JPH0638992A - Material for treatment of paradental disease - Google Patents
Material for treatment of paradental diseaseInfo
- Publication number
- JPH0638992A JPH0638992A JP4207148A JP20714892A JPH0638992A JP H0638992 A JPH0638992 A JP H0638992A JP 4207148 A JP4207148 A JP 4207148A JP 20714892 A JP20714892 A JP 20714892A JP H0638992 A JPH0638992 A JP H0638992A
- Authority
- JP
- Japan
- Prior art keywords
- lactic acid
- copolymer
- membrane
- polymer
- present
- 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
- 239000000463 material Substances 0.000 title claims abstract description 67
- 201000010099 disease Diseases 0.000 title abstract description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title abstract description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 44
- 239000004310 lactic acid Substances 0.000 claims abstract description 44
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000013769 triethyl citrate Nutrition 0.000 claims abstract description 21
- 239000001069 triethyl citrate Substances 0.000 claims abstract description 21
- 208000028169 periodontal disease Diseases 0.000 claims description 19
- 239000000470 constituent Substances 0.000 claims description 4
- 230000003239 periodontal effect Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 40
- 229960000448 lactic acid Drugs 0.000 description 38
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 8
- 229940107698 malachite green Drugs 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000001727 in vivo Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 210000002919 epithelial cell Anatomy 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009545 invasion Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000001225 therapeutic effect Effects 0.000 description 4
- 229960001005 tuberculin Drugs 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 210000004195 gingiva Anatomy 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- LCSKNASZPVZHEG-UHFFFAOYSA-N 3,6-dimethyl-1,4-dioxane-2,5-dione;1,4-dioxane-2,5-dione Chemical group O=C1COC(=O)CO1.CC1OC(=O)C(C)OC1=O LCSKNASZPVZHEG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 210000002379 periodontal ligament Anatomy 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XBBVURRQGJPTHH-DKWTVANSSA-N 2-hydroxyacetic acid;(2s)-2-hydroxypropanoic acid Chemical compound OCC(O)=O.C[C@H](O)C(O)=O XBBVURRQGJPTHH-DKWTVANSSA-N 0.000 description 1
- 102000007469 Actins Human genes 0.000 description 1
- 108010085238 Actins Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 241000483403 Lacanobia suasa Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005210 cementogenesis Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Dental Preparations (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は歯周病治療用素材に関
し、殊に歯周疾患の外科的処置治療及びインプラント治
療時に行う骨増大術に際して有用なる素材を提供するこ
とを目的とするものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for treating periodontal disease, and particularly to provide a material useful for bone augmentation performed during surgical treatment and implant treatment of periodontal disease. is there.
【０００２】[0002]
【従来の技術】歯周疾患により破壊された歯周組織の良
好な再生を行なう歯周外科処置方法については、従来よ
り歯根面の歯根膜由来細胞の増殖を促進し、上皮細胞、
歯肉由来細胞あるいは骨由来細胞の侵入を抑制すること
が有効であることが知られている(Milcherら,J. Period
ontol., 47,256(1976))。このことから、その処置療方
法として、ミリポアフィルター(MILLIPORE FILTER,ミリ
ポア社商品名)によって、歯根面への上皮細胞等の侵入
を抑制し、歯根膜細胞の増殖に必要な空間を形成させる
方法がＧＴＲ法(Guided Tissue Regeneration法)として
知られている(Nymanら,J. Clin. Periodontol.,9,290(1
982))。また、この方法の臨床への応用例として、生体
内で非分解性である多孔性ポリテトラフルオロエチレン
膜(コ゛ア テックス膜,ゴア社商品名)が知られている。しかし
ながら、このＧＴＲ法は術式的に熟練が必要であり、ま
た一定期間後には再び術部の外科処置を行ない、術部に
埋入した膜を摘出する必要があるため、患部周辺への損
傷を生起し易い。このようなことから生体内へ埋入後に
於て再手術の必要がない、生体内分解性を有する膜材料
が所望されている。2. Description of the Related Art A periodontal surgical treatment method for favorably regenerating periodontal tissue destroyed by periodontal disease is conventionally known to promote growth of periodontal ligament-derived cells on the root surface, epithelial cells,
It is known that it is effective to suppress the invasion of gingiva-derived cells or bone-derived cells (Milcher et al., J. Period.
ontol., 47 , 256 (1976)). From this, as a treatment and treatment method, there is a method of suppressing the invasion of epithelial cells and the like to the tooth root surface by Millipore filter (MILLIPORE FILTER, trade name of Millipore Company) and forming a space necessary for proliferation of periodontal ligament cells. It is known as the GTR method (Guided Tissue Regeneration method) (Nyman et al., J. Clin. Periodontol., 9 , 290 (1
982)). Further, as a clinical application example of this method, a porous polytetrafluoroethylene membrane (Goretex membrane, trade name of Gore Co.) which is non-degradable in vivo is known. However, this GTR method requires operative skill, and after a certain period of time, it is necessary to perform surgical treatment on the surgical site again and to remove the membrane embedded in the surgical site, resulting in damage to the affected area. It is easy to cause Therefore, there is a demand for a biodegradable membrane material that does not require re-operation after being implanted in a living body.
【０００３】この生体内で分解性を有する膜材料に関し
ては、天然高分子であるコラーゲン膜あるいは合成高分
子の脂肪族ポリエステルである乳酸系重合体膜が知られ
ている。しかしながら、コラーゲン膜はその分解が生体
内酵素による酵素分解によって進行することから分解速
度が一定せず、またコラーゲン中に残存しているテロペ
プタイドによって、生体に対し組織反応を生じる問題が
ある。このことから、その分解がエステル結合の加水分
解が主反応であって、生体内分解性に定常性があり、ま
た分解生成物も一般に代謝系に存在する成分となる乳酸
系重合体の応用が最近では主流となっている。As the membrane material which is degradable in vivo, a collagen membrane which is a natural polymer or a lactic acid polymer membrane which is an aliphatic polyester of a synthetic polymer is known. However, there is a problem that the decomposition rate of the collagen film is not constant because the decomposition proceeds by the enzymatic decomposition by the enzyme in the living body, and the telopeptide remaining in the collagen causes a tissue reaction to the living body. From this, the hydrolysis is mainly the hydrolysis of ester bond, there is a constant in vivo degradability, and the degradation products can be applied to the lactic acid-based polymer, which is a component that generally exists in the metabolic system. It has become mainstream these days.
【０００４】このような乳酸系重合体を応用した材料と
して、L-乳酸重合体膜(Magnussonら,J. Periodontol.,5
9,1(1988))、100μmの孔を有する乳酸-グリコール酸共
重合体であるバイクリル メッシュ(Vicryl mesh,Polygl
actin 910,エチコン社商品名)(Fleisherら,Int. J. Per
io. Rest. Dent., 2,45(1988))、L-乳酸重合体膜及び乳
酸-グリコール酸共重合体膜(久保田ら,日歯周誌,31,870
(1989)）等が知られており、これらの材料を用い保護膜
として使用することが報告されている。更に、特開平2-
63465号公報では、乳酸-グリコール酸共重合体、乳酸-
ε-カプロラクトン共重合体を素材とした材料を使用す
ることが知られている。しかしながら、これら乳酸系重
合体材料は、その膜が硬質であるため歯牙表面へ膜を固
定することが非常に困難であり、歯牙面と膜との密着性
に問題がある。従って、このような膜を装着した場合、
上皮細胞等の侵入や歯肉等の圧迫により、膜の離脱、剥
離等を生じた。As a material to which such a lactic acid-based polymer is applied, an L-lactic acid polymer film (Magnusson et al., J. Periodontol., 5
9 , 1 (1988)), Vicryl mesh, which is a lactic acid-glycolic acid copolymer with 100 μm pores.
actin 910, trade name of Ethicon) (Fleisher et al., Int. J. Per
io. Rest. Dent., 2 , 45 (1988)), L-lactic acid polymer film and lactic acid-glycolic acid copolymer film (Kubota et al., Nihigashou, 31 , 870).
(1989)) and the like, and it has been reported to use these materials as a protective film. Furthermore, JP-A-2-
In 63465, lactic acid-glycolic acid copolymer, lactic acid-
It is known to use a material based on ε-caprolactone copolymer. However, since these lactic acid-based polymer materials have a hard film, it is very difficult to fix the film to the tooth surface, and there is a problem in the adhesion between the tooth surface and the film. Therefore, when wearing such a membrane,
The invasion of epithelial cells or the like and the compression of the gingiva or the like resulted in detachment or peeling of the membrane.
【０００５】このような乳酸重合体からなる保護膜材料
と歯牙面との密着性を改善する方法として、本発明者ら
は乳酸及び／又はグリコール酸の(共)重合体にアルコー
ルを含有せしめた材料が歯周病治療用素材として優れる
ことを見いだし、先に出願を行った(特願平3-237465号)
が、実用面で以下の問題点が明かとなった。即ち、こ
の素材を軟化するために使用時に加温するが、アルコー
ル含有物の加温を使用者が好まないこと。作業上、更
に柔軟性があった方が好ましいことアルコールの揮散
により素材の貯蔵安定性が必ずしも充分でないこと。As a method for improving the adhesion between the protective film material composed of such a lactic acid polymer and the tooth surface, the present inventors have made a (co) polymer of lactic acid and / or glycolic acid contain alcohol. We found that the material is excellent as a material for treatment of periodontal disease, and filed an application first (Japanese Patent Application No. 3-237465).
However, the following problems became clear in terms of practical use. That is, the material is heated to soften it at the time of use, but the user does not like to heat the alcohol-containing material. It is preferable that it is more flexible in terms of work. Storage stability of the material is not always sufficient due to volatilization of alcohol.
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発者らは更
に検討を重ね、柔軟性に優れ、貯蔵安定性も良く、しか
も上皮細胞等の侵入や歯肉等の圧迫により膜の離脱、剥
離が生じない密着性に優れた歯周病治療用素材を得るべ
く鋭意研究を重ねた結果、クエン酸トリエチルを乳酸重
合体又は乳酸とグリコール酸との共重合体に含有させた
ものが優れた歯周病治療素材となることを見い出し本発
明に到達したものである。Therefore, the present inventors have further studied, and have excellent flexibility and good storage stability, and further, the detachment and peeling of the membrane due to the invasion of epithelial cells and the like and the compression of the gingiva and the like can be prevented. As a result of intensive studies to obtain a material for periodontal disease treatment which has excellent adhesion, it has been found that those containing triethyl citrate in a lactic acid polymer or a copolymer of lactic acid and glycolic acid are excellent in periodontal disease. The present invention has been achieved by finding that it can be used as a disease treatment material.
【０００７】[0007]
【課題を解決するための手段】即ち本発明は、主構成成
分として、乳酸重合体又は乳酸とグリコール酸との共重
合体にクエン酸トリエチルを含有せしめた成分からなる
歯周病治療用素材に関する。Means for Solving the Problems That is, the present invention relates to a material for treating periodontal disease, which comprises, as a main constituent, a lactic acid polymer or a copolymer of lactic acid and glycolic acid containing triethyl citrate. .
【０００８】[0008]
【作用】本発明の素材は、主構成成分として乳酸重合体
又は乳酸とグリコール酸との共重合体にクエン酸トリエ
チルを含有せしめた素材である。本発明の素材は、乳酸
系重合体からなる多孔性分解性膜、即ち乳酸及び／叉は
グリコール酸の共重合体からなる膜素材と歯牙との間に
充填して使用することにより、生体内分解性膜の離脱、
剥離を生じず、その密着性を改善し、以て歯周組織を良
好に再生することを目的とする。The material of the present invention is a material in which triethyl citrate is contained in a lactic acid polymer or a copolymer of lactic acid and glycolic acid as a main constituent. INDUSTRIAL APPLICABILITY The material of the present invention can be used in vivo by filling it between a tooth and a porous degradable film made of a lactic acid-based polymer, that is, a film material made of a copolymer of lactic acid and / or glycolic acid. Detachment of degradable membrane,
The purpose of the present invention is not to cause peeling and to improve the adhesiveness thereof, thereby favorably regenerating the periodontal tissue.
【０００９】この素材の製造に使用する原料である、乳
酸重合体又は乳酸とグリコール酸との共重合体に関して
は、DL-乳酸の重合体、L-乳酸-グリコール酸の共重合
体、DL-乳酸-グリコール酸の共重合体を使用する。また
これら原料の内、乳酸とグリコール酸との共重合体につ
いては、その組成はL-乳酸-グリコール酸の共重合体の
場合には、L-乳酸共重合体のL-乳酸含量は20〜80モル
%、DL-乳酸-グリコール酸の共重合体の場合には、DL-乳
酸含量は20モル％以上の範囲のものを使用する。Regarding the lactic acid polymer or the copolymer of lactic acid and glycolic acid, which is the raw material used in the production of this material, a polymer of DL-lactic acid, a copolymer of L-lactic acid-glycolic acid, DL- A lactic acid-glycolic acid copolymer is used. Further, among these raw materials, for the copolymer of lactic acid and glycolic acid, the composition is L-lactic acid-in the case of a glycolic acid copolymer, the L-lactic acid content of the L-lactic acid copolymer is 20 to 80 mol
%, In the case of a DL-lactic acid-glycolic acid copolymer, a DL-lactic acid content of 20 mol% or more is used.
【００１０】これらの乳酸重合体又は乳酸とグリコール
酸との共重合体は、公知のいずれの方法で製造したもの
であってもよい。例えば、乳酸、グリコール酸を酸化亜
鉛等の触媒の存在下でオリゴマーから環状二量体を得た
後、これをジエチル亜鉛、塩化スズ等の触媒存在下で開
環重合を行なうことにより得ることができる。また、本
発明で使用する乳酸重合体又は乳酸とグリコール酸との
共重合体の分子量に関しては、その数平均分子量が10,0
00〜90,000のものを使用する。即ち、分子量がこの範囲
の共重合体を使用することにより、これに後述するクエ
ン酸トリエチルを含有させた場合に、本発明の最も優れ
た歯周病用治療素材を得ることができる。本発明歯周病
治療用素材は、前述のような乳酸系重合体からなる生体
内分解性膜と歯牙との間隙に充填されるものであること
から、その特性として適度の粘弾性と曳糸性が要求さ
れ、ゴム状で或いは曳糸性を有することが要求され、こ
の特性はその共重合体の分子量に関係する。These lactic acid polymers or copolymers of lactic acid and glycolic acid may be produced by any known method. For example, lactic acid or glycolic acid can be obtained by obtaining a cyclic dimer from an oligomer in the presence of a catalyst such as zinc oxide, and then subjecting this to ring-opening polymerization in the presence of a catalyst such as diethylzinc or tin chloride. it can. Regarding the molecular weight of the lactic acid polymer or the copolymer of lactic acid and glycolic acid used in the present invention, the number average molecular weight is 10,0.
Use from 00 to 90,000. That is, by using a copolymer having a molecular weight in this range, the most excellent therapeutic material for periodontal disease of the present invention can be obtained when it contains triethyl citrate described later. Since the material for treating periodontal disease of the present invention is to be filled in the gap between the biodegradable film made of the lactic acid-based polymer and the tooth as described above, the properties thereof are appropriate viscoelasticity and stringiness. Property is required, it is required to be rubbery or to have spinnability, and this property is related to the molecular weight of the copolymer.
【００１１】従って、その分子量が10,000を下廻ると、
得られる歯周病用治療素材は室温で流動性のものとな
り、生体内分解性膜と歯牙の間隙から流出することか
ら、その使用が困難となる。またpH7.4のリン酸緩衝液
に37℃、24時間の浸漬により体積が2倍に膨潤してしま
う物性を示し、これは生体内において、体液によって膨
張し強度が下がることを意味する。反対に、共重合体の
分子量が90,000を上廻ると、得られる歯周病用治療素材
は硬く、生体内分解性や付着性が悪くなり好ましくな
い。Therefore, when the molecular weight is less than 10,000,
The resulting therapeutic material for periodontal disease becomes fluid at room temperature and flows out from the gap between the biodegradable membrane and the tooth, which makes its use difficult. In addition, it shows the physical property that the volume swells twice when it is immersed in a phosphate buffer of pH 7.4 at 37 ° C for 24 hours, which means that in vivo, it expands due to body fluid and its strength decreases. On the other hand, if the molecular weight of the copolymer exceeds 90,000, the resulting therapeutic material for periodontal disease will be hard, and its biodegradability and adhesiveness will be poor, such being undesirable.
【００１２】これらの原料を使用し、本発明の主構成成
分となる乳酸重合体又は乳酸とグリコール酸との共重合
体にクエン酸トリエチルを含有せしめた成分からなる歯
周病用治療素材を製造する方法は次の通りである。先
ず、乳酸重合体又は乳酸とグリコール酸との共重合体を
150μm程度以下に粉砕または裁断する。そして、それを
塩化メチレン又はクロロホルムやアセトン等ポリマーが
溶解する溶媒に溶解させる。次に、この溶液にクエン酸
トリエチルを乳酸重合体又は乳酸とグリコール酸との共
重合体に対して1/2倍量程度添加し、室温〜70℃程度の
温度で約1時間攪拌分散させる。溶媒の一部が揮発し、
クエン酸トリエチルが乳酸重合体又は乳酸とグリコール
酸との共重合体に十分に均一化した状態になったところ
で室温〜70℃で真空乾燥する。また有機溶媒を用いず乳
酸重合体又は乳酸とグリコール酸との共重合体を100〜1
50℃に加温し軟化した後、クエン酸トリエチルを攪拌分
散させることもできる。この場合に於てクエン酸トリエ
チル含量は、乳酸共重合体又は乳酸とグリコール酸の共
重合体に対し10〜40重量％の範囲であることが必要であ
って、この範囲を逸脱するクエン酸トリエチル含量で
は、本発明の優れた歯周病用治療素材を得ることが困難
となる。即ち、クエン酸トリエチル含量が10重量％を下
廻ると、素材が軟化せず、生体内分解性膜への付着性が
低下し、生体内分解性膜と歯牙との間に隙を生じる。ま
た反対に、クエン酸トリエチル含量が40重量％を上廻る
と、素材が体液等の水分により溶解することから好まし
くない。Using these raw materials, a therapeutic material for periodontal disease comprising a lactic acid polymer or a copolymer of lactic acid and glycolic acid, which is the main constituent of the present invention, containing triethyl citrate is produced. The method of doing is as follows. First, a lactic acid polymer or a copolymer of lactic acid and glycolic acid is used.
Grind or cut to 150 μm or less. Then, it is dissolved in a solvent in which the polymer is dissolved such as methylene chloride or chloroform or acetone. Next, triethyl citrate is added to this solution in an amount about 1/2 times that of the lactic acid polymer or the copolymer of lactic acid and glycolic acid, and the mixture is stirred and dispersed at a temperature of room temperature to 70 ° C. for about 1 hour. Part of the solvent volatilizes,
When triethyl citrate is sufficiently homogenized with the lactic acid polymer or the copolymer of lactic acid and glycolic acid, it is vacuum dried at room temperature to 70 ° C. In addition, lactic acid polymer or a copolymer of lactic acid and glycolic acid was used in an amount of 100 to 1 without using an organic solvent.
After heating to 50 ° C. to soften it, triethyl citrate can be dispersed by stirring. In this case, the triethyl citrate content needs to be in the range of 10 to 40% by weight with respect to the lactic acid copolymer or the lactic acid / glycolic acid copolymer, and the triethyl citrate content outside this range is required. With the content, it becomes difficult to obtain the excellent material for periodontal disease treatment of the present invention. That is, when the content of triethyl citrate is less than 10% by weight, the material is not softened and the adhesion to the biodegradable film is lowered, and a gap is generated between the biodegradable film and the tooth. On the other hand, if the content of triethyl citrate exceeds 40% by weight, the raw material will be dissolved by water such as body fluid, which is not preferable.
【００１３】このようにして得られる本発明素材の使用
方法としては、予め生体内分解性膜にこれを付着させ、
ローラー等によってこれを均一に圧延し歯牙と固定して
もよいし、或は予め本発明の素材を歯牙に付着させ、生
体内分解性膜を固定してもよい。また、生体内分解性膜
と歯牙を固定させ、その間隙にこの素材を充填してもよ
い。尚、これらの方法を行う際に、本発明の素材中に抗
菌剤、経口防腐剤、抗生物質、局所麻酔剤あるいは生理
活性物質等を予め混合しておくことも可能である。The method of using the material of the present invention thus obtained is to attach it to a biodegradable membrane in advance,
This may be uniformly rolled by a roller or the like and fixed to the tooth, or the material of the present invention may be previously attached to the tooth and the biodegradable film may be fixed. Alternatively, the biodegradable membrane and the tooth may be fixed and the gap may be filled with this material. When carrying out these methods, it is possible to previously mix an antibacterial agent, an oral antiseptic, an antibiotic, a local anesthetic, a physiologically active substance or the like in the material of the present invention.
【００１４】[0014]
【実施例】以下に本発明の実施例を掲げ更に説明を行な
うが、本発明はこれらに限定されるものではない。ま
た、本発明実施例に於て％は特に断らない限り全て重量
％を示す。The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited thereto. In the examples of the present invention, all percentages are by weight unless otherwise specified.
【００１５】（実施例 1）塩化メチレン（関東化学(株)
製試薬）400mlに粉砕したD,L-乳酸重合体（数平均分子
量 27000）22gを加え室温で攪拌溶解させた。これにク
エン酸トリエチル（関東化学(株)製試薬）12gを添加
し、40℃に加温して混合した。重合体濃度が塩化メチレ
ンの揮散による重量変化により約10%になったところで
これをテフロンフィルム上に延伸させ、70℃で減圧乾燥
し本発明の素材を得た。尚、本発明の素材中のクエン酸
トリエチル含量は31%と求められた。(Example 1) Methylene chloride (Kanto Chemical Co., Inc.)
22 g of D, L-lactic acid polymer (number average molecular weight 27,000) pulverized in 400 ml of reagent) was added and dissolved with stirring at room temperature. To this, 12 g of triethyl citrate (Kanto Chemical Co., Inc. reagent) was added, and the mixture was heated to 40 ° C. and mixed. When the polymer concentration became about 10% due to the weight change due to volatilization of methylene chloride, this was stretched on a Teflon film and dried under reduced pressure at 70 ° C to obtain the material of the present invention. The content of triethyl citrate in the material of the present invention was calculated to be 31%.
【００１６】本発明の素材をツベルクリン用1ml容シリ
ンジ（テルモ社製）に充填し、これをドライヤーで約60
℃に加温軟化させ、別に製造したL-乳酸重合体（数平均
分子量 26000）からなる多孔性生体内分解性膜10mm×15
mm×150μm の片面端にシリンジを押し付けながらピス
トンを押し、1.5mm幅で付着させた。本発明の素材が付
着した多孔性生体内分解性膜をポリエチレン袋に入れ50
℃の温水に漬ける。5分間加温した後軟化させ付着部分
の厚みを均一化した。次いで膜からはみでた部分の素材
を切断した。The material of the present invention was filled in a 1 ml volume syringe for tuberculin (made by Terumo Corp.), and this was dried with a dryer to about 60
Porous biodegradable membrane 10 mm x 15 made of L-lactic acid polymer (number average molecular weight 26000) that was separately softened by heating to ℃
While pushing the syringe against the one-sided edge of mm × 150 μm, the piston was pushed to attach it with a width of 1.5 mm. The porous biodegradable membrane to which the material of the present invention is attached is put in a polyethylene bag 50
Soak in warm water at ℃. After heating for 5 minutes, it was softened to make the thickness of the adhered portion uniform. Then, the raw material of the portion protruding from the film was cut.
【００１７】この本発明の素材を付着させた多孔性生体
内分解性膜を用い、雑種成犬の歯牙の標本を使用して素
材の性能評価を行った。評価方法は雑種成犬の歯牙の歯
根面を周着するように上記の膜で被覆した後、この周囲
を縫合糸で結び付けた。この部分に1％マラカイトグリ
ーン水溶液をスポイトで100ml滴下し、3時間後に膜を取
り外した結果、多孔性生体内分解性膜で覆われた部分に
はマラカイトグリーンの着色は全く見られず、本発明の
素材による膜の固定は良好に成されていた。Using the porous biodegradable membrane to which the material of the present invention is adhered, the performance of the material was evaluated using a tooth sample of a hybrid dog. As the evaluation method, the root surface of the tooth of a hybrid dog was covered with the above-mentioned film so as to lap it, and the periphery was tied with a suture. 100 ml of a 1% malachite green aqueous solution was dropped into this portion with a dropper, and the membrane was removed after 3 hours. As a result, no coloring of malachite green was observed in the portion covered with the porous biodegradable membrane. Fixing of the membrane with the material of 1. was performed well.
【００１８】（比較例 1）D,L-乳酸重合体(数平均分子
量27000)をツベルクリン用1ml容シリンジ（テルモ社
製）に充填し、これをドライヤーで約80℃に加温軟化さ
せ、別に製造したL-乳酸重合体（数平均分子量 26000）
からなる多孔性生体内分解性膜10mm×15mm×150μm の
片面端にシリンジを押し付けながらピストンを押し、1.
5mm幅で付着させた。これをポリエチレン袋に入れ80℃
の温水に漬け、5分間加温し軟化させ付着部分の厚みを
均一化した。次いで膜からはみでた部分の素材を切断し
た。Comparative Example 1 D, L-lactic acid polymer (number average molecular weight 27,000) was filled in a 1 ml syringe for tuberculin (manufactured by Terumo Corp.), and this was softened by heating with a dryer to about 80 ° C. Produced L-lactic acid polymer (number average molecular weight 26000)
Porous biodegradable membrane consisting of 10 mm × 15 mm × 150 μm, pushing the piston while pushing the syringe against one side edge, 1.
It was attached with a width of 5 mm. Put this in a polyethylene bag, 80 ℃
It was soaked in warm water and heated for 5 minutes to soften it to make the thickness of the adhered part uniform. Then, the raw material of the portion protruding from the film was cut.
【００１９】この素材を付着させた多孔性生体内分解性
膜を用い、雑種成犬の歯牙の標本を使用して素材の性能
評価を行った。評価方法は雑種成犬の歯牙の歯根面を周
着するように上記の膜で被覆したが歯牙との接着性が悪
く、この部分に1％マラカイトグリーン水溶液をスポイ
トで100ml滴下し、3時間後に膜を取り外した結果、多孔
性生体内分解性膜で覆われた部分にはマラカイトグリー
ンの着色が見らた。このことから膜と歯牙とに間隙が生
じていたことが確認され、本発明の素材を使用した場合
と明らかに相違していた。The performance of the material was evaluated by using a porous biodegradable membrane to which this material was attached and using a tooth sample of a hybrid dog. The evaluation method was to coat the tooth root surface of the hybrid adult dog's tooth with the above-mentioned film, but the adhesion to the tooth was poor, and 100 ml of a 1% malachite green aqueous solution was dropped into this part with a dropper, and after 3 hours As a result of removing the membrane, malachite green coloring was observed in the portion covered with the porous biodegradable membrane. From this, it was confirmed that a gap was formed between the membrane and the tooth, which was clearly different from the case where the material of the present invention was used.
【００２０】（実施例 2）塩化メチレン（関東化学(株)
製試薬）400mlに粉砕したL-乳酸含量が80モル％のL-乳
酸-グリコール酸共重合体（数平均分子量 90000）41gを
加え室温で攪拌溶解させた。これにクエン酸トリエチル
（関東化学(株)製試薬）28gを添加し、40℃に加温して
混合した。重合体濃度が重量変化により約20%になった
ところでこれをテフロンフィルム上に延伸させ、70℃で
減圧乾燥し本発明の素材を得た。尚、本発明の素材中の
クエン酸トリエチル含量は40%と求められた。(Example 2) Methylene chloride (Kanto Chemical Co., Inc.)
(Reagent manufactured by Japan Co., Ltd.) 41 g of L-lactic acid-glycolic acid copolymer (number average molecular weight 90,000) having an L-lactic acid content of 80 mol% crushed into 400 ml was added and dissolved with stirring at room temperature. To this, 28 g of triethyl citrate (Kanto Chemical Co., Inc. reagent) was added, and the mixture was heated to 40 ° C. and mixed. When the polymer concentration reached about 20% due to the weight change, the polymer was stretched on a Teflon film and dried under reduced pressure at 70 ° C. to obtain a material of the present invention. The content of triethyl citrate in the material of the present invention was calculated to be 40%.
【００２１】この素材をツベルクリン用1ml容シリンジ
（テルモ社製）に充填し、これをドライヤーで約60℃に
加温軟化させ、別に製造したL-乳酸-グリコール酸共重
合体膜 （数平均分子量 131000，L-乳酸含量 78モル
％）からなる多孔性生体内分解性膜10mm×15mm×150μm
の片面端にシリンジを押し付けながらピストンを押
し、1.5mm幅で付着させた。This material was filled in a 1 ml syringe for tuberculin (made by Terumo Co., Ltd.) and softened by heating with a dryer to about 60 ° C., and separately manufactured L-lactic acid-glycolic acid copolymer film (number average molecular weight Porous biodegradable membrane consisting of 131000, L-lactic acid content 78 mol%) 10mm × 15mm × 150μm
While pressing the syringe against the one surface end of the, the piston was pressed to attach it with a width of 1.5 mm.
【００２２】この素材を付着させた多孔性生体内分解性
膜を用い、雑種成犬の歯牙の標本を使用して素材の性能
評価を行った。評価方法は雑種成犬の歯牙の歯根面を周
着するように上記の膜で被覆した後、この周囲を縫合糸
で結び付けた。この部分に1％マラカイトグリーン水溶
液をスポイトで100ml滴下し、3時間後に膜を取り外した
結果、多孔性生体内分解性膜で覆われた部分にはマラカ
イトグリーンの着色は全く見られず、本発明の素材によ
る膜の固定は良好に成されていた。The performance of the material was evaluated by using a porous biodegradable membrane to which the material was attached and using a tooth sample of a hybrid dog. As the evaluation method, the root surface of the tooth of a hybrid dog was covered with the above-mentioned film so as to lap it, and the periphery was tied with a suture. 100 ml of a 1% malachite green aqueous solution was dropped into this portion with a dropper, and the membrane was removed after 3 hours. As a result, no coloring of malachite green was observed in the portion covered with the porous biodegradable membrane. Fixing of the membrane with the material of 1. was performed well.
【００２３】（実施例 3）塩化メチレン（関東化学(株)
製試薬）50mlに粉砕したD,L-乳酸含量が50モル％のD,L-
乳酸-グリコール酸共重合体（数平均分子量 45000）5.1
gを加え室温で攪拌溶解させた。これにクエン酸トリエ
チル（関東化学(株)製試薬）0.57gを添加し、40℃に加
温して混合した。重合体濃度が重量変化により約10%に
なったところでこれをテフロンフィルム上に延伸させ、
70℃で減圧乾燥し本発明の素材を得た。尚、本発明の素
材中のクエン酸トリエチル含量は10％と求められた。(Example 3) Methylene chloride (Kanto Chemical Co., Inc.)
Reagent) 50 ml D, L-D-L-lactic acid content of 50 mol%
Lactic acid-glycolic acid copolymer (number average molecular weight 45,000) 5.1
g was added and dissolved by stirring at room temperature. To this, 0.57 g of triethyl citrate (Kanto Chemical Co., Inc. reagent) was added, and the mixture was heated to 40 ° C. and mixed. At a polymer concentration of about 10% due to weight change, stretch this on a Teflon film,
The material of the present invention was obtained by drying under reduced pressure at 70 ° C. The content of triethyl citrate in the material of the present invention was calculated to be 10%.
【００２４】この素材をツベルクリン用1ml容シリンジ
（テルモ社製）に充填し、これをドライヤーで約60℃に
加温軟化させ、別に製造したD,L-乳酸-グリコール酸共
重合体からなる多孔性生体内分解性膜（数平均分子量 2
51000、D,L-乳酸含量 59モル％）10mm×15mm×150μm
の片面端にシリンジを押し付けながらピストンを押し、
1.5mm幅で付着させた。この素材が付着した多孔性生体
内分解性膜をポリエチレン袋に入れ50℃の温水に漬け、
5分間加温した後付着部分の厚みを温度と水圧によって
均一化した。次いで膜からはみでた部分の素材を切断し
た。This material was filled in a 1 ml syringe for tuberculin (manufactured by Terumo Corp.), softened by heating it to about 60 ° C. with a dryer, and made of a separately produced D, L-lactic acid-glycolic acid copolymer. Biodegradable membrane (number average molecular weight 2
51000, D, L-lactic acid content 59 mol%) 10mm × 15mm × 150μm
While pushing the syringe on one side of the, push the piston,
It was attached with a width of 1.5 mm. Put the porous biodegradable membrane with this material in a polyethylene bag and immerse it in warm water at 50 ℃.
After heating for 5 minutes, the thickness of the adhered portion was made uniform by temperature and water pressure. Then, the raw material of the portion protruding from the film was cut.
【００２５】この素材を付着させた多孔性生体内分解性
膜を用い、雑種成犬の歯牙の標本を使用して素材の性能
評価を行った。評価方法は雑種成犬の歯牙の歯根面を周
着するように上記の膜で被覆した後、この周囲を縫合糸
で結び付けた。この部分に1％マラカイトグリーン水溶
液をスポイトで100ml滴下し、3時間後に膜を取り外した
結果、多孔性生体内分解性膜で覆われた部分にはマラカ
イトグリーンの着色は全く見られず、本発明の素材によ
る膜の固定は良好に成されていた。また、実施例 3で得
られた本発明の素材が付着した生体内分解性膜を下顎 P
3、P4歯に5mmφの骨欠損を形成させた雑種成犬の歯根面
に装着させ、縫合糸であるコーティドバイクリル(coate
d Vicryl，エチコン社製商品名)で縫合糸8週間後に観察
した結果、上皮の侵入は見られず歯冠側へのセメント質
形成と新付着が見られ、膜の固定が良好になされてい
た。Using the porous biodegradable membrane to which this material was adhered, the performance of the material was evaluated using a sample of the teeth of a hybrid dog. As the evaluation method, the root surface of the tooth of a hybrid dog was covered with the above-mentioned film so as to lap it, and the periphery was tied with a suture. 100 ml of a 1% malachite green aqueous solution was dropped into this portion with a dropper, and the membrane was removed after 3 hours. As a result, no coloring of malachite green was observed in the portion covered with the porous biodegradable membrane. Fixing of the membrane with the material of 1. was performed well. In addition, the biodegradable membrane to which the material of the present invention attached in Example 3 was attached was placed on the lower jaw P
3 、 P4 To be attached to the root surface of a hybrid dog with a 5 mmφ bone defect formed on the tooth, and a suede
Observation of the suture with d Vicryl (trade name, manufactured by Ethicon) 8 weeks later revealed that no infiltration of epithelium was observed, cementum formation and new adhesion to the coronal side were observed, and the membrane was well fixed. .
【００２６】[0026]
【発明の効果】本発明の歯周病治療用素材は、従来の素
材よりも柔軟性が高く、あらかじめ生体内分解性膜と付
着させた場合も膜に対する影響はなく、貯蔵安定性が高
い。また、生体組織反応もなく患者への負担も少なくて
すむ特徴を有する。また、生体内分解性膜として使用す
る乳酸系重合体からなる生体内分解性膜との付着性に優
れ、更に、歯牙との親和性が優れることから、生体内分
解性膜と歯牙との密着性に優れ、歯牙との間に隙を生じ
ず生体内に於いて膜の離脱、剥離が生じない特徴をも有
する。従ってこれらの特徴によって、本発明の素材は歯
周疾患により破壊された歯周組織の再生を良好にする場
を形成し、歯周病治療用素材として有用なものである。EFFECTS OF THE INVENTION The material for treating periodontal disease of the present invention has higher flexibility than conventional materials, has no effect on the membrane even when previously attached to a biodegradable membrane, and has high storage stability. In addition, there is a characteristic that there is no reaction in the living tissue and the burden on the patient is small. In addition, it has excellent adhesion to the biodegradable film made of a lactic acid-based polymer used as a biodegradable film, and further has excellent affinity with teeth, so that the adhesion between the biodegradable film and teeth is good. It has excellent properties, and it also has the characteristics that no gap is formed between the teeth and the membrane does not detach or peel off in vivo. Therefore, due to these characteristics, the material of the present invention forms a field for improving the regeneration of periodontal tissue destroyed by periodontal disease, and is useful as a material for treating periodontal disease.
フロントページの続き (72)発明者 岡田 隆雄 兵庫県加古川市平岡町新在家2081−５番地 (72)発明者 永岡 陽一 兵庫県加古川市別府町新野辺1406−１番地Continued Front Page (72) Inventor Takao Okada 2081-5 Shinya, Hiraoka-cho, Kakogawa-shi, Hyogo (72) Inventor Yoichi Nagaoka 1406-1 Shinnobe, Beppu-cho, Kakogawa-shi, Hyogo
Claims (3)
とグリコール酸との共重合体にクエン酸トリエチルを含
有せしめた成分からなる歯周病治療用素材。1. A material for treating periodontal disease, which comprises, as a main constituent, a lactic acid polymer or a copolymer of lactic acid and glycolic acid containing triethyl citrate.
共重合体の数平均分子量が10,000〜90,000の範囲である
請求項１の歯周病治療用素材。2. The material for treating periodontal disease according to claim 1, wherein the lactic acid polymer or the copolymer of lactic acid and glycolic acid has a number average molecular weight in the range of 10,000 to 90,000.
共重合体に対するクエン酸トリエチルの含量が10〜40重
量％の範囲である請求項１の歯周病治療用素材。3. The material for treating periodontal disease according to claim 1, wherein the content of triethyl citrate in the lactic acid polymer or the copolymer of lactic acid and glycolic acid is in the range of 10 to 40% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20714892A JP3217861B2 (en) | 1992-07-10 | 1992-07-10 | Materials for treating periodontal disease |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20714892A JP3217861B2 (en) | 1992-07-10 | 1992-07-10 | Materials for treating periodontal disease |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0638992A true JPH0638992A (en) | 1994-02-15 |
| JP3217861B2 JP3217861B2 (en) | 2001-10-15 |
Family
ID=16535011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20714892A Expired - Fee Related JP3217861B2 (en) | 1992-07-10 | 1992-07-10 | Materials for treating periodontal disease |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3217861B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002020530A (en) * | 2000-07-05 | 2002-01-23 | Toyo Cloth Co Ltd | Biodegradable porous membrane, structural material and method for producing the same |
| CN1317321C (en) * | 2005-04-15 | 2007-05-23 | 浙江工业大学 | Method for plasticizing resin granules of poly lactic acid |
-
1992
- 1992-07-10 JP JP20714892A patent/JP3217861B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002020530A (en) * | 2000-07-05 | 2002-01-23 | Toyo Cloth Co Ltd | Biodegradable porous membrane, structural material and method for producing the same |
| CN1317321C (en) * | 2005-04-15 | 2007-05-23 | 浙江工业大学 | Method for plasticizing resin granules of poly lactic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3217861B2 (en) | 2001-10-15 |
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