WO2005056680A1 - Biodegradable hot-melt adhesive - Google Patents

Biodegradable hot-melt adhesive Download PDF

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Publication number
WO2005056680A1
WO2005056680A1 PCT/DE2004/002724 DE2004002724W WO2005056680A1 WO 2005056680 A1 WO2005056680 A1 WO 2005056680A1 DE 2004002724 W DE2004002724 W DE 2004002724W WO 2005056680 A1 WO2005056680 A1 WO 2005056680A1
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WIPO (PCT)
Prior art keywords
caprolactone
polycaprolactone
adhesive composition
lactide
poly
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PCT/DE2004/002724
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German (de)
French (fr)
Inventor
Berthold Nies
Frank Schilke
Ludwig Daum
Original Assignee
Biomet Deutschland Gmbh
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Publication date
Application filed by Biomet Deutschland Gmbh filed Critical Biomet Deutschland Gmbh
Priority to EP04802929A priority Critical patent/EP1692224A1/en
Publication of WO2005056680A1 publication Critical patent/WO2005056680A1/en

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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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0042—Materials resorbable by the body
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the invention relates to a biodegradable adhesive composition based on polymers or polymer blends consisting of caprolactone copolymers or caprolactone copolymers and
  • Polycaprolactone which may also contain additives.
  • Hot melt adhesives have found a wide range of uses in industry and household in the past decades. They are easy to use, have a very fast curing and are unlike many
  • Reactive adhesives are not toxic. These "hot melts" are bonded without the use of solvents. Nevertheless, adhesive strengths are achieved which are sufficient for the bonding of mechanically highly stressed structures. Conventional hot melt adhesives are not biodegradable or absorbable.
  • EP 772464 (3M Comp.) Describes a polycaprolactone as a building block of a crosslinking agent for proteins that can be used as adhesives.
  • WO 00/47686 (Henkel KGaA) discloses an adhesive composition based on at least one binder containing di- or polysulfide bonds for the production of adhesive bonds which use polyols based on polycaprolactone as a building block.
  • WO 99/48989 (Henkel KGaA) describes a dimensionally stable glue stick consisting of an aqueous preparation of synthetic polymers with adhesive character and a soap gel as the shaping framework substance.
  • EP 773979 (Henkel KGaA) discloses the use of polycaprolactone as a building block for radical-curing substances for reactive adhesives.
  • EP 946 223 JVS-Polymers OY describes a plasticizable
  • Implant material consisting of lactide and caprolactone as monomers, the polymer composition having melting points between 37 ° and 55 ° C. They are used to fill holes, fractures, caves or spaces. However, these copolymers are not used as adhesives or hot-melt adhesives because they are low
  • Melting points in the body temperature range are only suitable for defect-filling, but not for load-bearing applications.
  • the temperature of the transition to the polymer melt drops further due to swelling and polymer degradation, so that the polymers described here very quickly lose their dimensional stability.
  • the object of the present invention was therefore to develop a hot-melt adhesive which has the abovementioned. Does not have disadvantages.
  • polymers and polymer blends based on polycaprolactone and caprolactone are also known.
  • Copolymers are suitable for use as biodegradable and resorbable hot melt adhesives. Since the polymer materials according to the invention have melting points between 57 and 100 ° C, preferably between 60 and 70 ° C, they can e.g. Use as medical tissue glue, without major heat related ones
  • the hot melt adhesive consists of 25 - 95% polycaprolactone,
  • the hot melt adhesive is preferably used for the temporary bonding of biological tissue and other materials in medicine.
  • other uses such as fixing screws and nails in the bone tissue or the temporary structural stabilization of tissue are also possible.
  • Poly (caprolactone-co-D, L-lactide) are preferably used as caprolactone copolymers.
  • the molar masses of the polycaprolactone are between 2000-120,000, preferably between 65,000 and 80,000 g / mol.
  • the molar masses of the poly (lactide-co-caprolactone) are between 2000-250,000 g / mol, preferably over 100,000 g / mol.
  • biocompatible additives can be added to the copolymer mixtures during the synthesis, which further improve the adhesive properties.
  • Derivatives of starch carboxymethyl starch, hydroxyethyl starch), cellulose, are preferably used as additives
  • the polymers and copolymers listed in the following examples are synthesized by conventional ring opening polymerization processes (see, for example, WH Carothers, GL Dorough, FJ. Van Natta, J. Am. Soc. 54, 761 (1932) and HR Kricheldorf (ed.) Handbook of Polymer Synthesis, Marcel Decker Inc., New York 1992).
  • the polymer blends are produced by mixing the melted polymers, copolymers and additives in a kneader.
  • the melting point is 62.5 ° C.
  • Polymer blend consisting of:
  • the melting point is 69.2 ° C.
  • Polymer blend consisting of:
  • Caprolactone (Mw> 100,000 g / mol) and 20% calcium phosphate.
  • the melting point is 61.5 ° C

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Materials For Medical Uses (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to an adhesive composition based on polymers or polymer blends consisting of caprolactone copolymers or caprolactone copolymers and polycaprolactone, wherein the composition is biodegradable or resorbable and has a melting point ranging between 57 and 100 °C. The invention also relates to the utilization of said composition as hot-melt adhesive for temporarily gluing together biological tissue and other materials in medicine.

Description

Biodegradierbarer Schmelzkleber Biodegradable hot melt adhesive
Gegenstand der Erfindung ist eine biodegradierbare Klebstoff-Zusammensetzung auf der Basis von Polymeren oder Polymerblends bestehend aus Caprolacton-Copolymeren bzw. Caprolacton-Copolymeren undThe invention relates to a biodegradable adhesive composition based on polymers or polymer blends consisting of caprolactone copolymers or caprolactone copolymers and
Polycaprolacton, die gegebenenfalls noch Additive enthalten kann.Polycaprolactone, which may also contain additives.
Schmelzkleber haben in den letzten Jahrzehnten vielfältige Anwendung in Industrie und Haushalt gefunden. Sie sind einfach zu handhaben, weisen eine sehr schnelle Aushärtung auf und sind im Gegensatz zu vielenHot melt adhesives have found a wide range of uses in industry and household in the past decades. They are easy to use, have a very fast curing and are unlike many
Reaktivklebern nicht toxisch. Die Verklebung mit diesen „Hotmelts" erfolgt ohne den Einsatz von Lösungsmitteln. Trotzdem werden Klebefestigkeiten erreicht, die für den Verbund von mechanisch hoch belasteten Strukturen ausreichend sind. Herkömmliche Schmelzkleber sind nicht biodegradierbar bzw. resorbierbar.Reactive adhesives are not toxic. These "hot melts" are bonded without the use of solvents. Nevertheless, adhesive strengths are achieved which are sufficient for the bonding of mechanically highly stressed structures. Conventional hot melt adhesives are not biodegradable or absorbable.
Sie können daher bislang nicht zur temporären Verklebung von Geweben oder Materialien z.B. in der Humanmedizin eingesetzt werden. Die hohe Schmelztemperatur dieser Kleber (z.T. > 200 °C) ist ein weiterer Grund, warum Schmelzkleber in der Medizin bisher nicht zum Einsatz kommen.So far they have not been used for the temporary bonding of fabrics or materials e.g. be used in human medicine. The high melting temperature of these adhesives (sometimes> 200 ° C) is another reason why hot melt adhesives have not been used in medicine until now.
EP 772464 (3M Comp.) beschreibt ein Polycaprolacton als Baustein eines Vernetzers für Proteine, die als Klebstoffe verwendet werden können.EP 772464 (3M Comp.) Describes a polycaprolactone as a building block of a crosslinking agent for proteins that can be used as adhesives.
WO 00/47686 (Henkel KGaA) offenbart eine Klebstoff-Zusammensetzung auf der Basis von mindestens einem Di- oder Polysulfidbindungen enthaltenden Bindemittel zur Herstellung von Klebeverbindungen, die Polyole auf Basis von Polycaprolacton als Baustein verwenden.WO 00/47686 (Henkel KGaA) discloses an adhesive composition based on at least one binder containing di- or polysulfide bonds for the production of adhesive bonds which use polyols based on polycaprolactone as a building block.
WO 99/48989 (Henkel KGaA) beschreibt einen formstabilen Klebestift bestehend aus einer wässrigen Zubereitung von synthetischen Polymeren mit Klebstoffcharakter und einem Seifengel als formgebender Gerüstsubstanz. EP 773979 (Henkel KGaA) offenbart die Verwendung von Polycaprolacton als Baustein für radikalisch härtende Substanzen für Reaktivklebstoffe.WO 99/48989 (Henkel KGaA) describes a dimensionally stable glue stick consisting of an aqueous preparation of synthetic polymers with adhesive character and a soap gel as the shaping framework substance. EP 773979 (Henkel KGaA) discloses the use of polycaprolactone as a building block for radical-curing substances for reactive adhesives.
EP 946 223 (JVS-Polymers OY) beschreibt ein plastizierbaresEP 946 223 (JVS-Polymers OY) describes a plasticizable
Implantatmaterial bestehend auf aus Lactid und Caprolacton als Monomere, wobei die Polymerzusammensetzung Schmelzpunkte zwischen 37° und 55 °C aufweisen. Sie werden verwendet, um Löcher, Frakturen, Höhlen oder Räume zu füllen. Als Klebstoffe bzw. Schmelzkleber werden diese Copolymere jedoch nicht eingesetzt, da sie aufgrund ihrer niedrigenImplant material consisting of lactide and caprolactone as monomers, the polymer composition having melting points between 37 ° and 55 ° C. They are used to fill holes, fractures, caves or spaces. However, these copolymers are not used as adhesives or hot-melt adhesives because they are low
Schmelzpunkte im Bereich der Körpertemperatur nur für defektfüllende, nicht jedoch für lasttragende Anwendung geeignet sind. Zudem sinkt bei resorbierbaren Materialien durch Quellung und Polymerdegradation die Temperatur des Übergangs zur Polymerschmelze noch weiter ab, so dass die hier beschriebenen Polymere sehr schnell ihre Formstabilität verlieren.Melting points in the body temperature range are only suitable for defect-filling, but not for load-bearing applications. In addition, in the case of resorbable materials, the temperature of the transition to the polymer melt drops further due to swelling and polymer degradation, so that the polymers described here very quickly lose their dimensional stability.
Aufgabe der vorliegenden Erfindung war es daher, einen Schmelzkleber zu entwickeln, der die o.g. Nachteile nicht aufweist. Überraschenderweise wurde nun gefunden, dass Polymere und Polymerblends basierend auf Polycaprolacton und Caprolacton-The object of the present invention was therefore to develop a hot-melt adhesive which has the abovementioned. Does not have disadvantages. Surprisingly, it has now been found that polymers and polymer blends based on polycaprolactone and caprolactone
Copolymeren für den Einsatz als biodegradierbare und resorbierbare Schmelzkleber geeignet sind. Da die erfindungsgemäßen Polymermaterialien Schmelzpunkte zwischen 57 und 100 °C, vorzugsweise zwischen 60 und 70 ° C besitzen, lassen sie sich z.B. als medizinische Gewebekleber einsetzen, ohne größere durch Hitze bedingteCopolymers are suitable for use as biodegradable and resorbable hot melt adhesives. Since the polymer materials according to the invention have melting points between 57 and 100 ° C, preferably between 60 and 70 ° C, they can e.g. Use as medical tissue glue, without major heat related ones
Gewebeschäden zu verursachen. Durch diese vergleichsweise hohen Schmelzpunkte ist gewährleistet, dass die Kleber auch während der Polymerdegradation eine über den Zeitraum der Wundheilung ausreichend hohe mechanische Stabilität aufweisen. Durch geeignete Wahl der Zusammensetzung dieser Polymerblends werden Klebefestigkeiten erreicht, die mit nichtresorbierbaren herkömmlichen Schmelzklebern vergleichbar sind. Der Schmelzkleber besteht aus 25 - 95 % Polycaprolacton,To cause tissue damage. These comparatively high melting points ensure that the adhesives have a sufficiently high mechanical stability over the period of wound healing, even during polymer degradation. A suitable choice of the composition of these polymer blends achieves adhesive strengths that are comparable to non-resorbable conventional hot melt adhesives. The hot melt adhesive consists of 25 - 95% polycaprolactone,
5 - 75 % Poly(caprolacton-co-D,L-lactid) und zusätzlich 0 - 20 % biokompatiblen Additiven5 - 75% poly (caprolactone-co-D, L-lactide) and additionally 0 - 20% biocompatible additives
Vorzugsweise wird der Schmelzkleber zur temporären Verklebung von biologischem Gewebe und sonstigen Materialien in der Medizin verwendet. Es sind aber auch andere Verwendungen wie Fixierung von Schrauben und Nägeln im Knochengewebe oder die temporäre strukturelle Stabilisierung von Gewebe möglich.The hot melt adhesive is preferably used for the temporary bonding of biological tissue and other materials in medicine. However, other uses such as fixing screws and nails in the bone tissue or the temporary structural stabilization of tissue are also possible.
Als Caprolacton-Copolymere werden vorzugsweise Poly(caprolacton-co-D,L- lactide) verwendet.Poly (caprolactone-co-D, L-lactide) are preferably used as caprolactone copolymers.
Die Molmassen des Polycaprolactons betragen zwischen 2000 - 120.000, bevorzugt zwischen 65.000 bis 80.000 g/mol.The molar masses of the polycaprolactone are between 2000-120,000, preferably between 65,000 and 80,000 g / mol.
Die Molmassen des Poly(lactid-co-caprolacton) betragen zwischen 2000 - 250.000 g/mol, bevorzugt über 100.000 g/mol.The molar masses of the poly (lactide-co-caprolactone) are between 2000-250,000 g / mol, preferably over 100,000 g / mol.
Zusätzlich können den Copolymermischungen während der Synthese bis zu 20 % biokompatible Additive zugesetzt werden, die die Klebeeigenschaften nochmals verbessern. Als Additive kommen vorzugsweise Derivate der Stärke (Carboxymethylstärke, Hydroxyethylstärke), der CelluloseIn addition, up to 20% biocompatible additives can be added to the copolymer mixtures during the synthesis, which further improve the adhesive properties. Derivatives of starch (carboxymethyl starch, hydroxyethyl starch), cellulose, are preferably used as additives
(Carboxymethylcellulose, Hxdroxyethylcellulose), des Chitosan, Polyvinylpyrolidon (PVP) oder Polyethylenglycole in Frage. Besonders bevorzugt sind Carboxymethylstärke und Chitosan. Die in Fig. 1 dargestellten Proben beziehen sich auf Beispiel 2, wobei(Carboxymethylcellulose, Hxdroxyethylcellulose), chitosan, polyvinylpyrolidone (PVP) or polyethylene glycols in question. Carboxymethyl starch and chitosan are particularly preferred. The samples shown in Fig. 1 refer to Example 2, wherein
Poly(lactid-co-caprolacton) als TK, Polycaprolacton als PCL und Carboxymethylstärke als CMS bezeichnet sind. Der Fehlerbalken gibt die Standardabeichung an.Poly (lactide-co-caprolactone) as TK, polycaprolactone as PCL and carboxymethyl starch as CMS. The error bar indicates the standard deviation.
Die in den folgenden Beispielen aufgeführten Polymer und Copoiymere werden nach üblichen Verfahren der Ringöffnungspolymerisation synthetisiert (siehe z.B. W.H. Carothers, G.L. Dorough, FJ. van Natta, J. Am. Soc. 54, 761 (1932) und H.R. Kricheldorf (Hrsg.) Handbook of Polymer Synthesis, Marcel Decker Inc., New York 1992). Die Polymerblends werden durch Vermischen der geschmolzenen Polymere, Copoiymere und Additive in einem Kneter hergestellt.The polymers and copolymers listed in the following examples are synthesized by conventional ring opening polymerization processes (see, for example, WH Carothers, GL Dorough, FJ. Van Natta, J. Am. Soc. 54, 761 (1932) and HR Kricheldorf (ed.) Handbook of Polymer Synthesis, Marcel Decker Inc., New York 1992). The polymer blends are produced by mixing the melted polymers, copolymers and additives in a kneader.
Beispiel 1 :Example 1 :
Poivmerblend bestehend ausr 75 % Polycaprolacton (Mw= 65.000 g/mol),Polymer blend consisting of 75% polycaprolactone (M w = 65,000 g / mol),
25 % Poly(lactid-co-caprolacton) mit einem 84:16 Verhältnis von D,L-Lactid :25% poly (lactide-co-caprolactone) with an 84:16 ratio of D, L-lactide:
Caprolacton (Mw > 100.000 g/mol) und einem Zusatz vonCaprolactone (M w > 100,000 g / mol) and an addition of
5 % Carboxymethylstärke.5% carboxymethyl starch.
Der Schmelzpunkt beträgt 62.5 °C.The melting point is 62.5 ° C.
ERSATZBLATT Beispiel 2:SUBSTITUTE SHEET Example 2:
Polymerblend bestehend aus:Polymer blend consisting of:
35 % Polycaprolacton (Mw= 65.000 g/mol),35% polycaprolactone (M w = 65,000 g / mol),
65 % Poly(lactid-co-caprolacton) mit einem 84:16 Verhältnis von Lactid65% poly (lactide-co-caprolactone) with an 84:16 ratio of lactide
Caprolacton (Mw > 100.000 g/mol) und einem Zusatz vonCaprolactone (M w > 100,000 g / mol) and an addition of
10 % Carboxymethylstärke.10% carboxymethyl starch.
Der Schmelzpunkt beträgt 69.2 °C.The melting point is 69.2 ° C.
Beispiel 3:Example 3:
Polymerblend bestehend aus:Polymer blend consisting of:
75 % Polycaprolacton (Mw = 65.000 g/mol),75% polycaprolactone (Mw = 65,000 g / mol),
5 % Poly(lactid-co-caprolacton) mit einem 84:16 Verhältnis von Lactid5% poly (lactide-co-caprolactone) with an 84:16 ratio of lactide
Caprolacton (Mw > 100.000 g/mol) und 20 % Calciumphosphat.Caprolactone (Mw> 100,000 g / mol) and 20% calcium phosphate.
Der Schmelzpunkt beträgt 61 ,5 °C The melting point is 61.5 ° C

Claims

Ansprüche Expectations
1. Klebstoff-Zusammensetzung auf der Basis von Polymeren oder Polymerblends bestehend aus Caprolacton-Copolymeren bzw. Caprolacton-Copolymeren und Polycaprolacton, dadurch gekennzeichnet, dass die Zusammensetzung biodegradierbar bzw. resorbierbar ist und einen Schmelzpunkt zwischen 57 °C und 100 °C hat.1. Adhesive composition based on polymers or polymer blends consisting of caprolactone copolymers or caprolactone copolymers and polycaprolactone, characterized in that the composition is biodegradable or resorbable and has a melting point between 57 ° C and 100 ° C.
2. Klebstoff-Zusammensetzung auf der Basis von Polymerblends nach Anspruch 1 , dadurch gekennzeichnet, dass sie aus Polycaprolacton und Poly(caprolacton-co-D,L-lactid) und gegebenenfalls Additiven besteht.2. Adhesive composition based on polymer blends according to claim 1, characterized in that it consists of polycaprolactone and poly (caprolactone-co-D, L-lactide) and optionally additives.
3. Klebstoff-Zusammensetzung nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass sie aus 25 - 95 % Polycaprolacton 5 - 75 % Poly(caprolacton-co-D,L-lactid) 0 - 20 % biokompatiblen Additiven besteht.3. Adhesive composition according to claim 1 and / or 2, characterized in that it consists of 25-95% polycaprolactone 5-75% poly (caprolactone-co-D, L-lactide) 0-20% biocompatible additives.
4. Klebstoff-Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als biokompatible Additive Stärkederivate, Cellulosederivate, Chitosan, Polyvinylpyrolidon (PVP) oder Polyethylenglykol zugesetzt sind.4. Adhesive composition according to one of claims 1 to 3, characterized in that starch derivatives, cellulose derivatives, chitosan, polyvinylpyrolidone (PVP) or polyethylene glycol are added as biocompatible additives.
5. Verwendung der Klebstoffzusammensetzung nach mindestens einem der Ansprüche 1 bis 4 zur temporären Verklebung von biologischem Gewebe und sonstigen Materialien in der Medizin. 5. Use of the adhesive composition according to at least one of claims 1 to 4 for the temporary bonding of biological tissue and other materials in medicine.
PCT/DE2004/002724 2003-12-12 2004-12-09 Biodegradable hot-melt adhesive WO2005056680A1 (en)

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EP04802929A EP1692224A1 (en) 2003-12-12 2004-12-09 Biodegradable hot-melt adhesive

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DE10358779.9 2003-12-12
DE10358779A DE10358779B4 (en) 2003-12-12 2003-12-12 Biodegradable adhesive composition and its use

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WO2017055045A1 (en) 2015-10-01 2017-04-06 Purac Biochem Bv Non-reactive hot-melt adhesive with specific resin
US11384260B1 (en) 2021-05-28 2022-07-12 Cohesys Inc. Adhesive devices and uses thereof

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
US9173970B2 (en) 2007-01-17 2015-11-03 University Of Massachusetts Lowell Biodegradable bone plates and bonding systems
US9597133B2 (en) 2007-01-17 2017-03-21 University Of Massachusetts Lowell Biodegradable bone plates and bonding systems
WO2017055045A1 (en) 2015-10-01 2017-04-06 Purac Biochem Bv Non-reactive hot-melt adhesive with specific resin
WO2017055044A1 (en) * 2015-10-01 2017-04-06 Purac Biochem Bv Non-reactive hot-melt adhesive with set time improver
CN108026426A (en) * 2015-10-01 2018-05-11 普拉克生化公司 Non-reacted hotmelt with hardening time modifier
CN108026427A (en) * 2015-10-01 2018-05-11 普拉克生化公司 Non-reacted hotmelt with specific resin
US10407599B2 (en) 2015-10-01 2019-09-10 Purac Biochem B.V. Non-reactive hot-melt adhesive with set time improver
EA033746B1 (en) * 2015-10-01 2019-11-21 Purac Biochem Bv Non-reactive hot-melt adhesive with set time improver
EA035805B1 (en) * 2015-10-01 2020-08-13 ПУРАК Биокем БВ Non-reactive hot-melt adhesive, method for manufacturing same and method for arranging substrates in a fixed position with respect to each other
US11008489B2 (en) 2015-10-01 2021-05-18 Purac Biochem Bv Non-reactive hot-melt adhesive with specific resin
US11384260B1 (en) 2021-05-28 2022-07-12 Cohesys Inc. Adhesive devices and uses thereof
US11643574B2 (en) 2021-05-28 2023-05-09 Cohesys Inc. Adhesive devices and uses thereof

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