WO2011069973A2 - Système composite adhésif servant à recouvrir, fermer ou coller du tissu cellulaire - Google Patents

Système composite adhésif servant à recouvrir, fermer ou coller du tissu cellulaire Download PDF

Info

Publication number
WO2011069973A2
WO2011069973A2 PCT/EP2010/068985 EP2010068985W WO2011069973A2 WO 2011069973 A2 WO2011069973 A2 WO 2011069973A2 EP 2010068985 W EP2010068985 W EP 2010068985W WO 2011069973 A2 WO2011069973 A2 WO 2011069973A2
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
composite system
adhesive composite
tissue
mol
Prior art date
Application number
PCT/EP2010/068985
Other languages
German (de)
English (en)
Other versions
WO2011069973A3 (fr
Inventor
Sebastian Dörr
Heike Heckroth
Christoph Eggert
Original Assignee
Bayer Materialscience Ag
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 Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to AU2010329976A priority Critical patent/AU2010329976A1/en
Priority to US13/515,100 priority patent/US20120276382A1/en
Priority to JP2012542496A priority patent/JP2013513679A/ja
Priority to BR112012014192A priority patent/BR112012014192A2/pt
Priority to CA 2783981 priority patent/CA2783981A1/fr
Priority to IN5173DEN2012 priority patent/IN2012DN05173A/en
Priority to CN2010800563529A priority patent/CN102725320A/zh
Publication of WO2011069973A2 publication Critical patent/WO2011069973A2/fr
Publication of WO2011069973A3 publication Critical patent/WO2011069973A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21—Paper; Textile fabrics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2210/00—Compositions for preparing hydrogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • Adhesive composite system for covering, closing or adhering cell tissue
  • the present invention relates to an adhesive composite system. Further objects of the invention are a process for the production of the adhesive composite system, an adhesive composite system obtainable by the process, an adhesive composite system for use as a means for covering, sealing or adhering cell tissue and the use of the adhesive composite system for producing a means for covering, closing or adhering cell tissue ,
  • tissue adhesives which are based on a hydrophilic two-component polyurethane system. These tissue adhesives can be used for covering, closing or adhering cell tissue and, in particular, for bonding wounds.
  • the tissue adhesives described here are characterized by a strong bond to the tissue, a high degree of flexibility of the joint seam obtained, easy applicability, a curing time that can be set in a wide range and high biocompatibility.
  • certain problems also arise when using the known tissue adhesives. Due to the hydrophilicity of the polyurethane systems, prolonged exposure to water may result in swelling of the tissue adhesive.
  • an adhesive composite system comprising an adhesive layer of a tissue adhesive and a protective layer applied over the surface of the adhesive layer, in which the tissue adhesive is based on hydrophilic polyurethane polymers and the protective layer is impermeable to water.
  • Waterproof in the context of the present invention is a protective layer which protects an underlying adhesive layer from swelling for at least 30 minutes when the adhesive layer / protective layer adhesive system is immersed in a water bath at a temperature of up to 40 ° C ,
  • the water-impermeable layer is preferably characterized in that when storing such a layer as a free film with a thickness of 100 microns in an excess of demineralized water at 23 ° C for a period of 2 hours, the masses of absorbed water, based on the starting material of Films, less than 100%, preferably less than 50%, more preferably less than 20% and most preferably less than 10%.
  • the tissue adhesive comprises
  • X is an n-valent organic radical obtained by removal of a primary amino group of an n-valent amine
  • Ri, P2 are the same or different organic radicals which have no Zerewitinoff active hydrogen and n is an integer of at least 2. and or
  • tissue adhesive is characterized by a strong bond to the tissue, a high flexibility of the obtained joint seam, easy applicability, a wide range adjustable curing time and a high biocompatibility.
  • Zerewitinoff-active hydrogen For the definition of Zerewitinoff-active hydrogen, reference is made to the corresponding entry "active hydrogen in Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart.
  • groups having Zerewitinoff-active hydrogen are OH, NH or SH.
  • isocyanates AI for example, monomeric aliphatic or cycloaliphatic diesters triisocyanates such as 1, 4-butylene diisocyanate (BDI), 1, 6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4 Trimethyl-hexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonanetriisocyanate), and also alkyl-2 , 6-diisocyanatohexanoate (lysine diisocyanate) with C 1 -C 8 alkyl groups are used. In a particularly preferred embodiment, exclusively hexamethylene diisocyanate is used.
  • BDI 1,
  • the isocyanates AI may preferably have exclusively aliphatically or cycloaliphatically bonded isocyanate groups.
  • the isocyanates or isocyanate mixtures AI) preferably have an average NCO functionality of 2 to 4, particularly preferably 2 to 2.6 and very particularly preferably 2 to 2.4.
  • polyols A2) it is possible to use in principle all polyhydroxy compounds known per se to the person skilled in the art having 2 or more OH functions per molecule.
  • polyester polyols polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols or any desired mixtures thereof.
  • the polyols A2) preferably have an average OH functionality of 3 to 4
  • the polyols A2) furthermore preferably have a number-average molecular weight of from 400 to 20 000 g / mol, more preferably from 2000 to 10 000 g / mol, and very preferably from 4000 to 8500.
  • Particularly preferred polyether polyols are polyalkylene oxide polyethers based on ethylene oxide and optionally propylene oxide.
  • polyether polyols are preferably based on di- or higher-functional starter molecules such as dihydric or higher-functional alcohols or amines.
  • initiators are water (considered as a diol), ethylene glycol, propylene glycol, butylene glycol, glycerol, TMP, sorbitol, pentaerythritol, triethanolamine, ammonia or ethylenediamine.
  • polyols A2) are polyalkylene oxide polyethers which in particular have a content of ethylene oxide-based units of 60 to 90% by weight, based on the total amounts of alkylene oxide units present.
  • Preferred polyester polyols are polycondensates of di- and optionally tri- and tetra-ols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (I, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexan
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • Suitable dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2-dimethylsuccinic acid.
  • the acid source used may also be the corresponding anhydrides. If the average functionality of the polyol to be esterified is greater than 2, monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may additionally be used.
  • Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
  • Hydroxycarboxylic acids which can be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.
  • hydroxyl-containing polycarbonates preferably polycarbonatediols, having number-average molecular weights Mn of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol.
  • carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
  • polyols preferably diols.
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxy-methylcyclohexane, 2-Methyl-l, 3-propanediol, 2,2,4-Trimethylpentandiol-l, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the aforementioned type in question.
  • isocyanates AI) can be reacted with polyols A2) at an NCO / OH ratio of preferably 4: 1 to 12: 1, particularly preferably 8: 1. Subsequently, the proportion of unreacted isocyanates AI) separated by suitable methods. Usually, the thin-film distillation is used for this purpose, low-monomer products having residual monomer contents of less than 1% by weight, preferably less than 0.5% by weight, very particularly preferably less than 0.1% by weight being obtained.
  • stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
  • the reaction temperature is in particular 20 to 120 ° C, preferably 60 to 100 ° C.
  • R 1, R 2 are the same or different, optionally branched or eye-soluble organic radicals which do not have Zerewitinoff-active hydrogen, having 1 to 20, preferably 1 to 10 carbon atoms, more preferably methyl or ethyl groups,, n is an integer from 2 to 4 and
  • X is an n-valent organic, optionally branched or cyclic organic radical having 2 to 20, preferably 5 to 10 carbon atoms, which is obtained by removal of a primary amino group of an n-valent primary amine.
  • n in the formula (I) can also represent a non-integer average.
  • the preparation of the amino-functional polyaspartic acid esters B1) can be carried out in a known manner by reacting the corresponding primary at least difunctional amines X (NH 2 ) n with maleic or fumaric acid esters of the general formula (II)
  • Preferred maleic or fumaric acid esters are dimethyl maleate, diethyl maleate, dibutyl maleate and the corresponding fumaric acid esters.
  • Preferred primary at least difunctional amines X (NH 2 ) n are ethylenediamine, 1, 2-diaminopropane, 1, 4-diaminobutane, 1, 3-diaminopentane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1, 6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-l, 6-diaminohexane, 1,1'-diaminoundecane, 1,12-diaminododecane , 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- and / or 2,6-hexahydrotoluylenediamine, 2,4'- and / or 4,4'-diamino-dicyclohexylmethane, 3,3
  • Particularly preferred primary at least difunctional amines are 1,3-diaminopentane, 1,5-diaminopentane, 2-methyl-l, 5-diaminopentane, 1,6-diaminohexane, l, 13-diamino-4,7,10-trioxatridecane.
  • Very particular preference is given to 2-methyl-1,5-diaminopentane.
  • the preparation of the amino-functional aspartic acid esters B1) from the abovementioned starting materials is carried out, for example, in DE-A 69 311 633, preferably within the temperature range from 0 to 100 ° C., the starting materials being used in proportions such that at least one, preferably at least one, primary amino group exactly one olefinic double bond is omitted, which can optionally be separated by distillation after the reaction, if used in excess starting materials.
  • the reaction can be carried out in bulk or in the presence of suitable solvents such as methanol, ethanol, propanol or dioxane or mixtures of such solvents.
  • ratios of isocyanate-reactive groups to isocyanate groups of from 50 to 1 to 1.5 to 1, more preferably from 15 to 1 to 4 to 1.
  • the isocyanate-functional prepolymer to be used for this purpose can correspond to that of component A) or else deviating from the components as listed as possible constituents of the isocyanate-functional prepolymers within the scope of this application.
  • the 2-component adhesive systems according to the invention are obtained by mixing the prepolymer with the hardener component B) or C).
  • the ratio of NCO-reactive NH groups to free NCO groups is preferably 1: 1, 5 to 1: 1, particularly preferably 1: 1.
  • the tissue adhesive does not comprise Aspai reester B) but exclusively reaction products C).
  • the adhesive layer may also contain one or more active ingredients.
  • the active substances may in particular be those substances which promote wound healing.
  • the protective layer has an elongation at break of> 100%, preferably of> 200%.
  • a protective layer is particularly deformable and in this respect corresponds particularly well with the mechanical properties of a polyurethane adhesive layer.
  • the elongation at break is determined according to DIN EN ISO 527-1.
  • the protective layer has a 100% modulus of from 0.5 to 20 MPa, preferably from 1 to 15 MPa, particularly preferably from 2 to 10 MPa.
  • Such protective layers are elastic, so that a high overall elasticity of the adhesive composite system results, even if the adhesive layer has corresponding mechanical properties. Particular advantages are therefore especially when the adhesive composite system has a polyurethane-based adhesive layer.
  • the 100% modulus is determined according to DIN EN ISO 527-1.
  • the protective layer may in particular be based on polymers.
  • the polymers may preferably be polyurethanes, polyesters, poly (meth) acrylates, polyepoxides, polyvinyl acetates, polyethylenes, polystyrenes, polybutadienes, polyvinyl chlorides and / or corresponding copolymers, preferably polyacrylates and / or polyurethanes.
  • the polymers are particularly preferably polyurethanes obtainable by a prepolymerization process in which a) isocyanate-functional prepolymers of al) organic polyisocyanates a2) of polymeric polyols having number average molecular weights of from 400 to
  • Suitable polyisocyanates a1) are aliphatic, aromatic or cycloaliphatic polyisocyanates having an NCO functionality of greater than or equal to 2.
  • polyisocyanates examples include 1, 4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4, 4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or he 1, 4-bis (2-isocyan
  • proportionally modified diisocyanates which have a functionality of> 2, with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione or oxadiazinetrione structures and mixtures thereof.
  • polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically or cycloaliphatically bound isocyanate groups or mixtures of these and an average NCO functionality of the mixture of from 2 to 4, preferably from 2 to 2.6 and more preferably from 2 to 2.4.
  • these are difunctional isocyanate units, preferably difunctional aliphatic isocyanate units.
  • polyisocyanates al) hexamethylene diisocyanate, isophorone diisocyanate or the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures of used the aforementioned diisocyanates.
  • a mixture of hexamethylene diisocyanate and isophorone diisocyanate is used.
  • the polymeric polyols a2) used are compounds having a number average molecular weight M n of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol. These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
  • Suitable polymeric polyols are the polyester polyols known per se in polyurethane coating technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols. These can be used individually or in any mixtures with each other.
  • Suitable polyester polyols are polycondensates of di- and optionally tri- and tetra-ols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol ( l, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hex
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • Suitable dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2-dimethylsuccinic acid.
  • the acid source used may also be the corresponding anhydrides.
  • monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may additionally be used.
  • Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
  • Hydroxycarboxylic acids which can be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.
  • Suitable polycarbonate polyols are hydroxyl-containing polycarbonates, preferably polycarbonatediols, with number-average molecular weights M n of 400 to 8000 g / mol, preferably 600 to 3000 g / mol. These are obtainable by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-Methyl-l, 3-propanediol, 2,2,4-Trimethylpentandiol-l, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the aforementioned kind.
  • the diol component preferably contains from 40 to 100% by weight of hexanediol; preference is given to 1,6-hexanediol and / or hexanediol derivatives.
  • hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups.
  • Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol.
  • polyether-polycarbonate diols instead of or in addition to pure polycarbonate diols, it is also possible to use polyether-polycarbonate diols. Hydroxyl-containing polycarbonates are preferably built linear.
  • Suitable polyether polyols are, for example, polytetramethylene glycol polyethers obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
  • starter molecules it is possible to use all compounds known from the prior art, for example water, butyl diglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.
  • Preferred polyols a2) are polytetramethylene glycol polyethers and polycarbonate polyols or mixtures thereof, and polytetramethylene glycol polyethers are particularly preferred.
  • Suitable hydroxy-functional compounds a3) can be polyols of the stated molecular weight range having up to 20 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexane diol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) ) propane), trimethylolpropane, trimethylolethane, glycerol, pentaerythritol and any mixtures thereof.
  • ethylene glycol diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-
  • ester diols of the stated molecular weight range, such as ⁇ -hydroxybutyl- ⁇ -hydroxy-caproic acid ester, ro-hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
  • monofunctional isocyanate-reactive hydroxyl-group-containing compounds examples include methanol, ethanol, isopropanol, n-propanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol mono-propyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2 Ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol. If such alcohols react with the isocyanate-functional prepolymer, the correspondingly reacted portions are no longer added to the solvents.
  • Suitable amino-functional compounds bl) can be organic di- or polyamines, such as, for example, 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomeric mixture of 2,2, 4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, and / or dimethylethylenediamine can be used.
  • 1,2-ethylenediamine 1,2- and 1,3-diaminopropane
  • 1,4-diaminobutane 1,6-diaminohexane
  • isophoronediamine isomeric mixture of 2,2, 4- and 2,4,4-trimethylhexamethylenediamine
  • 2-methylpentamethylenediamine diethylenetriamine
  • aminofunctional compounds b1) which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups.
  • primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.
  • amino-functional compounds bl) are also monofunctional isocyanate-reactive amine compounds, for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monoketim of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • monofunctional isocyanate-reactive amine compounds for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine
  • 1, 2-ethylenediamine, bis (4-aminocyclohexyl) methane, 1, 4-diaminobutane, isophoronediamine, ethanolamine, diethanolamine and diethylenetriamine are preferably used.
  • the components al), a2), a3) and bl) are selected such that no or only a small proportion of branching points is formed in the polyurethane, since otherwise a high solution viscosity results.
  • Particular preference is given to using exclusively components having an average functionality of ⁇ 2.2, very particularly preferably having an average functionality of ⁇ 2.05.
  • exclusively difunctional and mono-functional building blocks are used, and in a very particularly preferred embodiment exclusively difunctional building blocks are used.
  • the components al) to a3) and al) are used in the following amounts for the preparation of the polyurethane, i. incorporated in the polyurethane, wherein the individual amounts always add up to 100 wt .-%: 5 to 40 wt .-% component al),
  • the components al) to a3) and bl) are used in the following amounts for the preparation of the polyurethane, i. incorporated in the polyurethane, wherein the individual amounts always add up to 100 wt .-%:
  • the components al) to a3) and bl) are used in the following amounts to prepare the polyurethane, i. incorporated in the polyurethane, wherein the individual amounts always add up to 100 wt .-%: 10 to 30 wt .-% component al),
  • the abovementioned amounts of the individual components a1), a2), a3) and bl) denote the amounts used to prepare the polyurethane and do not take into account additional amounts of these components which are optionally present or added as solvents.
  • a dissolution step can take place. Also during or after the addition of b 1), a dissolution step can take place.
  • the components al), a2) and optionally a3) are preferably completely or partially initially charged for the preparation of an isocyanate-functional polyurethane prepolymer, optionally diluted with an isocyanate-inert solvent and at temperatures in the range from 50 to 120 ° C heated up.
  • the catalysts known in polyurethane chemistry can be used.
  • the constituents of al), a2) and, if appropriate, a3) which have not yet been added at the beginning of the reaction are subsequently metered in.
  • the molar ratio of isocyanate groups to isocyanate-reactive groups is generally 1.05 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2.5.
  • Isocyanate-reactive groups are to be understood as all groups reactive toward isocyanate groups, such as, for example, primary and secondary amino groups, hydroxyl groups or thiol groups.
  • the reaction of the components a1), a2) and optionally a3) to give the prepolymer takes place partially or completely, but preferably completely.
  • polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution.
  • the resulting prepolymer can be dissolved with the aid of one or more organic solvents.
  • NH 2 - and / or NH-functional components are reacted with the remaining isocyanate groups of the prepolymer.
  • the chain extension ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension and chain termination under b) to free NCO groups of the prepolymer prepared under a), is generally between 50 and 150%, preferably between 50 and 120%, especially preferably between 60 and 100% and most preferably around 100%.
  • the aminic components b1) can optionally be used individually or in mixtures in solvent-diluted form, it being possible in principle for any order of addition to be possible.
  • Alcoholic solvents can also be used for chain extension or chain termination. As a rule, only part of the alcoholic solvent contained is incorporated into the polymer chain.
  • the diluent content in the chain-extending component used in b) is preferably 1 to 95% by weight, more preferably 3 to 50% by weight, based on the total weight of component B 1) inclusive diluent.
  • the dilute polyurethane solutions contain at least 5% by weight of polyurethane, based on the solids content of all components included in the composition, ie, based on the total solids content.
  • Suitable solvents for the polyurethane solutions are, for example, esters, such as, for example, ethyl acetate or methoxypropyl acetate or butyrolactone, alcohols, for example ethanol, n-propanol or isopropanol, ketones, for example acetone or methyl ethyl ketone, ethers, for example tetrahydrofuran or tert-butyl methyl ether. Preference is given to using esters, alcohols, ketones and / or ethers.
  • esters such as, for example, ethyl acetate or methoxypropyl acetate or butyrolactone
  • alcohols for example ethanol, n-propanol or isopropanol
  • ketones for example acetone or methyl ethyl ketone
  • ethers for example tetrahydrofuran or tert-butyl methyl ether.
  • At least one alcohol preferably at least one aliphatic alcohol, more preferably at least one aliphatic alcohol having from 2 to 6 carbon atoms, such as, for example, ethanol, n-propanol and / or isopropanol and at least one further solvent selected from the groups of esters, ketones or ether.
  • the particularly preferred content of alcoholic solvents is from 10 to 80% by weight, very particularly preferably from 25 to 65% by weight, based on the total weight of all solvents.
  • Alcohols are referred to in the context of the invention as a solvent, as long as they are added after formation of the isocyanate-functional prepolymers.
  • the proportion of alcohols used as hydroxy-functional compound a3) in the preparation of the isocyanate-functional prepolymer and covalently incorporated into this is not one of the solvents.
  • the polyurethane solution contains less than 5 wt .-%, preferably less than 1 wt .-%, more preferably less than 0.3 wt .-% water based on the total weight of the solution.
  • Suitable are e.g. Mixtures of polymers based on polyurethanes, polyesters, poly (meth) acrylates, polyepoxides, polyvinyl acetates, polyethylene, polystyrene, polybutadienes, polyvinyl chloride and / or corresponding copolymers.
  • the polymers which can be used for the preparation of the protective layer may additionally contain auxiliaries and additives.
  • auxiliaries and additives are crosslinked, thickeners, cosolvents, thixotropic agents, stabilizers, antioxidants, light stabilizers, plasticizers, pigments, fillers, water repellents and leveling agents.
  • the polymers may additionally contain biocides, wound-healing or other active substances, for example analgesics or antiphlogistics.
  • the order of the polymers for example in the form of a solution, can be carried out according to all known forms of application, mention may be, for example, doctoring, brushing, pouring or spraying. Preference is given to spraying a solution of the polymers.
  • a multilayer application with possibly interim drying steps is also possible in principle.
  • the protective layer of the polymers may typically have a thickness of from 1 to 500 ⁇ m, preferably from 2 to 300 ⁇ m, more preferably from 5 to 200 ⁇ m, very particularly preferably from 5 to 50 ⁇ m.
  • Another object of the invention is a method for producing an adhesive composite system according to the invention in the
  • the water-impermeable protective layer is applied.
  • an adhesive composite system obtainable by the process according to the invention.
  • the invention also provides adhesive composite system according to the invention for use as a means for covering, closing or bonding cell tissue
  • the solids contents were determined according to DIN-EN ISO 3251.
  • NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
  • the indicated viscosities were determined by means of rotational viscometry according to DIN 53019 at 23 ° C. with a rotational viscometer from Anton Paar Germany GmbH, Ostfildern, DE.
  • Desmophen C2200 Polycarbonate polyol, OH number 56 mg KOH / g, number average
  • Desmophen ® C 1200 polycarbonate polyol, OH number 112 mg KOH / g, number average molecular weight 1000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)
  • PolyTHF 2000 polytetramethylene glycol polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (BASF AG, Ludwigshafen, DE)
  • PolyTHF 1000 polytetramethylene glycol polyol, OH number 1 12 mg KOH / g, number-average number average molecular weight 1000 g / mol (BASF AG, Ludwigshafen, DE)
  • Example 1 Polymer layers of polyurethane solution (according to the invention)
  • Viscosity (viscometer, 23 ° C): 4600 mPas
  • Example 2 Polyurethane Solution Polymeric Layers (Inventive) 200 g of Desmophen C 2200 and 50 g of Desmophen C 1200 were mixed in a standard
  • Example 3 Polymer layers of polyurethane solution (according to the invention)
  • Viscosity (viscometer, 23 ° C): 11200 mPas
  • Example 4 Polymer layers of polyurethane solution (according to the invention)
  • Isophorone diisocyanate and 500 g of ethyl acetate were added and stirred at reflux (about 8 hours) until the theoretical NCO value was reached.
  • the finished prepolymer was cooled to 20 ° C and then a solution of 31, 3 g of methylenebis (4-aminocyclohexan) and 500g isopropanol was added within 30 min. The mixture was then stirred until free isocyanate groups were no longer detectable by IR spectroscopy.
  • Viscosity (viscometer, 23 ° C): 4600 mPas
  • Example 5 Synthesis of a strongly swelling polyurethane wound adhesive which was used for the subsequent experiments
  • Example 6 Example of an unprotected polyurethane wound adhesive
  • Example 6 On a glass plate 3 cm long and 1 cm wide strips of the polyurethane wound adhesive from Example 6 were applied using an applicator. After 30 minutes, the polyurethane solutions from Example 1-4 were applied using a brush so that the wound adhesive and the surrounding glass plate were completely covered. After a drying time of 5 min. The plate was placed in warm water of up to 40 ° C. for 6 to 40 minutes and the behavior of the wound adhesive was examined with regard to swelling and / or detachment from the glass plate. Among the polyurethane protective films described, the wound adhesive remained optically unchanged at 40 ° C. for up to 30 minutes. There was no detachment from the glass plate.
  • Example 8 Application example of a polyacrylate system Analogously to Example 7, the wound adhesive from Example 6 was over-sprayed with an acrylate-based spray plaster consisting of polyisobutene, isopropyl hydrogen maleate, methyl acrylate, ethyl acetate and pentane. The protective film has protected the underlying adhesive from swelling for up to 40 minutes at 40 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un système composite adhésif comprenant une couche d'une colle tissulaire et une couche protectrice appliquée sur la surface de la couche de colle, la colle tissulaire étant à base de polymères de polyuréthane hydrophiles et la couche protectrice étant imperméable à l'eau. L'invention concerne également un procédé de préparation du système composite adhésif, un système composite adhésif pouvant être obtenu selon ledit procédé, un système composite adhésif destiné à être utilisé en tant que produit servant à recouvrir, fermer ou coller du tissu cellulaire et l'utilisation dudit système composite adhésif pour la préparation d'un produit servant à recouvrir, fermer ou coller du tissu cellulaire.
PCT/EP2010/068985 2009-12-12 2010-12-06 Système composite adhésif servant à recouvrir, fermer ou coller du tissu cellulaire WO2011069973A2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU2010329976A AU2010329976A1 (en) 2009-12-12 2010-12-06 Adhesive composite system for covering, closing or gluing cellular tissue
US13/515,100 US20120276382A1 (en) 2009-12-12 2010-12-06 Adhesive composite system for covering, closing or gluing cellular tissue
JP2012542496A JP2013513679A (ja) 2009-12-12 2010-12-06 細胞組織を閉合または接着するための接着組成物系
BR112012014192A BR112012014192A2 (pt) 2009-12-12 2010-12-06 sistema compósito adesivo para cobrir, fechar ou colar tecido celular
CA 2783981 CA2783981A1 (fr) 2009-12-12 2010-12-06 Systeme composite adhesif servant a recouvrir, fermer ou coller du tissu cellulaire
IN5173DEN2012 IN2012DN05173A (fr) 2009-12-12 2010-12-06
CN2010800563529A CN102725320A (zh) 2009-12-12 2010-12-06 用于覆盖、封闭或者粘结细胞组织的复合粘合体系

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20090015401 EP2336212B1 (fr) 2009-12-12 2009-12-12 Système composite de colle destiné à recouvrir, fermer ou coller des tissus cellulaires
EP09015401.4 2009-12-12

Publications (2)

Publication Number Publication Date
WO2011069973A2 true WO2011069973A2 (fr) 2011-06-16
WO2011069973A3 WO2011069973A3 (fr) 2011-09-29

Family

ID=41813755

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/068985 WO2011069973A2 (fr) 2009-12-12 2010-12-06 Système composite adhésif servant à recouvrir, fermer ou coller du tissu cellulaire

Country Status (13)

Country Link
US (1) US20120276382A1 (fr)
EP (1) EP2336212B1 (fr)
JP (1) JP2013513679A (fr)
KR (1) KR20120104994A (fr)
CN (1) CN102725320A (fr)
AT (1) ATE548400T1 (fr)
AU (1) AU2010329976A1 (fr)
BR (1) BR112012014192A2 (fr)
CA (1) CA2783981A1 (fr)
DK (1) DK2336212T3 (fr)
ES (1) ES2381528T3 (fr)
IN (1) IN2012DN05173A (fr)
WO (1) WO2011069973A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104105731A (zh) * 2011-12-20 2014-10-15 医用粘合剂革新有限责任公司 用于生物可降解组织粘合剂的异氰酸酯官能的预聚物
JP2015509090A (ja) * 2012-01-09 2015-03-26 メディカル・アドヒーシブ・レボリューション・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＭｅｄｉｃａｌ Ａｄｈｅｓｉｖｅ Ｒｅｖｏｌｕｔｉｏｎ ＧｍｂＨ 修飾ベータ−アミノ酸エステル（アスパラギン酸エステル）硬化剤およびポリ尿素組織接着剤におけるその使用

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT2673311E (pt) * 2011-02-09 2014-11-12 Bayer Materialscience Ag Adesivo para tecido à base de aspartatos trifuncionais
EP2543395A1 (fr) * 2011-07-04 2013-01-09 Bayer MaterialScience AG Montage en couche destiné à l'occlusion de fuites tissulaires
CN102977723B (zh) * 2011-09-02 2016-11-23 3M新设资产公司 保护性组合物
CN107429140B (zh) 2015-01-21 2021-03-16 3M创新有限公司 耐化学品性聚氨酯粘合剂
DE102016123121A1 (de) 2016-11-30 2018-05-30 Kömmerling Chemische Fabrik GmbH Vorrichtung und Verfahren zum Applizieren eines Reaktivmassenstrangs
US20200254136A1 (en) * 2017-10-02 2020-08-13 Aleo Bme, Inc. Water-based tissue adhesives
DE102018202050A1 (de) * 2018-02-09 2019-08-14 Glue Tec Industrieklebstoffe Gmbh & Co. Kg Zweikomponenten-strukturklebstoffe
CN116041661B (zh) * 2023-03-27 2023-05-30 北京艾方德科技有限公司 一种腔体止血用医用聚氨酯泡沫材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69311633T2 (de) 1992-06-10 1997-10-16 Bayer Ag Lagerstabile Polyharnstoffbeschichtungszusammensetzungen
EP2011808A1 (fr) 2007-07-03 2009-01-07 Bayer MaterialScience AG Colle médicale pour la chirurgie

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE58909489D1 (de) * 1988-11-26 1995-12-14 Stockhausen Chem Fab Gmbh Wässrige polyurethan- bzw. polyurethanharnstoffdispersionen, verfahren zum beflocken elastomerer formkörper sowie zur heissversiegelung von textilen flächengebilden unter verwendung dieser dispersionen.
DE3903796A1 (de) * 1989-02-09 1990-08-16 Stockhausen Chem Fab Gmbh Waessrige polyurethan- bzw. polyurethanharnstoffdispersionen, verfahren zum beflocken elastomerer formkoerper sowie zur heissversiegelung von textilen flaechengebilden unter verwendung dieser dispersionen
DE10330971B4 (de) * 2003-07-08 2007-03-29 Beiersdorf Ag Verfahren zur Herstellung von Haut- oder Wundauflagen mit verkapselten, wundheilungsfördernden und/oder hautpflegenden Substanzen
EP1732956A1 (fr) * 2004-03-22 2006-12-20 E. I. du Pont de Nemours and Company Polyols proteges par orthoester pour revetements a faible teneur en composes organiques volatiles
US20070100112A1 (en) * 2005-10-27 2007-05-03 Bayer Materialscience Llc Polyurethane-urea elastomers
US7960495B2 (en) * 2006-12-18 2011-06-14 Ppg Industries Ohio, Inc. (Meth)acrylate/aspartate amine curatives and coatings and articles comprising the same
EP2083025A1 (fr) * 2008-01-24 2009-07-29 Bayer MaterialScience AG Colle médicale pour la chirurgie

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69311633T2 (de) 1992-06-10 1997-10-16 Bayer Ag Lagerstabile Polyharnstoffbeschichtungszusammensetzungen
EP2011808A1 (fr) 2007-07-03 2009-01-07 Bayer MaterialScience AG Colle médicale pour la chirurgie

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
EINTRAG: "aktiver Wasserstoff in Römpp Chemie Lexikon", GEORG THIEME VERLAG

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104105731A (zh) * 2011-12-20 2014-10-15 医用粘合剂革新有限责任公司 用于生物可降解组织粘合剂的异氰酸酯官能的预聚物
JP2015508426A (ja) * 2011-12-20 2015-03-19 メディカル・アドヒーシブ・レボリューション・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＭｅｄｉｃａｌ Ａｄｈｅｓｉｖｅ Ｒｅｖｏｌｕｔｉｏｎ ＧｍｂＨ 生分解性組織接着剤用のイソシアネート官能性プレポリマー
US9375509B2 (en) 2011-12-20 2016-06-28 Medical Adhesive Revolution Gmbh Isocyanate-functional prepolymer for a biologically degradable fabric adhesive
US9468701B2 (en) 2011-12-20 2016-10-18 Adhesys Medical Gmbh Isocyanate-functional prepolymer for a biologically degradable fabric adhesive
CN108570140A (zh) * 2011-12-20 2018-09-25 阿德希西斯医疗有限公司 用于生物可降解组织粘合剂的异氰酸酯官能的预聚物
JP2015509090A (ja) * 2012-01-09 2015-03-26 メディカル・アドヒーシブ・レボリューション・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＭｅｄｉｃａｌ Ａｄｈｅｓｉｖｅ Ｒｅｖｏｌｕｔｉｏｎ ＧｍｂＨ 修飾ベータ−アミノ酸エステル（アスパラギン酸エステル）硬化剤およびポリ尿素組織接着剤におけるその使用
JP2017047203A (ja) * 2012-01-09 2017-03-09 アドヒーシス・メディカル・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＡｄｈｅｓｙｓ Ｍｅｄｉｃａｌ ＧｍｂＨ 修飾ベータ−アミノ酸エステル（アスパラギン酸エステル）硬化剤およびポリ尿素組織接着剤におけるその使用

Also Published As

Publication number Publication date
ES2381528T3 (es) 2012-05-29
AU2010329976A1 (en) 2012-06-21
KR20120104994A (ko) 2012-09-24
EP2336212A1 (fr) 2011-06-22
WO2011069973A3 (fr) 2011-09-29
EP2336212B1 (fr) 2012-03-07
US20120276382A1 (en) 2012-11-01
CA2783981A1 (fr) 2011-06-16
CN102725320A (zh) 2012-10-10
DK2336212T3 (da) 2012-06-18
JP2013513679A (ja) 2013-04-22
BR112012014192A2 (pt) 2016-05-31
IN2012DN05173A (fr) 2015-10-23
ATE548400T1 (de) 2012-03-15

Similar Documents

Publication Publication Date Title
EP2336212B1 (fr) Système composite de colle destiné à recouvrir, fermer ou coller des tissus cellulaires
EP2182018B1 (fr) Colle chirurgicale
EP2232601B1 (fr) Convertisseur d'énergie composé de dispersions filmogènes aqueuses de polyuréthane
EP2331156B1 (fr) Solutions de polyuréthane hydrophiles à base de tcd
EP3545025B1 (fr) Procédé de fabrication d'un objet revêtu au moins partiellement
EP2459611B1 (fr) Convertisseur électromécanique doté d'un élément polymère basé sur un mélange en polyisocyanate et de pré-polymères fonctionnels avec de l'isocyanate et sur une liaison dotée d'au moins deux groupes hydroxy réactifs à isocyanate
EP1920017A1 (fr) Dispersions de polyurethane-polyuree
EP2340575B1 (fr) Convertisseur d'énergie à base de solutions de polyuréthane
EP2331596B1 (fr) Dispersions de polyuréthane hydrophiles à base de tcd
EP2377895A1 (fr) Dispersions aqueuses de poly-résine de polyuréthane
WO2010012389A1 (fr) Transducteur électromécanique avec un élément en polymère à base de polyisocyanate
EP2389402A1 (fr) Mousses polyuréthane stabilisées au moyen de polyuréthanes/tensioactifs
EP2012747B1 (fr) Utilisation de dispersions d'polyurethane aqueouses pour produits à mâcher en produits cosmétiques
EP2257581A1 (fr) Solutions de polyuréthane hydrophiles
WO2009024272A1 (fr) Dispersions nc-pu à séchage accéléré
EP2478026B1 (fr) Urées de polyuréthane hydrophiles à base de cyclo-hexane-di-méthanol
EP3177656B1 (fr) Solutions de polyuréthane pour revêtements textiles
WO2010043333A1 (fr) Dispersions aqueuses de polyuréthanne-polyurée

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080056352.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10787450

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010329976

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2783981

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 20127014974

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2012542496

Country of ref document: JP

Ref document number: 13515100

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 5173/DELNP/2012

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2010329976

Country of ref document: AU

Date of ref document: 20101206

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012014192

Country of ref document: BR

122 Ep: pct application non-entry in european phase

Ref document number: 10787450

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 112012014192

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20120612