EP0944377A1 - Biologically resorbable polymerization products made of binding agent systems which can be hardened by radiation - Google Patents

Biologically resorbable polymerization products made of binding agent systems which can be hardened by radiation

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Publication number
EP0944377A1
EP0944377A1 EP97912224A EP97912224A EP0944377A1 EP 0944377 A1 EP0944377 A1 EP 0944377A1 EP 97912224 A EP97912224 A EP 97912224A EP 97912224 A EP97912224 A EP 97912224A EP 0944377 A1 EP0944377 A1 EP 0944377A1
Authority
EP
European Patent Office
Prior art keywords
polymerization
bioresorbable
polymerization products
tooth
dental
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.)
Withdrawn
Application number
EP97912224A
Other languages
German (de)
French (fr)
Inventor
Robert Wenz
Berthold Nies
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0944377A1 publication Critical patent/EP0944377A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/908—Dental utility

Definitions

  • the invention relates to a process for the preparation of bioresorbable polymerization products, characterized in that monomeric compounds consisting essentially of compositions of the formula I.
  • R 1 , R 2 , R 3 each independently of one another - (CH 2 ) -, -CH (CH 3 ) -, -CH 2 -CH -, -CH 2 -CH 2 -CH -, -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 3 ) -, 1, 2-, 1, 3- or 1, 4-phenylene,
  • R 4 , R 4 , R 4 "each independently of one another H or CH 3 , i, j, k each independently of one another 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and n 0 or 1 mean
  • the invention also relates to a process, characterized in that the compositions of the formula I are polymerized at temperatures between 0 and 80 ° C.
  • Another object of the invention is a process, characterized in that the polymerization of the compositions of the formula I are carried out with the addition of a starter and / or an accelerator.
  • the invention also relates to a bioresorbable polymerization product based on ethylene glycol and / or glycerol oligoester (meth) acrylates, obtainable by one of the processes mentioned.
  • Polymerizable binder systems based on (meth) acrylic acid esters on polyester oligomer chains from hydroxycarboxylic acids are e.g. known from EP 0 085 944 and EP 0 086 401.
  • the object of the invention was to provide bioabsorbable polymers which are easy to produce, in particular those which can be used for the production of bone and denture materials.
  • (meth) acrylic acid esters as monomers for use in dental materials is e.g. described in EP 0 206 074.
  • Prefabricated molded articles (inserts) based on ethylenically polymerizable materials are e.g. disclosed in DE 43 39 399.
  • Other molded articles with a predetermined pore structure based on hydroxylapatite are e.g. described in DE 42 05 969.
  • a method for producing tooth fillings from light-curing plastic is described in DE 40 30 168.
  • Photopolymerizable compositions for dental treatment based on phenylene, diphenylene or bridged phenylene are disclosed in DE 21 26 419.
  • Other photopolymerizable compositions with ketone additives are described in EP 0 090493. It has been found that the compositions of the formula I can be polymerized very easily by irradiation, and the polymer products thus obtained, in addition to their bioresorbability or biodegradability, have very valuable properties in processing products such as dental enamel, tooth inlays or porous moldings.
  • bioresorbable polymerization products based on ethylene glycol and / or glycerol oligoester (meth) acrylates according to claim 4 can be used in dental and bone surgery.
  • the invention accordingly relates to a process for the preparation of bioresorbable polymerization products, characterized in that monomeric compounds, consisting essentially of compositions of the formula I, are polymerized by means of electromagnetic radiation.
  • the radiation used for the polymerization is in the range from 800 nm (near infrared / visible light) to 10 "4 nm ( ⁇ -rays or X-rays).
  • the range of visible and UV light in the range from 800 nm to is particularly preferred 1 nm, very particularly preferred is the range from 800 to 50 nm, whereas another preferred range has wavelengths from 1 to 10 "4 nm.
  • the ethylene glycol or glycero-oligoester (meth) acrylates are preferably formed from one mole of ethylene or glycerol, 2 to 10, in particular 2 to 6 moles of monohydroxy-monocarboxylic acid and 2 to 3, preferably 2 moles of methacrylic acid.
  • Preferred monohydroxy-monocarboxylic acids are glycolic acid, hydroxypropionic acid, hydroxybutyric acid and / or hydroxybenzoic acid, lactic acid is very particularly preferred.
  • preferred compositions of the formula I are the ethylene glycol and / or glyceroligolactide bismethacrylates.
  • the polymerization takes place at temperatures from 0 to 80 ° C., preferably between 10 and 60 ° C., very particularly preferably between 20 and 40 ° C.
  • Initiators can also be added. Suitable initiators are, for example, boron compounds as described in EP 0 085 944.
  • the invention further relates to a tooth enamel based on bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 0.05 to 4% by weight camphorquinone, b) applying the mixture to the tissue or tooth to be lacquered and c ) Polymerization by means of electromagnetic radiation in the range from 50 to 800 nm.
  • the chemical structure of the dental enamel according to the invention is absorbable. For this reason, it is particularly suitable for the treatment of periodontitis, which is characterized by gingival pockets, formation of populated plaques and finally with increasing loss of the periodontal ligament, which represents the connection between the root cement and the alveolar compartment.
  • periodontitis which is characterized by gingival pockets, formation of populated plaques and finally with increasing loss of the periodontal ligament, which represents the connection between the root cement and the alveolar compartment.
  • the loss of this tooth retention apparatus leads to loosening and loss of the tooth.
  • the current status of dental treatment consists of the debridement of the space formed between the alveolar compartment and the tooth root, smoothing of the root surface and sewing in a film or membrane (eg Gore membrane) for the purpose of preventing connective tissue ingrowth from the gingiva in the sense of the controlled Tissue regeneration.
  • a film or membrane eg Gore membrane
  • the dental lacquer according to the invention serves to anchor the film or membrane occlusively in the alveolar compartment or the lacquer is introduced into the defect in the sense of a placeholder for controlled tissue regeneration.
  • a rapidly resorbable material such as a bone seal
  • a rapidly resorbable material can first be introduced into the alveolar compartment and then the dental enamel applied and brought to the polymerization.
  • Antibiotics or disinfectants can be mixed into the tooth enamel to improve the root cement formation by the odontoblasts calcium salts, against bacterial colonization.
  • Another option is to mix in elastase inhibitors.
  • elastase inhibitors In periodontal diseases, high concentrations of elastase originating from polymorphonuclear granulocytes are found in the sulcus fluid. These high elastase concentrations are partly responsible for the fact that tissue of the periodontal tooth holder is degraded and the attachment loss progresses.
  • Sodium monofluorophosphate, amine fluorides and / or other fluorine donors can also be added.
  • Tooth enamel containing amine fluoride or local anesthetics is applied in order to make the tooth necks less sensitive or to harden the tooth necks through the release of amine or other fluorides.
  • these tooth varnishes have a short shelf life on the tooth surface, usually only a few hours.
  • camphorquinone By mixing camphorquinone, the tooth enamel is hardened more quickly.
  • the amounts to be mixed are preferably between 0.05 and 4% by weight camphorquinone, in particular between 0.1 and 0.5% by weight.
  • the polymerization takes place e.g. by irradiation with visible or UV radiation at wavelengths of 800 to 50 nm, preferably between 500 and 300 nm.
  • Dental varnishes with different viscosities can be obtained by admixing, for example, glycero-oligoesters and / or glycero-oligoester (meth) acrylates to ethylene glycol and / or glycero-oligoester (meth) acrylates, which are already mixed with camphorquinone.
  • glycero-oligolactides which are formed from one mole of glycerol and 6 to 14 moles of lactic acid, are preferably admixed to give ethylene glycol oligolactide bismethacrylates.
  • Glycero-oligolactides (1: 8 to 1:12), which consist of one mole of glycerol and 8 to 12 moles of lactic acid, are very particularly preferred as the binders to be mixed.
  • the amounts to be mixed are preferably between 20 and 60% by weight of glycero-oligolactide, in particular between 30 and 50% by weight.
  • the invention further relates to tooth inlays based on initially bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 10 to
  • the inlays according to the invention have no such shrinkage.
  • the inlays can be obtained by mixing ethylene glycol oligoester (meth) acrylate with 10 to 80% by weight of hydroxylapatite, preferably with 20 to 70% by weight.
  • the highly viscous mass before the polymerization is introduced into a dental impression material (negative impression) and cured by ⁇ -radiation with wavelengths ⁇ 10 nm, especially in the range from 1 to 10 ⁇ nm, preferably in the range from 10 "1 to 10 " 3 nm .
  • the corresponding intensities (radiation densities) for the radiation sources to be used are 10 to 60 kGray, preferably 20 to 50 kGray [rem / cm 2 ].
  • the resulting bodies can be machined by sawing or drilling.
  • the inlays obtained in this way can then be introduced into the prepared tooth and, for example, by using a Glue in the bone glue consisting, for example, of ethylene glycol oligolactide bis methacrylate and a starter.
  • the invention furthermore relates to implantable molded articles with an interconnecting pore system based on bioresorbable polymerization products according to claim 4, obtainable a) by introducing the monomeric composition into a porous matrix and b) polymerization by means of electromagnetic radiation ⁇ 10 nm.
  • the forms according to the invention are included as bone substitute material
  • Placeholder function ideally suited, since the trabeculae forming the pore system can serve as a guide for the newly formed bone. After a certain time, the polymer is completely broken down, so that only newly formed bone remains, which can then optimally adapt to the corresponding load directions of the bone.
  • the shaped bodies with interconnecting pore system are produced by using matrices, e.g. Sugar cubes are introduced into a silicone mold and these are then impregnated with the monomeric ethylene glycol and / or glycerol oligoester (meth) acrylate.
  • the monomer is polymerized by irradiation with ⁇ radiation.
  • ⁇ -radiation with wavelengths ⁇ 10 nm is used, particularly in the range from 1 to 10 ⁇ nm, preferably in the range from 10 "1 to 10 " 3 nm.
  • the corresponding radiation sources are used
  • the polymerized sugar cubes can then be processed for further shaping or the sugar can then be removed by treatment with water or alcohol.
  • the invention further relates to the use of bioresorbable polymerization products according to claim 4 for the production of dental lacquers, tooth inlays and / or implantable moldings.
  • ethylene glycol oligolactide bis methacrylate 50 ml is mixed with 1% camphorquinone for 20 minutes with stirring, protected from light, and poured into an amber glass bottle.
  • the mixture is applied to the tooth and with a light pen, e.g. from Kulzer, Translux EC, 200 watts hardened 2 x 30 seconds.
  • the resulting polymer layer on the tooth surface is very strong and mechanically resistant to abrasion.
  • Example 1 For a periodontitis treatment on beagle dogs, highly viscous to plastically deformable "tooth enamel" systems are suitable.
  • the mixture prepared in Example 1 is mixed with 40% by weight glycero-oligolactide (1: 8), which was previously heated to 50 ° C., and mixed.
  • a sugar cube is placed in a silicone mold that is designed so that the edges of the sugar cube are surrounded on all sides by the silicone. is closed, but the top and bottom are left open.
  • a vacuum By applying a vacuum to the underside of the silicone mold, after 5 ml of ethylene glycol oligolactide bismethacrylate has been applied to the top of the sugar cubes, the sugar is sucked into and through the sugar.
  • the sugar cube loaded in this way can be stored at 0 to 4 ° C.
  • the polymerization is carried out by irradiating the material at 25 kGy.
  • the loading technique can also be modified in such a way that the cube sugar enclosed in the silicone mold is first loaded with 3 ml of 60 ° C. hot ethylene glycol oligolactide bis methacrylate, which contains 8% by weight of 9-BBN (borobicyclononan). 5 ml of ethylene glycol oligolactide bis methacrylate are then sucked through.
  • 9-BBN boric acid
  • Another way of loading is by inserting several sugar cubes in an excess of adhesive monomer in a desiccator and applying a vacuum.
  • the polymerized sugar cubes were tested for compressive strength using an Instron testing machine. Moldings in which the sugar matrix was not dissolved out by water or alcohol showed compressive strengths of 30 MPa; in the case of moldings with the matrix released, the compressive strength was 3 MPa.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Polymers & Plastics (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Engineering & Computer Science (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dental Preparations (AREA)

Abstract

The invention relates to a method for producing biologically resorbable polymerization products, characterized in that momomer compounds, mainly consisting of compositions of formula (I), are polymerized by means of electromagnetic radiation. In formula (I) R<1>, R<2>, R<3> mean individually -(CH2)-, -CH(CH3)-, - CH2-CH2-, -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, 1.2-, 1.3-, or 1.4 phenylene; R<4>, R<4'>, R<4''> mean individually - H or CH3; i, j, k mean individually 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and n means 0 or 1. Also described is the use of biologically resorbable polymerization products in the production of tooth enamel, tooth inlays and/or implantable moulded bodies.

Description

Bioresorbierbare Polymerisationsprodukte aus strahlungshärtbaren Bindemittelsystemen Bioresorbable polymerization products from radiation-curable binder systems
Die Erfindung betrifft ein Verfahren zur Herstellung von bioresorbierbaren Polymerisationsprodukten, dadurch gekennzeichnet, daß monomere Verbindungen, im wesentlichen bestehend aus Zusammensetzungen der Formel IThe invention relates to a process for the preparation of bioresorbable polymerization products, characterized in that monomeric compounds consisting essentially of compositions of the formula I.
worin wherein
R1, R2, R3 jeweils unabhängig voneinander -(CH2)-, -CH(CH3)-, -CH2-CH -, -CH2-CH2-CH -, -CH(CH3)-CH2-, -CH2-CH(CH3)-, 1 ,2- , 1 ,3- oder 1 ,4-Phenylen,R 1 , R 2 , R 3 each independently of one another - (CH 2 ) -, -CH (CH 3 ) -, -CH 2 -CH -, -CH 2 -CH 2 -CH -, -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 3 ) -, 1, 2-, 1, 3- or 1, 4-phenylene,
R4, R4 , R4" jeweils unabhängig voneinder H oder CH3, i, j, k jeweils unabängig voneinander 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9 oder 10 und n 0 oder 1 bedeuten,R 4 , R 4 , R 4 "each independently of one another H or CH 3 , i, j, k each independently of one another 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and n 0 or 1 mean
mittels elektromagnetischer Strahlung polymerisiert werden.be polymerized by means of electromagnetic radiation.
Gegenstand der Erfindung ist auch ein Verfahren, dadurch gekennzeich- net, daß die Zusammensetzungen der Formel I bei Temperaturen zwischen 0 und 80 °C polymerisiert werden.The invention also relates to a process, characterized in that the compositions of the formula I are polymerized at temperatures between 0 and 80 ° C.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren, dadurch gekennzeichnet, daß die Polymerisation der Zusammensetzungen der Formel I unter Zusatz eines Starters und/oder eines Beschleunigers durchgeführt werden. Gegenstand der Erfindung ist auch ein bioresorbierbares Polymerisationsprodukt auf Basis von Ethylenglycol- und/oder Glycero-oligoester- (meth)acrylaten, erhältlich nach einem der genannten Verfahren.Another object of the invention is a process, characterized in that the polymerization of the compositions of the formula I are carried out with the addition of a starter and / or an accelerator. The invention also relates to a bioresorbable polymerization product based on ethylene glycol and / or glycerol oligoester (meth) acrylates, obtainable by one of the processes mentioned.
Polymerisierbare Bindemittelsysteme auf Basis von (Meth)acrylsäure- estem an Polyester-Oligomerketten aus Hydroxycarbonsäuren sind z.B. aus der EP 0 085 944 und EP 0 086 401 bekannt.Polymerizable binder systems based on (meth) acrylic acid esters on polyester oligomer chains from hydroxycarboxylic acids are e.g. known from EP 0 085 944 and EP 0 086 401.
Knochenersatzmaterialien und implantierbare Pharmakadepots, die aufBone replacement materials and implantable pharmaceutical depots based on
/trylatkunsts offen basieren, sind seit langem bekannt. Polymermaterialien auf Basis von Acryl- und/oder Methacrylsäureestern haben sich hier aufgrund ihrer Biokompatibilität, ihrer vorzüglichen Festigkeitseigenschaften, ihrer günstigen Eigenschaften bei der Freisetzung eingelagerter pharma- zeutischer Wirkstoffe und nicht zuletzt aufgrund ihrer anwendungsgerechten Verarbeitbarkeit bewährt./ Trylatkunsts based open have been known for a long time. Polymer materials based on acrylic and / or methacrylic acid esters have proven themselves here because of their biocompatibility, their excellent strength properties, their favorable properties when releasing stored pharmaceutical active ingredients, and last but not least because of their processability which is suitable for the application.
Der Erfindung lag die Aufgabe zugrunde, bioresorbierbare Polymere, die leicht herzustellen sind, zur Verfügung zu stellen, insbesondere solche, die zur Herstellung von Knochen- und Zahnersatzmaterialien verwendet werden können.The object of the invention was to provide bioabsorbable polymers which are easy to produce, in particular those which can be used for the production of bone and denture materials.
Die Verwendung von (Meth)acrylsäurestern als Monomere für die Anwendung in Dentalwerkstoffen ist z.B. in der EP 0 206 074 beschrieben. Vorgefertigte Formkörper (Inserts) auf der Basis von ethylenisch polymeri- sierbarer Materialien sind z.B. in der DE 43 39 399 offenbart. Andere Formkörper mit vorbestimmter Porenstruktur auf Hydroxylapatit- basis sind z.B. in der DE 42 05 969 beschrieben. Ein Verfahren zur Herstellung von Zahnfüllungen aus lichthärtendem Kunststoff ist in der DE 40 30 168 beschrieben.The use of (meth) acrylic acid esters as monomers for use in dental materials is e.g. described in EP 0 206 074. Prefabricated molded articles (inserts) based on ethylenically polymerizable materials are e.g. disclosed in DE 43 39 399. Other molded articles with a predetermined pore structure based on hydroxylapatite are e.g. described in DE 42 05 969. A method for producing tooth fillings from light-curing plastic is described in DE 40 30 168.
Photopolymerisierbare Massen für die Zahnbehandlung auf Basis von Phenylen, Diphenylen oder überbrücktem Phenylen sind in der DE 21 26 419 offenbart. Andere photopolymerisierbare Massen mit Ketonzusätzen sind in der EP 0 090493 beschrieben. Es wurde gefunden, daß die Zusammensetzungen der Formel I sehr leicht durch Bestrahlung polymerisiert werden können, und die so erhaltenen Polymerprodukte, neben ihrer Bioresorbierbarkeit bzw. Biodegradationsfähigkeit sehr wertvolle Eigenschaften in Verarbeitungsprodukten wie Zahnlack, Zahn-Inlays oder porösen Formkörpern besitzen.Photopolymerizable compositions for dental treatment based on phenylene, diphenylene or bridged phenylene are disclosed in DE 21 26 419. Other photopolymerizable compositions with ketone additives are described in EP 0 090493. It has been found that the compositions of the formula I can be polymerized very easily by irradiation, and the polymer products thus obtained, in addition to their bioresorbability or biodegradability, have very valuable properties in processing products such as dental enamel, tooth inlays or porous moldings.
Die bioresorbierbaren Polymerisationsprodukte auf Basis von Ethylen- glycol- und/oder Glycero-oligoester-(meth)acrylaten gemäß Anspruch 4 können in der Zahn- und Knochenchirurgie verwendet werden.The bioresorbable polymerization products based on ethylene glycol and / or glycerol oligoester (meth) acrylates according to claim 4 can be used in dental and bone surgery.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung von bioresorbierbaren Polymerisationsprodukten, dadurch gekennzeichnet, daß monomere Verbindungen, im wesentlichen bestehend aus Zusammensetzungen der Formel I mittels elektromagnetischer Strahlung polymerisiert werden.The invention accordingly relates to a process for the preparation of bioresorbable polymerization products, characterized in that monomeric compounds, consisting essentially of compositions of the formula I, are polymerized by means of electromagnetic radiation.
Die zur Polymerisation eingesetzte Strahlung liegt im Bereich von 800 nm (nahes Infrarot/sichtbares Licht) bis zu 10"4 nm (γ-Strahlen bzw. Röntgenstrahlen). Besonders bevorzugt ist der Bereich des sichtbaren und UV- Lichtes im Bereich von 800 nm bis 1 nm, ganz besonders bevorzugt ist hierbei der Bereich von 800 bis 50 nm, wohingegen ein weiterer bevorzugter Bereich Wellenlängen von 1 bis 10"4 nm aufweist.The radiation used for the polymerization is in the range from 800 nm (near infrared / visible light) to 10 "4 nm (γ-rays or X-rays). The range of visible and UV light in the range from 800 nm to is particularly preferred 1 nm, very particularly preferred is the range from 800 to 50 nm, whereas another preferred range has wavelengths from 1 to 10 "4 nm.
Die Ethylenglycol- bzw. Glycero-oligoester-(meth)acrylate sind vorzugsweise aus einem Mol Ethylen oder Glycerin, 2 bis 10, insbesondere 2 bis 6 Mol Monohydroxy-monocarbonsäure und 2 bis 3, vorzugsweise 2 Mol Methacrylsäure, gebildet.The ethylene glycol or glycero-oligoester (meth) acrylates are preferably formed from one mole of ethylene or glycerol, 2 to 10, in particular 2 to 6 moles of monohydroxy-monocarboxylic acid and 2 to 3, preferably 2 moles of methacrylic acid.
Bevorzugte Monohydroxy-monocarbonsäuren sind Glycolsäure, Hydroxy- propionsäure, Hydroxybuttersäure und/oder Hydroxybenzoesäure, ganz besonders bevorzugt ist Milchsäure. Infolgedessen sind bevorzugte Zu- sammensetzungen der Formel I die Ethylenglycol- und/oder Glycero- oligolactid-bismethacrylate.Preferred monohydroxy-monocarboxylic acids are glycolic acid, hydroxypropionic acid, hydroxybutyric acid and / or hydroxybenzoic acid, lactic acid is very particularly preferred. As a result, preferred compositions of the formula I are the ethylene glycol and / or glyceroligolactide bismethacrylates.
Die Polymerisation erfolgt bei Temperaturen von 0 bis 80 °C, vorzugsweise zwischen 10 und 60 °C, ganz besonders bevorzugt zwischen 20 und 40 °C. Es können auch Initiatoren zugesetzt werden. Als geeignete Initiatoren kommen z.B. Borverbindungen, wie in EP 0 085 944 beschrieben, in Frage.The polymerization takes place at temperatures from 0 to 80 ° C., preferably between 10 and 60 ° C., very particularly preferably between 20 and 40 ° C. Initiators can also be added. Suitable initiators are, for example, boron compounds as described in EP 0 085 944.
Gegenstand der Erfindung ist weiterhin ein Zahnlack auf Basis von bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4, erhältlich a) durch Vermischen der monomeren Zusammensetzung mit 0,05 bis 4 Gew. % Campherchinon, b) Aufbringen der Mischung auf das zu lackierende Gewebe oder den Zahn und c) Polymerisation mittels elektromagnetischer Strahlung im Bereich von 50 bis 800 nm.The invention further relates to a tooth enamel based on bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 0.05 to 4% by weight camphorquinone, b) applying the mixture to the tissue or tooth to be lacquered and c ) Polymerization by means of electromagnetic radiation in the range from 50 to 800 nm.
Der erfindungsgemäße Zahnlack ist von seinem chemischen Aufbau her resorbierbar. Aus diesem Grund eignet er sich besonders zur Behandlung von Parodonditis, die gekennzeichnet ist durch Zahnfleischtaschen, Bildung besiedelter Plaques und schließlich mit zunehmendem Verlust des peridontalen Ligamentes, welches die Verbindung zwischen Wurzelzement und Alveolarfach darstellt. Durch den Verlust dieses Zahnhalteapparates kommt es schließlich zur Lockerung und zum Verlust des Zahnes.The chemical structure of the dental enamel according to the invention is absorbable. For this reason, it is particularly suitable for the treatment of periodontitis, which is characterized by gingival pockets, formation of populated plaques and finally with increasing loss of the periodontal ligament, which represents the connection between the root cement and the alveolar compartment. The loss of this tooth retention apparatus leads to loosening and loss of the tooth.
Der derzeitige Stand der zahnmedizinischen Behandlung besteht aus dem Debridement des gebildeten Zwischenraumes zwischen Alveolarfach und Zahnwurzel, Glättung der Wurzeloberfläche und Einnähen einer Folie oder Membran (z.B. Gore-Membran) zum Zwecke der Verhinderung des Ein- Wachsens von Bindegewebe aus der Gingivia im Sinne der gesteuerten Geweberegeneration.The current status of dental treatment consists of the debridement of the space formed between the alveolar compartment and the tooth root, smoothing of the root surface and sewing in a film or membrane (eg Gore membrane) for the purpose of preventing connective tissue ingrowth from the gingiva in the sense of the controlled Tissue regeneration.
Das Einbringen der Folie bzw. Membran sowie deren Befestigung stellen hohe Anforderungen an den Operateur. Der erfindungsgemäße Zahnlack dient dazu die Folie bzw. Membran okklusiv im Alveolarfach zu verankern oder der Lack wird in den Defekt im Sinne eines Platzhalters zur gesteuerten Geweberegeneration eingebracht.The insertion of the film or membrane and its attachment place high demands on the surgeon. The dental lacquer according to the invention serves to anchor the film or membrane occlusively in the alveolar compartment or the lacquer is introduced into the defect in the sense of a placeholder for controlled tissue regeneration.
Zur Beschleunigung der Regeneration des Zahnhalteapparates kann in das Alveolarfach zunächst ein schnell resorbierbares Material wie z.B. Knochensiegel, eingebracht werden und darauf im Anschluß der Zahnlack aufgetragen und zur Polymerisation gebracht werden. ln den Zahnlack kann, zur Verbesserung der Wurzelzementbildung durch die Odontoblasten Calcium-Salze, gegen bakterielle Besiedlung Antibiotika oder Desinfektiva eingemischt werden. Eine wertere Möglichkeit ist das Einmischen von Elastase-Inhibitoren. Bei paradontalen Erkrankungen werden in der Sulcus-Flüssigkeit hohe, aus polymorphkernigen Granulo- zyten stammende Elastasekonzentrationen gefunden. Diese hohen Elas- tasekonzentrationen sind mitverantwortlich, daß Gewebe des peridontalen Zahnhalteapparates abgebaut wird und der Attachment-Verlust fortschreitet. Weiterhin können Natrium-Monofluor-phosphat, Aminfluoride und/oder andere Fluordonatoren beigemischt werden.In order to accelerate the regeneration of the tooth retention apparatus, a rapidly resorbable material, such as a bone seal, can first be introduced into the alveolar compartment and then the dental enamel applied and brought to the polymerization. Antibiotics or disinfectants can be mixed into the tooth enamel to improve the root cement formation by the odontoblasts calcium salts, against bacterial colonization. Another option is to mix in elastase inhibitors. In periodontal diseases, high concentrations of elastase originating from polymorphonuclear granulocytes are found in the sulcus fluid. These high elastase concentrations are partly responsible for the fact that tissue of the periodontal tooth holder is degraded and the attachment loss progresses. Sodium monofluorophosphate, amine fluorides and / or other fluorine donors can also be added.
Bei der Behandlung von freiliegenden Zahnhälsen wird derzeit z.B. Amin- fluorid oder Lokalanästhetika enthaltender Zahnlack aufgetragen, um die Zahnhälse unempfindlicher zu machen bzw. durch die Freisetzung von Amin- oder anderer Fluoride die Zahnhälse zu härten. Diese Zahnlacke haben jedoch nur eine kurze Haltbarkeit auf der Zahnoberfläche, in der Regel von nur wenigen Stunden.In the treatment of exposed tooth necks, e.g. Tooth enamel containing amine fluoride or local anesthetics is applied in order to make the tooth necks less sensitive or to harden the tooth necks through the release of amine or other fluorides. However, these tooth varnishes have a short shelf life on the tooth surface, usually only a few hours.
Durch die Einmischung von Campherchinon wird der Zahnlack schneller zum Aushärten gebracht. Die zuzumischenden Mengen liegen vorzugsweise zwischen 0,05 und 4 Gew. % Campherchinon, insbesondere zwischen 0,1 und 0,5 Gew. %.By mixing camphorquinone, the tooth enamel is hardened more quickly. The amounts to be mixed are preferably between 0.05 and 4% by weight camphorquinone, in particular between 0.1 and 0.5% by weight.
Die Polymerisation erfolgt z.B. durch Bestrahlung mit sichtbarer oder UV- Strahlung bei Wellenlängen von 800 bis 50 nm, vorzugsweise zwischen 500 und 300 nm.The polymerization takes place e.g. by irradiation with visible or UV radiation at wavelengths of 800 to 50 nm, preferably between 500 and 300 nm.
Zahnlacke mit unterschiedlichen Viskositäten sind durch Zumischen von z.B. Glycero-oligoestern und/oder Glycero-oligoester-(meth)acrylaten zu Ethylenglycol- und/oder Glycero-oligoester-(meth)acrylaten, die schon mit Campherchinon versetzt sind, erhältlich. Vorzugsweise werden z.B. Gly- cero-oligolactide, die aus einem Mol Glycerin und 6 bis 14 Mol Milchsäure gebildet sind, zu Ethylenglycol-oligolactid-bismethacrylaten, zugemischt. Ganz besonders bevorzugt sind als zuzumischende Bindemittel Glycero- oligolactide (1:8 bis 1:12), die aus einem Mol Glycerin und 8 bis 12 Mol Milchsäure bestehen. Die zuzumischenden Mengen liegen vorzugsweise zwischen 20 und 60 Gew. % Glycero-oligolactid, insbesonders zwischen 30 und 50 Gew. %.Dental varnishes with different viscosities can be obtained by admixing, for example, glycero-oligoesters and / or glycero-oligoester (meth) acrylates to ethylene glycol and / or glycero-oligoester (meth) acrylates, which are already mixed with camphorquinone. For example, glycero-oligolactides, which are formed from one mole of glycerol and 6 to 14 moles of lactic acid, are preferably admixed to give ethylene glycol oligolactide bismethacrylates. Glycero-oligolactides (1: 8 to 1:12), which consist of one mole of glycerol and 8 to 12 moles of lactic acid, are very particularly preferred as the binders to be mixed. The amounts to be mixed are preferably between 20 and 60% by weight of glycero-oligolactide, in particular between 30 and 50% by weight.
Nach dem Einmischen der Glycero-oligoester- bzw. Glyceroligoester- (meth)acrylate bleibt das System lichthärtend.After the glycero-oligoester or glyceroligoester (meth) acrylates have been mixed in, the system remains light-curing.
Gegenstand der Erfindung sind weiterhin Zahn-Inlays auf Basis von zunächst bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4, erhältlich a) durch Vermischen der monomeren Zusammensetzung mit 10 bisThe invention further relates to tooth inlays based on initially bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 10 to
80 Gew. % Hydroxylapatit, b) Einbringen der Masse in einen zahntechnischen Negativabdruck und c) Polymerisation mittels elektromagnetischer Strahlung < 10 nm.80% by weight of hydroxylapatite, b) introduction of the mass into a dental negative impression and c) polymerization by means of electromagnetic radiation <10 nm.
Ein in der restaurativen Zahnheilkunde beim Füllen von Zahnlöchern auftretendes Problem, stellt der Polymerisationsschrumpf der Materialien (Inserts) dar, der zur Bildung von Spalten im Zahnseitenbereich führt.A problem that occurs in restorative dentistry when filling tooth holes is the polymerization shrinkage of the materials (inserts), which leads to the formation of gaps in the tooth side area.
Die erfindungsgemäßen Inlays weisen keine derartige Schrumpfung auf.The inlays according to the invention have no such shrinkage.
Die Inlays sind erhältlich durch Vermischung von Ethylenglycol-oligoester- (meth)acrylat mit 10 bis 80 Gew. % Hydroxylapatit, vorzugsweise mit 20 bis 70 Gew. %. Die vor der Polymerisation hochviskose Masse wird in ein zahntechnisches Abformmaterial (Negativabdruck) eingebracht und durch γ-Strahlung mit Wellenlängen < 10 nm, besonders im Bereich von 1 bis lO^ nm, vorzugsweise im Bereich von 10"1 bis 10"3 nm, ausgehärtet. Bei den zu verwenden Strahlungsquellen liegen die entsprechenden In- tensitäten (Strahlungsdichten) bei 10 bis 60 kGray, vorzugsweise bei 20 bis 50 kGray [rem/cm2].The inlays can be obtained by mixing ethylene glycol oligoester (meth) acrylate with 10 to 80% by weight of hydroxylapatite, preferably with 20 to 70% by weight. The highly viscous mass before the polymerization is introduced into a dental impression material (negative impression) and cured by γ-radiation with wavelengths <10 nm, especially in the range from 1 to 10 ^ nm, preferably in the range from 10 "1 to 10 " 3 nm . The corresponding intensities (radiation densities) for the radiation sources to be used are 10 to 60 kGray, preferably 20 to 50 kGray [rem / cm 2 ].
Die entstehenden Körper sind durch Sägen oder Bohren mechanisch bearbeitbar. Die so erhaltenen Inlays lassen sich anschließend in den vorbe- reiteten Zahn einbringen und beispielsweise durch Verwendung eines Knochenklebers, bestehend z.B. aus Ethylenglycol-oligolactid-bis- methacrylat und einem Starter, einkleben.The resulting bodies can be machined by sawing or drilling. The inlays obtained in this way can then be introduced into the prepared tooth and, for example, by using a Glue in the bone glue consisting, for example, of ethylene glycol oligolactide bis methacrylate and a starter.
Einlagerungsversuche der erfindungsgemäßen Inlays über 6 Monate bei 60 °C zeigten, daß das Material kein Wasser aufnimmt. Ein Masseverlust wie er durch Degradation entstehen könnte, ist nicht festzustellen.Storage tests of the inlays according to the invention over 6 months at 60 ° C. showed that the material does not absorb water. A loss of mass such as might result from degradation cannot be determined.
Gegenstand der Erfindung sind weiterhin implantierbare Formkörper mit interkonnektierendem Porensystem auf Basis von bioresorbierbaren Poly- merisationsprodukten gemäß Anspruch 4, erhältlich a) durch Einbringen der monomeren Zusammensetzung in eine poröse Matrix und b) Polymerisation mittels elektromagnetischer Strahlung < 10 nm.The invention furthermore relates to implantable molded articles with an interconnecting pore system based on bioresorbable polymerization products according to claim 4, obtainable a) by introducing the monomeric composition into a porous matrix and b) polymerization by means of electromagnetic radiation <10 nm.
Die erfindungsgemäßen Formen sind als Knochenersatzmaterial mitThe forms according to the invention are included as bone substitute material
Platzhalterfunktion bestens geeignet, da die das Porensystem bildenden Trabekel dem neugebildeten Knochen als Leitschiene dienen können. Nach einer gewissen Zeit wird das Polymer vollständig abgebaut, so daß nur noch neugebildeter Knochen verbleibt, der sich dann den entspre- chenden Belastungsrichtungen des Knochens optimal anpassen kann.Placeholder function ideally suited, since the trabeculae forming the pore system can serve as a guide for the newly formed bone. After a certain time, the polymer is completely broken down, so that only newly formed bone remains, which can then optimally adapt to the corresponding load directions of the bone.
Die Formkörper mit interkonnektierendem Porensystem werden hergestellt, indem Matrizen, wie z.B. Zuckerwürfel in eine Siliconform eingebracht werden und diese dann mit dem monomeren Ethylenglycol- und/oder Glycero-oligoester-(meth)acrylat getränkt werden. Das Monomer wird durch Bestrahlen mit γ-Strahlung zur Polymerisation gebracht.The shaped bodies with interconnecting pore system are produced by using matrices, e.g. Sugar cubes are introduced into a silicone mold and these are then impregnated with the monomeric ethylene glycol and / or glycerol oligoester (meth) acrylate. The monomer is polymerized by irradiation with γ radiation.
Benutzt wird γ-Strahlung mit Wellenlängen < 10 nm, besonders im Bereich von 1 bis lO^ nm, vorzugsweise im Bereich von 10"1 bis 10"3 nm. Bei den zu verwenden Strahlungsquellen liegen die entsprechendenΓ-radiation with wavelengths <10 nm is used, particularly in the range from 1 to 10 ^ nm, preferably in the range from 10 "1 to 10 " 3 nm. The corresponding radiation sources are used
Strahlungsdichten bei 10 bis 60 kGray, vorzugsweise bei 20 bis 50 kGray [rem/cm2].Radiation densities at 10 to 60 kGray, preferably at 20 to 50 kGray [rem / cm 2 ].
Die auspolymerisierten Zuckerwürfel können anschließend zur weiteren Formgebung bearbeitet werden oder der Zucker anschließend durch Behandeln mit Wasser oder Alkohol herausgelöst werden. Gegenstand der Erfindung ist ferner die Verwendung von bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4 zur Herstellung von Zahnlacken, Zahn-Inlays und/oder implantierbaren Formkörpern.The polymerized sugar cubes can then be processed for further shaping or the sugar can then be removed by treatment with water or alcohol. The invention further relates to the use of bioresorbable polymerization products according to claim 4 for the production of dental lacquers, tooth inlays and / or implantable moldings.
Beispiel 1example 1
50 ml Ethylenglycol-oligolactid-bismethacrylat wird mit 1 % Campherchinon 20 Minuten unter Rühren lichtgeschützt gemischt und in eine Braunglasflasche abgefüllt. Die Mischung wird auf den Zahn aufgetragen und mit einem Lichtgriffel, z.B. der Fa. Kulzer, Translux EC, 200 Watt 2 x 30 Sekunden gehärtet.50 ml of ethylene glycol oligolactide bis methacrylate is mixed with 1% camphorquinone for 20 minutes with stirring, protected from light, and poured into an amber glass bottle. The mixture is applied to the tooth and with a light pen, e.g. from Kulzer, Translux EC, 200 watts hardened 2 x 30 seconds.
Die entstehende polymere Schicht auf der Zahnoberfläche ist sehr fest und mechanisch abriebstabil.The resulting polymer layer on the tooth surface is very strong and mechanically resistant to abrasion.
Beispiel 2Example 2
Für eine Parodontitis-Behandlung am Beagle-Hund sind höher viskose bis plastisch verformbare "Zahnlack"-Systeme geeignet. In einem Kneter wird die in Beispiel 1 hergestellte Mischung mit 40 Gew. % Glycero-oligolactid (1 :8), das vorher auf 50 °C erhitzt wurde, versetzt und gemischt.For a periodontitis treatment on beagle dogs, highly viscous to plastically deformable "tooth enamel" systems are suitable. In a kneader, the mixture prepared in Example 1 is mixed with 40% by weight glycero-oligolactide (1: 8), which was previously heated to 50 ° C., and mixed.
Nach Auftragen des Zahnlackes wird mit einem Lichtgriffel, Translux EC, 200 Watt 2 x 40 Sekunden gehärtet.After applying the tooth varnish, harden with a light pen, Translux EC, 200 watts 2 x 40 seconds.
Beispiel 3Example 3
Durch Einmischung von 30 Gew. % Hydroxylapatit zu Ethylenglycol- oligolactid-bismethacrylat (1 :8) erhält man eine hochviskose, fest-poröse Masse. Diese wird in einen Negativabdruck eingebracht und durch γ- Bestrahlung bei 25-50 kGy zur Polymerisation gebracht.Mixing 30% by weight of hydroxyapatite into ethylene glycol oligolactide bismethacrylate (1: 8) gives a highly viscous, solid-porous mass. This is placed in a negative impression and brought to polymerization by γ-irradiation at 25-50 kGy.
Beispiel 4Example 4
Ein Zuckerwürfel wird in eine Siliconform eingebracht, die so beschaffen ist, daß die Kantenflächen des Zuckerwürfels allseitig vom Silicon um- schlossen ist, die Ober- und Unterseite aber offen belassen ist. Durch Anlegen eines Vakuums an die Unterseite der Siliconform wird nach Aufbringen von 5 ml Ethylenglycol-oligolactid-bismethacrylat auf die Oberseite des Würfelzuckers, dieses in und durch den Zucker gesaugt. Der so bela- dene Zuckerwürfel kann bei 0 bis 4°C gelagert werden. Die Polymerisation erfolgt durch Bestrahlen des Materials bei 25 kGy.A sugar cube is placed in a silicone mold that is designed so that the edges of the sugar cube are surrounded on all sides by the silicone. is closed, but the top and bottom are left open. By applying a vacuum to the underside of the silicone mold, after 5 ml of ethylene glycol oligolactide bismethacrylate has been applied to the top of the sugar cubes, the sugar is sucked into and through the sugar. The sugar cube loaded in this way can be stored at 0 to 4 ° C. The polymerization is carried out by irradiating the material at 25 kGy.
Die Beladungstechnik kann auch derart modifiziert werden, indem der von der Siliconform umschlossene Würfelzucker zunächst mit 3 ml 60 °C hei- ßem Ethylenglycol-oligolactid-bismethacrylat, das 8 Gew. % 9-BBN (Bora- bicyclononan) enthält, beladen wird. Anschließend werden 5 ml Ethy- lenglycol-oligolactid-bismethacrylat hindurchgesaugt.The loading technique can also be modified in such a way that the cube sugar enclosed in the silicone mold is first loaded with 3 ml of 60 ° C. hot ethylene glycol oligolactide bis methacrylate, which contains 8% by weight of 9-BBN (borobicyclononan). 5 ml of ethylene glycol oligolactide bis methacrylate are then sucked through.
Eine weitere Möglichkeit der Beladung besteht durch das Einlegen mehrer Zuckerwürfel in einem Überschuß Klebermonomer in einem Exsiccator und Anlegen eines Vakuums.Another way of loading is by inserting several sugar cubes in an excess of adhesive monomer in a desiccator and applying a vacuum.
Die auspolymerisierten Zuckerwürfel wurden mit einer Instron Prüfmaschine auf Druckfestigkeit geprüft. Formkörper, bei denen die Zuckermatrix nicht durch Wasser oder Alkohol herausgelöst wurde, zeigten Druckfestigkeiten von 30 MPa, bei Formkörpern mit herausgelöster Matrix betrug die Druckfestigkeit 3 MPa. The polymerized sugar cubes were tested for compressive strength using an Instron testing machine. Moldings in which the sugar matrix was not dissolved out by water or alcohol showed compressive strengths of 30 MPa; in the case of moldings with the matrix released, the compressive strength was 3 MPa.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von bioresorbierbaren Polymerisationsprodukten, dadurch gekennzeichnet, daß monomere Verbindungen, im wesentlichen bestehend aus Zusammensetzungen der Formel I1. A process for the preparation of bioresorbable polymerization products, characterized in that monomeric compounds consisting essentially of compositions of the formula I.
worin wherein
R1, R2, R3 jeweils unabhängig voneinander -(CH2)-, -CH(CH3)-, -CH2-CH2-, -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, 1 ,2- , 1 ,3- oder 1 ,4-Phenylen,R 1 , R 2 , R 3 each independently of one another - (CH 2 ) -, -CH (CH 3 ) -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, 1, 2-, 1, 3- or 1, 4-phenylene,
R4, R4 , R4" jeweils unabhängig voneinder H oder CH3, i, j, k jeweils unabängig voneinander 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 oder 10 und n 0 oder 1 bedeuten,R 4 , R 4 , R 4 "each independently of one another H or CH 3 , i, j, k each independently of one another 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and n 0 or 1 mean
mittels elektromagnetischer Strahlung polymerisiert werden.be polymerized by means of electromagnetic radiation.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzungen der Formel I bei Temperaturen zwischen 0 und 80 °C polymerisiert werden.2. The method according to claim 1, characterized in that the compositions of formula I are polymerized at temperatures between 0 and 80 ° C.
3. Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß die Polymerisation der Zusammensetzungen der Formel I unter Zusatz eines Starters und/oder eines Beschleunigers durchgeführt werden. 3. The method according to claims 1 or 2, characterized in that the polymerization of the compositions of the formula I are carried out with the addition of a starter and / or an accelerator.
4. Bioresorbierbares Polymerisationsprodukt auf Basis von Ethylenglycol- und/oder Glycero-oligoester-(meth)acrylaten, erhältlich nach einem Verfahren der Ansprüche 1 - 3.4. Bioresorbable polymerization product based on ethylene glycol and / or glycero-oligoester (meth) acrylates, obtainable by a process of claims 1-3.
5. Zahnlack auf Basis von bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4, erhältlich a) durch Vermischen der monomeren Zusammensetzung mit 0,05 bis 4 Gew. % Campherchinon, b) Aufbringen der Mischung auf das zu lackierende Gewebe oder den Zahn und c) Polymerisation mittels elektromagnetischer Strahlung im Bereich von 50 bis 800 nm.5. Dental varnish based on bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 0.05 to 4% by weight camphorquinone, b) applying the mixture to the tissue or tooth to be painted and c) polymerization by means of electromagnetic Radiation in the range of 50 to 800 nm.
6. Zahn-Inlays auf Basis von bioresorbierbaren Polymerisationsproduk- ten gemäß Anspruch 4, erhältlich a) durch Vermischen der monomeren Zusammensetzung mit 10 bis 80 Gew. % Hydroxylapatit, b) Einbringen der Masse in einen zahntechnischen Negativabdruck und c) Polymerisation mittels elektromagnetischer Strahlung < 10 nm.6. Dental inlays based on bioresorbable polymerization products according to claim 4, obtainable a) by mixing the monomeric composition with 10 to 80% by weight of hydroxyapatite, b) introducing the composition into a dental negative impression and c) polymerization by means of electromagnetic radiation < 10 nm.
7. Implantierbare Formkörper mit interkonnektierendem Porensystem auf Basis von bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4, erhältlich a) durch Einbringen der monomeren Zusammensetzung in eine poröse Matrix und b) Polymerisation mittels elektromagnetischer Strahlung < 10 nm.7. Implantable shaped bodies with an interconnecting pore system based on bioresorbable polymerization products according to claim 4, obtainable a) by introducing the monomeric composition into a porous matrix and b) polymerization by means of electromagnetic radiation <10 nm.
8. Verwendung von bioresorbierbaren Polymerisationsprodukten gemäß Anspruch 4 zur Herstellung von Zahnlacken, Zahn-Inlays und/oder implantierbaren Formkörpern. 8. Use of bioresorbable polymerization products according to claim 4 for the production of dental lacquers, tooth inlays and / or implantable moldings.
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DE19646782C2 (en) 2000-05-25
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ZA9710206B (en) 1998-07-28
JP2001505196A (en) 2001-04-17
WO1998020839A1 (en) 1998-05-22

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