、高さ１２ｍｍの円筒型
の全型に流し込み、両面を水浸透性のフィルム（細孔径
０．４５μｍ）でおおい、３７℃の水中に浸漬した。４
８時間後に取り出した硬化体はＸ線回折図からヒドロキ
シアパタイトであることを確認した。又、この硬化体の
圧縮強度は９７ｋｇ／−であった。Further, this paste was poured into a cylindrical mold with a diameter of 6 mm and a height of 12 mm, both sides of which were covered with a water-permeable film (pore diameter: 0.45 μm), and immersed in water at 37°C. 4
The cured product taken out after 8 hours was confirmed to be hydroxyapatite from an X-ray diffraction diagram. Moreover, the compressive strength of this cured product was 97 kg/-.
実施例２、比較例１
実施例１において、ポリエチレングリコール２００００
の添加量及び粉液比を変えて同様な保存安定性試験を行
った。初期の粘度と比較して３ヶ月後及び振動をかけた
後の粘度が±２％以内の変動であれば、実用上全つく問
題がな（、保存安定性は良好である。結果を表１に示す
。又比較例としてポリエチレングリコール２０．０００
を添加しない場合の結果を表１に示す。Example 2, Comparative Example 1 In Example 1, polyethylene glycol 20000
A similar storage stability test was conducted by changing the amount of addition and powder/liquid ratio. If the viscosity changes within ±2% after 3 months and after vibration compared to the initial viscosity, there is no practical problem (storage stability is good.The results are shown in Table 1). As a comparative example, polyethylene glycol 20.000
Table 1 shows the results when no addition of .
また、各実施例について上記保存安定性試験後、実施例
１と同様にして硬化体を得たところ、同様にヒドロキシ
アパタイトよりなり、充分な強度を有していることが確
認された。Furthermore, after the above-mentioned storage stability test for each example, a cured product was obtained in the same manner as in Example 1, and it was confirmed that it was also made of hydroxyapatite and had sufficient strength.
実施例３、比較例２．３
実施例１においてポリエチレングリコール２０．０００
の代わりに種々の分子量のポリエチレングリコールを添
加して保存安定性を調べた。結果を表２に示す。Example 3, Comparative Example 2.3 In Example 1, polyethylene glycol 20.000
Instead, polyethylene glycols of various molecular weights were added to investigate storage stability. The results are shown in Table 2.
また、各実施例について上記保存安定性試験後、実施例
１と同様にして硬化体を得たところ、同様にヒドロキシ
アパタイトよりなり、充分な強度を有していることが確
認された。Furthermore, after the above-mentioned storage stability test for each example, a cured product was obtained in the same manner as in Example 1, and it was confirmed that it was also made of hydroxyapatite and had sufficient strength.
実施例４
実施例１においてリン酸カルシウム混合粉体のかわりに
リン酸四カルシウム粉末単独、α−リン酸三カルシウム
粉末単独又はリン酸四カルシウム粉末と他のリン酸カル
シウム粉末とをＣａ／Ｐ原子比が１．６７となるように
混合粉体を用いて保存安定性を測定した。結果を表３に
示す。Example 4 In Example 1, instead of the calcium phosphate mixed powder, tetracalcium phosphate powder alone, α-tricalcium phosphate powder alone, or tetracalcium phosphate powder and other calcium phosphate powder were used with a Ca/P atomic ratio of 1. The storage stability was measured using a mixed powder so that the ratio was 67. The results are shown in Table 3.
また、各実施例について上記保存安定性試験後、実施例
１と同様にして硬化体を得たところ、同様にヒドロキシ
アパタイトよりなり、充分な強度を有していることが確
認された。Furthermore, after the above-mentioned storage stability test for each example, a cured product was obtained in the same manner as in Example 1, and it was confirmed that it was also made of hydroxyapatite and had sufficient strength.
Claims (1)
はリン酸四カルシウムとＣａ／Ｐ原子比が１．６７未満
のリン酸カルシウムとの混合物、（ｉｉ）室温で液状の
ポリエチレングリコール及び（ｉｉｉ）該液状ポリエチ
レングリコールに対して１〜２０重量％の分子量１００
０以上の高分子量ポリエチレングリコールよりなるペー
スト状硬化性組成物。(i) α-tricalcium phosphate, tetracalcium phosphate or a mixture of tetracalcium phosphate and calcium phosphate having a Ca/P atomic ratio of less than 1.67, (ii) polyethylene glycol that is liquid at room temperature, and (iii) the 1 to 20% by weight of liquid polyethylene glycol with a molecular weight of 100
A paste-like curable composition comprising a high molecular weight polyethylene glycol of 0 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150248A JPH01320251A (en) | 1988-06-20 | 1988-06-20 | Pasty hardenable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150248A JPH01320251A (en) | 1988-06-20 | 1988-06-20 | Pasty hardenable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01320251A true JPH01320251A (en) | 1989-12-26 |
| JPH0559859B2 JPH0559859B2 (en) | 1993-09-01 |
Family
ID=15492797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63150248A Granted JPH01320251A (en) | 1988-06-20 | 1988-06-20 | Pasty hardenable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01320251A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105170A1 (en) * | 2004-04-27 | 2005-11-10 | Kyphon Inc. | Bone substitute compositions and method of use |
| EP1742648A2 (en) * | 2004-04-15 | 2007-01-17 | Etex Corporation | Delayed-setting calcium phosphate pastes |
| US9089625B2 (en) | 2005-08-29 | 2015-07-28 | Kyphon Sarl | Bone cement composition and method of making the same |
-
1988
- 1988-06-20 JP JP63150248A patent/JPH01320251A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1742648A2 (en) * | 2004-04-15 | 2007-01-17 | Etex Corporation | Delayed-setting calcium phosphate pastes |
| JP2007533376A (en) * | 2004-04-15 | 2007-11-22 | エテックス コーポレーション | Delayed solidification calcium phosphate paste |
| EP1742648A4 (en) * | 2004-04-15 | 2009-03-04 | Etex Corp | Delayed-setting calcium phosphate pastes |
| WO2005105170A1 (en) * | 2004-04-27 | 2005-11-10 | Kyphon Inc. | Bone substitute compositions and method of use |
| US9089625B2 (en) | 2005-08-29 | 2015-07-28 | Kyphon Sarl | Bone cement composition and method of making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0559859B2 (en) | 1993-09-01 |
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