EP1611272B1 - Corps façonnes cellulosiques a action fonctionnelle et leur procede de fabrication - Google Patents

Corps façonnes cellulosiques a action fonctionnelle et leur procede de fabrication Download PDF

Info

Publication number
EP1611272B1
EP1611272B1 EP04725036A EP04725036A EP1611272B1 EP 1611272 B1 EP1611272 B1 EP 1611272B1 EP 04725036 A EP04725036 A EP 04725036A EP 04725036 A EP04725036 A EP 04725036A EP 1611272 B1 EP1611272 B1 EP 1611272B1
Authority
EP
European Patent Office
Prior art keywords
fibres
ions
fibers
silver
process according
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.)
Expired - Lifetime
Application number
EP04725036A
Other languages
German (de)
English (en)
Other versions
EP1611272A1 (fr
Inventor
Reiner BÜTTNER
Hardy Markwitz
Carmen Knobelsdorf
Ralf Bauer
Frank Meister
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.)
Thueringisches Institut fuer Textil und Kunststoff Forschung eV
Original Assignee
Thueringisches Institut fuer Textil und Kunststoff Forschung eV
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 Thueringisches Institut fuer Textil und Kunststoff Forschung eV filed Critical Thueringisches Institut fuer Textil und Kunststoff Forschung eV
Priority to PL04725036T priority Critical patent/PL1611272T3/pl
Publication of EP1611272A1 publication Critical patent/EP1611272A1/fr
Application granted granted Critical
Publication of EP1611272B1 publication Critical patent/EP1611272B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D06M11/42—Oxides or hydroxides of copper, silver or gold
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • Y10T428/2905—Plural and with bonded intersections only

Definitions

  • the invention relates to a cellulosic molded body and to a process for the production of cellulosic molded bodies by the dry-wet extrusion process with improved and extended functional effects, in particular for use in medicine, hygiene, clothing, papermaking and the packaging industry.
  • the functional effect relates to a uniform and finely dosed bactericidal action, especially in wound dressings, sports and leisure clothing, hospital textiles, filter and packaging papers.
  • the moldings are able to adsorb metals from heavy metal-containing media.
  • the heavy metal loaded moldings can be used as antibacterial and / or fungicidal material.
  • the content of adsorbed heavy metals in these cellulosic moldings is at least about 70 mg / kg, based on the total weight of the cellulosic molding.
  • the invention has for its object to provide a cellulosic molded body and a method for the production of cellulosic moldings having a functional effect in particular for use in medicine, hygiene and clothing, which shows a bactericidal effect and this particular connects with the advantages of a breathable garment.
  • Patent Abstracts of Japan Vol. 0152. No. 01 (C-0834) of the JP 3 054234 discloses the preparation of a cellulose composition having an ion exchange function useful as a metal ion binder by mixing a specific regenerated cellulose and an anionic polymer and solidifying the mixture.
  • the drug concentration to be delivered should be controllable.
  • the shaped bodies produced by the process according to the invention in particular fibers and films, are to be created in such a way that they are suitable for production as wound dressings, plasters, hygiene articles, textiles, specialty papers and as packaging material due to their high adsorption capacity.
  • composites of mixtures with other fibers should be produced.
  • Weakly crosslinked ion exchangers for the purposes of the present invention are ion exchangers which are provided with a reduced proportion of crosslinking agents.
  • Conventional ion exchange resins have a crosslinker content of 4 to 12% by weight, based on the mass of the exchange resin.
  • Weakly crosslinked ion exchangers for the purposes of the present invention have a crosslinker content of from 0.1 to 2.0% by weight, preferably from 0.3 to 1.5% by weight, particularly preferably from 0.5 to 1.2% by weight.
  • the fibers produced with incorporated weakly crosslinked cation exchangers exceed those of the brown algae with their binding capacity for silver ions DE 10 140 772 by up to 28 times. It is thus given the opportunity to produce fibers or films, the z. B. can be highly loaded with cationic bactericidal agents such as silver ions.
  • a fiber with 15% by mass of moderately cross-linked cation exchanger can be loaded with about 80 g of silver. Silver loading of the fiber with> 100 g Ag / kg fiber is possible with a corresponding increase in the mass fraction of the incorporated weakly crosslinked cation exchanger.
  • These fibers can then be prepared by mixing with other fibers, such as.
  • fibers which have a sufficient content in terms of silver content per fiber to show a sufficient bactericidal effect, but show no disadvantages in terms of textile-physical parameters.
  • from 0.5 to 1.5% by weight, based on the cellulosic mass of the fiber of 5000 to 10000 mg Ag / kg of fiber incorporated in the weakly crosslinked cation exchanger can be bound to the fiber.
  • Such fibers show a completely sufficient bactericidal action in the hitherto known fields of use and are equal in their textile-physical values to unmodified fibers. The processing of these fibers and yarns made from them is possible on all textile machines.
  • a measure of the expected bactericidal effect of the fibers or yarns is the equilibrium concentration of the active ingredients in aqueous solutions such.
  • the free Ag ions are consistently discharged, with the equilibrium concentration being maintained over time by the Ag deposited in the fiber. Due to the increased depot effect of the fibers according to the invention thus the equilibrium concentration can be maintained over an increased period.
  • these functionalized with cationic active ingredients fibers are possible. So these fibers can be active ingredients such.
  • the fibers may be processed in the form of patches and used as transdermal therapeutic systems.
  • the loading of the functionalized fibers may conveniently be done by dipping in a solution with the appropriate ions. Diving can be done both in batch mode and continuously. In continuous dipping, preferably the cut fiber is loaded in a separate bath in the after-treatment.
  • a 12% by mass cellulose solution in N-methylmorpholine N-oxide monohydrate is a powdery weakly crosslinked cation exchanger based on a crosslinked copolymer of acrylic acid and sodium acrylate having a particle size ⁇ 10 .mu.m in a weight fraction of 15 mass%, based a cellulose content added.
  • This spinning solution is homogenized in a kneader and spun at a temperature of about 90 ° C through a spinneret with 480 holes and a nozzle hole diameter of 80 microns.
  • the take-off speed is 30 m / min.
  • the multifilament yarn is passed through several washing baths to leach the N-methylmorpholine N-oxide.
  • the fibers are spun off and loaded with 10 liters of a 0.1 M silver nitrate solution per kg of fiber material. After loading, the fibers are spun and washed free from adhering silver nitrate. Subsequently, the fibers are dried at about 80 ° C. Table 2: fineness dtex 0.7 Fineness-based tear strength dry CN / tex 22.5 Stretching dry % 14.8 Fineness-related loop tear force CN / tex 7.5 silver content g / kg fiber 80
  • Table 2 shows the fiber parameters and the silver content of the fiber.
  • Such a highly loaded fiber has the advantage that by blending the fiber with other textile fibers such.
  • Yarns produced in this way can be processed very well on knitting and knitting machines, in contrast to galvanized polyamide threads.
  • Fibers are spun according to Example 1 with a titer of 0.17 tex and a content of weakly crosslinked cation exchanger of 6% by mass, based on the Cellulose content. These fibers are loaded according to Example 1 with silver ions. The fiber parameters are listed in Table 3.
  • Fibers are prepared according to Example 1 with a titer of 0.5 tex and a content of weakly crosslinked cation exchanger of 0.5% by mass, based on the cellulose content.
  • the loading with silver ions is carried out analogously to Example 1.
  • the fiber parameters are shown in Table 3.
  • Table 3 a fiber without weakly crosslinked cation exchanger was included for comparison.
  • Example 2 Example 3 Fiber without weakly crosslinked cation exchanger fineness dtex 0.17 0.5 0.5 Fineness-based tear strength dry CN / tex 35.8 37.6 38.1 Stretching dry % 13.0 11.4 11.8 Fineness-related loop tear force CN / tex 8.2 9.1 9.5 silver content g / kg fiber 36.6 4.6 -
  • Example 4 Example 5 fineness dtex 0.5 0.5 Fineness-based dry breaking strength CN / tex 31.2 30.9 Stretching dry % 14.2 13.5 Fineness-related loop tear force CN / tex 9.1 8.5 silver content g / kg fiber 17.5 13.6
  • Example 5 Working analogously to Example 4 and gives the mash 6% by mass of a weakly acidic macroporous cation exchanger based on crosslinked polyacrylate in the sodium form, so that in the spun fiber 6% by mass of ion exchange based on the cellulose content, this washes Fiber and loaded with silver ions as described in Example 1, we obtain a fiber with 13.6 g Ag / kg fiber. It is surprisingly clear from example 5 that the polyacrylate-based ion exchanger absorbs less than half of silver ions than the weakly crosslinked polyacrylate-based cation exchanger.
  • Fibers with weakly crosslinked cation exchangers as well as conventional prior art ion exchanges prepared according to Examples 1 to 5 were loaded with silver, cupric and zinc ions. The results are shown in Table 5.
  • Table 5 Fiber incorporated with Metal content g / kg fiber copper silver Silver / zinc 20 mass% ion exchanger after Example 4 (Vergeleichsbeispiel) 23.7 57.1 23.9 / 27.5 20 mass% ion exchanger after Example 5 (Vergeleichsbeispiel) 11.5 41.7 36.4 / 24.5 15% by mass of weakly crosslinked cation exchanger as in Examples 1 to 3 25.5 85.8 59.5 / 30.5
  • Fibers loaded with copper ions, silver ions or with a combination of silver and zinc ions can be used as bactericidal fibers.
  • a 11% by mass cellulose solution in N-methylmorpholine N-oxide monohydrate is a suspension of a weakly crosslinked cation exchanger based on a crosslinked copolymer of acrylic acid and sodium acrylate and a strongly basic anion exchanger based on a styrene-divinylbenzene copolymer with trialkylammonium Groups in chloride form in 85% N-methylmorpholine N-oxide in such a concentration that the spinning solution 11% by mass of cellulose and based on the cellulose content 8% by mass of the weakly crosslinked cation exchanger and 8% by mass of the anion exchanger.
  • the spinning solution according to Example 1 is spun with a titer of 0.5 tex.
  • the fibers have a tenacity of 26.3 cN / tex, an elongation of 12.1% and a fineness-related loop tearing force of 8.6 cN / tex.
  • the silver loading is 52.4 g silver / kg fiber and the loading with benzoate is 16.6 g benzoate / kg fiber. These fibers have a very strong bactericidal action.
  • the example demonstrates the suitability of the fibers of the present invention for combined use with prior art anion exchange and cation exchange loaded fibers.
  • Inventive ion exchange fibers or films with incorporated cation exchangers prepared according to Example 2 are loaded with nicotine.
  • the loaded fibers or films are washed and dried. These fibers or films can be processed into textile depots and used as transdermal therapeutic systems.
  • Fibers prepared according to Example 1 were applied to their bactericidal Effect in the style of the European Pharmacopaeia (EP 2002), Chapter 2.6.12 , Bioburden determination tested.
  • Papers containing fibers according to Example 1 were tested in an amount such that a gradation of the silver contents in the paper was 190 mg Ag / kg, 760 mg Ag / kg and 3800 mg Ag / kg paper.
  • the test was carried out on the following microorganisms (Tables 6 - 9): Pseudomonas aeruginosa ATCC 9027 Staphylococcus aureus ATCC 6538 Bacillus subtilis spores ATCC 6633 Fusarium solani spores ATCC 36031.
  • Table 6 - Pseudomonas aeruginosa silver content Germ numbers after incubation period 0 min.
  • the comparative sample was a paper without silver-containing fibers. Dependencies of the microbiocidal activity with regard to exposure time and concentration of the silver loading could be detected for all test germs. As expected, Bacillus subtilis spores showed the highest resistance. But even with these a lowering of the germs could be achieved.
  • Fibers made according to Example 1 were spun with cotton to stocking yarn with a denier Nm 68/1 and a silver content of 1300 mg Ag / kg yarn. From this yarn, a knitted tube was made and tested for bactericidal action (sample 31444083). The test was carried out in accordance with SN195924. The test organism was Lactobacillus brevis DSM 20054. The control sample used was non-antimicrobial cotton fabric (Table 10). In each case 5 measurements were carried out on the basis of the same sample material and the control sample. Table 10 - Results of the test of antibacterial activity in the germ carrier test on the test bacterium Lactobacillus brevis.
  • the 24-hour value of the growth control (control or standard tissue) must be at least two orders of magnitude above the initial value (AE ⁇ -2).

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Biochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Artificial Filaments (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Knitting Of Fabric (AREA)
  • Nonwoven Fabrics (AREA)
  • Paper (AREA)

Claims (13)

  1. Une méthode de fabrication de produits cellulosiques fonctionnels, moulés selon le procédé d'extrusion sec-humide, caractérisée par le fait que les fibres ou les feuilles cellulosiques comprenant au moins un échangeur d'ions cationique incorporé, à faible réticulation, ayant des ions métalliques à action bactéricide et/ou des agents ioniques pharmaceutiques, sont chargées de manière à ce qu'un dépôt de ces agents est formé dans la fibre et que ces agents seront libérés à la longue, suivant leur taux de concentration, lorsque ces fibres ou ces feuilles sont appliquées en solutions aqueuses.
  2. Une méthode conformément à la revendication 1, caractérisée par le fait que l' échangeur d'ions cationique à faible réticulation est un polyacrylate.
  3. Une méthode conformément aux revendications 1 ou 2, caractérisée par le fait que les ions métalliques sont des ions d'argent.
  4. Une méthode conformément à la revendication 2, caractérisée par le fait que d'autres ions métalliques à action bactéricide sont utilisés comme ions métalliques, en particulier les ions de cuivre, de mercure, de zircon ou de zinc.
  5. Une méthode conformément à l'une des revendications sus-mentionnées, caractérisée par le fait que les agents ioniques pharmaceutiques sont des agents anioniques, en particulier l'acide benzoïque ou l'acide sorbique.
  6. Une méthode conformément à l'une des revendications sus-mentionnées, caractérisée par le fait que la concentration de l'agent se situe entre 0,005 et > 100g d'agent par kilo de produit moulé.
  7. Une méthode conformément à l'une des revendications sus-mentionnées, caractérisée par le fait que les fibres chargées d'agent sont mélangées à des fibres textiles et manufacturées en produits de forme plane.
  8. Une méthode conformément à la revendication 7, caractérisée par le fait que les fibres textiles sont choisies hors du groupe comprenant le coton, la laine, les fibres polyamides, les fibres polyacryliques, les fibres de polypropylène et les fibres cellulosiques régénérées.
  9. Une méthode conformément à l'une des revendications sus-mentionnées, caractérisée par le fait que les produits cellulosiques contiennent en plus des échangeurs d'ions cationiques et/ou anioniques.
  10. Des produits cellulosiques fonctionnels, caractérisés par le fait que des échangeurs d'ions cationiques à faible réticulation sont incorporés, l'échangeur d'ions étant chargé d'ions métalliques à action bactéricide et/ou d'agents ioniques pharmaceutiques, et que de plus, le produit moulé libère à la longue en solutions aqueuses les ions métalliques et/ou les agents, suivant leur taux de concentration.
  11. Un produit cellulosique conformément à la revendication 10, caractérisé par le fait que les ions métalliques sont en partie au moins des ions d'argent.
  12. Un produit de forme plane contenant au moins une part de produit cellulosique conformément à l'une des revendications 10 ou 11.
  13. Un produit de forme plane conformément à la revendication 12, caractérisé par le fait que la texture est un papier, une peau de saucisse ou un revêtement en nappe de fibres.
EP04725036A 2003-04-04 2004-04-01 Corps façonnes cellulosiques a action fonctionnelle et leur procede de fabrication Expired - Lifetime EP1611272B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04725036T PL1611272T3 (pl) 2003-04-04 2004-04-01 Kształtki celulozowe o funkcjonalnym działaniu oraz sposób ich wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10315749A DE10315749A1 (de) 2003-04-04 2003-04-04 Verfahren zur Herstellung von cellulosischen Formkörpern mit funktionaler Wirkung
PCT/EP2004/003466 WO2004088009A1 (fr) 2003-04-04 2004-04-01 Corps façonnes cellulosiques a action fonctionnelle, et leur procede de fabrication

Publications (2)

Publication Number Publication Date
EP1611272A1 EP1611272A1 (fr) 2006-01-04
EP1611272B1 true EP1611272B1 (fr) 2009-08-26

Family

ID=32981104

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04725036A Expired - Lifetime EP1611272B1 (fr) 2003-04-04 2004-04-01 Corps façonnes cellulosiques a action fonctionnelle et leur procede de fabrication

Country Status (9)

Country Link
US (1) US20060283567A1 (fr)
EP (1) EP1611272B1 (fr)
JP (1) JP2006522232A (fr)
CN (1) CN100545325C (fr)
AT (1) ATE440981T1 (fr)
DE (2) DE10315749A1 (fr)
PL (1) PL1611272T3 (fr)
RU (1) RU2340710C2 (fr)
WO (1) WO2004088009A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006056977B3 (de) * 2006-11-30 2008-05-08 Smart Fiber Ag Verwendung eines textilen mikrobioziden Speichers
DE102007012972B4 (de) * 2007-03-14 2010-09-02 Smart Fiber Ag Vorrichtung zur bioziden Behandlung von Wäsche
DE102007019768A1 (de) * 2007-04-25 2008-11-13 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung einer bioaktiven Cellulosefaser mit hohem Weißgrad
DE102007054702B4 (de) * 2007-11-14 2018-10-18 Smartpolymer Gmbh Verfahren zur Herstellung von cellulosischen Formkörpern, cellulosischer Formkörper und dessen Verwendung
DE102009010968A1 (de) 2009-02-27 2010-09-02 Flockfaser GmbH Thüringen Antibakteriell aktive Flockfasern
CN102220730B (zh) * 2011-04-13 2013-08-28 成都印钞有限公司 钞票用银锌磷酸锆复合抗菌剂及其制备方法
RU2472892C1 (ru) * 2011-10-13 2013-01-20 Леонид Асхатович Мазитов Способ получения бактерицидной бумаги
GB2511528A (en) 2013-03-06 2014-09-10 Speciality Fibres And Materials Ltd Absorbent materials
CN104389245B (zh) * 2014-09-29 2016-02-17 吉特利环保科技（厦门）有限公司 一种纳米银抗菌纤维餐具的制备工艺
CN105200844A (zh) * 2015-08-21 2015-12-30 西南石油大学 一种抗菌消毒薄页纸的制备方法
DE102022109459A1 (de) 2021-04-21 2022-10-27 Smartpolymer Gmbh Waschpermanente bioaktive Cellulosefaser mit antibakteriellen und antiviralen Eigenschaften

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0622540B2 (ja) * 1985-12-18 1994-03-30 株式会社祥光化学研究所 消臭抗菌能を有する構造物
JP2528914B2 (ja) * 1986-12-16 1996-08-28 株式会社日本触媒 体液吸収物品
US4842593A (en) * 1987-10-09 1989-06-27 The Procter & Gamble Company Disposable absorbent articles for incontinent individuals
JPH0813905B2 (ja) * 1989-06-23 1996-02-14 大和紡績株式会社 イオン交換機能を持ったセルロース系組成物
JP2520321B2 (ja) * 1990-06-19 1996-07-31 大和紡績株式会社 イオン交換機能を持ったセルロ―ス系組成物
US5853867A (en) * 1995-09-14 1998-12-29 Nippon Shokubai Co., Ltd. Absorbent composite, method for production thereof, and absorbent article
TW474961B (en) * 1996-10-14 2002-02-01 Nippon Catalytic Chem Ind Water-swelling crosslinked polymer, production process thereof, and measurement method for pore volume of swollen crosslinked polymer
US6258368B1 (en) * 1997-06-04 2001-07-10 The Procter & Gamble Company Antimicrobial wipes
DE19805447A1 (de) * 1998-02-11 1999-08-12 Bayer Ag Modifizierte Superabsorber auf Basis von Polyacrylnitril-Emulsionen
US6110533A (en) * 1998-03-16 2000-08-29 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Polymeric desiccant articles and process for their manufacture
JP2000211901A (ja) * 1998-11-17 2000-08-02 Hisao Ishiguro 二酸化塩素含有ゲル状組成物とその製造方法及びその保管方法並びに二酸化塩素含有ゲル状組成物の充填体と二酸化塩素含有ゲル状組成物の充填体収納袋及び二酸化塩素含有ゲル状組成物収納容器
JP2000273313A (ja) * 1999-03-23 2000-10-03 Mizusawa Ind Chem Ltd 繊維乃至膜用配合剤及び繊維乃至膜形成用樹脂組成物
DE19917614C2 (de) * 1999-04-19 2001-07-05 Thueringisches Inst Textil Verfahren zur Herstellung von cellulosischen Formkörpern mit hohem Adsorptionsvermögen
US6660903B1 (en) * 1999-10-01 2003-12-09 Kimberly-Clark Worldwide, Inc. Center-fill absorbent article with a central rising member
DE10009471B4 (de) * 2000-02-28 2006-07-27 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung einer Lösung erhöhter thermischer Stabilität von Cellulose in wässrigem Aminoxid
US6828014B2 (en) * 2001-03-22 2004-12-07 Kimberly-Clark Worldwide, Inc. Water-dispersible, cationic polymers, a method of making same and items using same
DE10140772A1 (de) * 2001-08-20 2003-03-13 Zimmer Ag Verfahren zur Entfernung von Schwermetallen aus schwermetallhaltigen Medien unter Verwendung eines Lyocell-Formkörpers sowie Lyocell-Formkörper mit adsorbierten Schwermetallen und deren Verwendung
US7655112B2 (en) * 2002-01-31 2010-02-02 Kx Technologies, Llc Integrated paper comprising fibrillated fibers and active particles immobilized therein
JP2004123662A (ja) * 2002-10-07 2004-04-22 Lion Corp 角質除去シート

Also Published As

Publication number Publication date
ATE440981T1 (de) 2009-09-15
JP2006522232A (ja) 2006-09-28
US20060283567A1 (en) 2006-12-21
CN100545325C (zh) 2009-09-30
PL1611272T3 (pl) 2009-12-31
WO2004088009A1 (fr) 2004-10-14
DE502004009966D1 (de) 2009-10-08
EP1611272A1 (fr) 2006-01-04
RU2340710C2 (ru) 2008-12-10
DE10315749A1 (de) 2004-10-14
CN1816651A (zh) 2006-08-09
RU2005134210A (ru) 2006-05-10

Similar Documents

Publication Publication Date Title
DE102006056977B3 (de) Verwendung eines textilen mikrobioziden Speichers
DE60305172T2 (de) Antimikrobielles garn mit nanosilberpartikeln und verfahren zu seiner herstellung
DE60102291T2 (de) Antimikrobielle und antivirale polymermaterialien
EP1536848B1 (fr) Procede de fabrication d'un produit antimicrobien en matiere plastique
DE69521082T2 (de) Metallisches bakterizides Mittel
DE10140772A1 (de) Verfahren zur Entfernung von Schwermetallen aus schwermetallhaltigen Medien unter Verwendung eines Lyocell-Formkörpers sowie Lyocell-Formkörper mit adsorbierten Schwermetallen und deren Verwendung
EP1611272B1 (fr) Corps façonnes cellulosiques a action fonctionnelle et leur procede de fabrication
DE102006001954A1 (de) Antiseptische Alginatzubereitung
DE102005031711A1 (de) Vor mikrobiellem Befall geschützte Textilien
WO2008131720A1 (fr) Procédé de production d'une fibre cellulosique bioactive à haut degré de blanc
DE112013007131T5 (de) Verfahren zum Behandeln von Textilien während Nasswaschens
EP2334853B1 (fr) Corps moulés cellulosiques fonctionnels
EP1210386B1 (fr) Procede de fabrication de corps en plastique anti-microbiens a comportement ameliore sur la duree
CA3199096A1 (fr) Composition antimicrobienne incolore
DE102022109459A1 (de) Waschpermanente bioaktive Cellulosefaser mit antibakteriellen und antiviralen Eigenschaften
EP1383947A2 (fr) Produits fibreux bioactifs
DE69126520T2 (de) Antimikrobielle Zusammensetzung mit einer Hitze- und Witterungsbeständigkeit
EP2819711B1 (fr) Pansement antiseptique
DE602004004090T2 (de) Zum einmaligen gebrauch in krankenhaus und operationssaal bestimmte erzeugnisse auf basis von papier
DE602004007106T2 (de) Wegwerfprodukte für die weibliche hygiene
WO2001038615A1 (fr) Fibre synthetique monofilaire
DE112020000627T5 (de) Schmelzfasern für antimikrobielle Mittel und deren Herstellungsmethoden
KR102609452B1 (ko) 항균력을 갖는 멜트블로운 부직포 및 그 제조방법
DE10331324A1 (de) Verfahren zur Herstellung eines antimikrobiellen Kunststoffproduktes
WO2002042549A2 (fr) Sous-vetement a action antimicrobrienne et utilisation d'un textile pour sa fabrication

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20051001

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL HR LT LV MK

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BAUER, RALF

Inventor name: BUETTNER, REINER

Inventor name: MEISTER, FRANK

Inventor name: KNOBELSDORF, CARMEN

Inventor name: MARKWITZ, HARDY

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502004009966

Country of ref document: DE

Date of ref document: 20091008

Kind code of ref document: P

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091126

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091228

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20100329

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20100527

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20100422

Year of fee payment: 7

Ref country code: PL

Payment date: 20100325

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091127

BERE Be: lapsed

Owner name: THURINGISCHES INSTITUT FUR TEXTIL- UND KUNSTSTOFF

Effective date: 20100430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110401

REG Reference to a national code

Ref country code: PL

Ref legal event code: LAPE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100227

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110401

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502004009966

Country of ref document: DE

Representative=s name: PATENTANWAELTE FRITZ & BRANDENBURG, DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502004009966

Country of ref document: DE

Representative=s name: PATENTANWAELTE FRITZ & BRANDENBURG, DE

Effective date: 20150323

Ref country code: DE

Ref legal event code: R081

Ref document number: 502004009966

Country of ref document: DE

Owner name: SMARTPOLYMER GMBH, DE

Free format text: FORMER OWNER: THUERINGISCHES INSTITUT FUER TEXTIL- UND KUNSTSTOFF-FORSCHUNG E.V., 07407 RUDOLSTADT, DE

Effective date: 20150323

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: SMARTPOLYMER GMBH, DE

Free format text: FORMER OWNER: THUERINGISCHES INSTITUT FUER TEXTIL- UND KUNSTSTOFF-FORSCHUNG E.V., DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20150420

Year of fee payment: 12

Ref country code: CH

Payment date: 20150420

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20150421

Year of fee payment: 12

REG Reference to a national code

Ref country code: AT

Ref legal event code: PC

Ref document number: 440981

Country of ref document: AT

Kind code of ref document: T

Owner name: SMARTPOLYMER GMBH, DE

Effective date: 20150831

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: SMARTPOLYMER GMBH, DE

Effective date: 20151022

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20161230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160430

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160502

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160401

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502004009966

Country of ref document: DE

Representative=s name: DUDA, RAFAEL THOMAS, DIPL.-ING. DR. RER. NAT., DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230420

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20230420

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 502004009966

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 440981

Country of ref document: AT

Kind code of ref document: T

Effective date: 20240401