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 cellulosic forms as well as a method for producing cellulosic forms by the dry-wet extrusion process with improved and enhanced functional effects, especially applicable in medicine, hygiene, garment, paper manufacturing and packaging industry.
• the functional effect is directed to a steady and meticulously adjustable bactericide effect, especially for wound contact material, sports and leisure clothing, hospital textiles, filter and packaging papers.
• silver is for example galvanically deposited on the surface of polyamide silk.
• Working up of said galvanically silver-plated polyamide silk on knitters and moulders is problematical, since the silver layer of the polyamide silk is partially deposited on the yarn leading devices leading to numerous shut downs of said devices.
• metallic silver, silver-zeolite or silver-glass ceramics into the matrix of the fibre of melt spun fibres like polypropylene fibres, polyester fibres and polyamide fibres (Taschenbuch für die Textilindustrie 2003, Schiele & Schön Berlin, P. 124 ff).
• DE 10 140 772 discloses a method for producing cellulosic forms with incorporated algae. Said forms are able to adsorb metals from heavy metal containing media. The heavy metal loaded forms may be used as antibacterial and/or fungicidal material. The content of adsorbed heavy metals in said cellulosic forms is given as at least about 70 mg/kg, related to the total weight of the cellulosic forms.
• Patent Abstracts of Japan, Edition 0152, No. 01 (C-0834) of JP 3 054234 discloses the production of a cellulosic composition comprising an ion exchanger functionality, useful as binder for metal ions, wherein said production process consists of mixing a specifically generated cellulose and an anionic polymer followed by solidification of said mixture.
• Aim of the present invention is to provide a cellulosic form with functional effect as well as a method for preparing said cellulosic form, especially for the use in medicine, hygiene and garment, wherein said forms have a bactericide effect and wherein especially said advantages go along with breathable clothing.
• a further aim is to keep said active agents in a textile depot and further to obtain sufficient release of said agents from said depot over a period of time.
• the released concentrations of said agent should be controllable.
• the forms, especially fibres or foils, obtainable by the method of the invention should be formed thus, that they are useful for preparing wound overlays, band-aids, sanitary products, textiles, special papers and packaging material, because of the high adsorption ability of active agents.
• composites including differing fibres should be producible.
• the aim is reached in combination with the aforementioned discussed method according to the present invention by charging the cellulosic forms, wherein said forms are spun according to the dry-wet extrusion method and having incorporated weakly linked cationic active ion exchangers with active agents.
• the binding capacity for said active agents depends on the degree of cross-linking of the ion exchanger.
• the binding capacity for the cationic active agents like e.g. silver could be increased by more than the double amount, if polyacrylates are used, which were weakly cross-linked by a multifunctional cross-linker.
• Weakly cross-linked ion exchangers according to the present invention are ion exchangers with a decreased amount of cross-linkers.
• Usual ion exchanger resins show an amount of cross-linkers of 4 to 12 weight-%, based on the weight of the ion exchanger resin.
• Weakly cross-linked ion exchangers according to the present invention have an amount of cross-linkers ranging from 0.1 to 2.0 weight-%, preferably 0.3 to 1.5 weight-%, particularly preferably 0.5 to 1.2 weight-%.
• Fibres made with incorporated weakly cross-linked cation exchangers show a capacity for binding silver ions which surpasses the capacity of fibres with brown algae according to DE 10 140 772 up to the 28-fold.
• a fibre with 15 weight-% incorporated weakly cross-linked cationic ion exchanger may be loaded with about 80 g silver. Silver loads of fibres of >100 g Ag/kg fibre are possible, if the amount of the incorporated weakly cross-linked cation exchanger is increased accordingly.
• Said fibres may be mixed with other fibres, e.g. cotton, wool or synthetic fibres, to produce yarns with the desired silver content. This procedure allows the production of bactericidic yarns in a very economic way.
• ion exchangers are used on the basis of acrylic acid-divinylbenzene-copolymer-bound carboxyl groups or on the basis of a styrene-divinylbenzene-copolymer bound chelat forming imino-diacetic-acid as described in DE 19 917 614, fibres are obtained, which are comparable in their bactericide effect.
• the capacity for silver ions is less than 50% of the aforementioned weakly cross-linked cation exchangers.
• a measure for the bactericide effect of the fibres or yarns is the equilibration concentration of the active agent in aqueous solutions e.g. the concentration of the silver ions.
• fibres or yarns loaded with silver ions are put into distilled water at a temperature of 20° C., followed by a measurement of the equilibration concentration of the silver ions after 24 h.
• Table 1 shows the equilibration concentrations of silver ions and the load of silver in the fibres, while using weakly cross-linked cation exchangers or known ion exchangers cross-linked with divinyl-benzene.
• the equilibration concentration of silver ions is on a level which is above the necessary concentration of 0.01 to 1 mg/l to obtain a bactericide effect.
• the equilibration concentration may be controlled to each desired concentration level by mixing with other kinds of fibres.
• the fibres according to the present invention provide the equilibration concentration which is necessary to obtain an antimicrobial effect, at an increased Ag-content of the fibre at the same time.
• the advantages thereof are obvious.
• the equilibration concentration is uphold by the Ag deposited in the fibre. Due to the improved storing properties of the inventive fibres the equilibration concentration may be uphold over an extended period of time.
• fibres may be loaded with cation-active and anion-active bactericide ions, like silver ions and benzoic acid or asorbic acid.
• Such functionalised fibres with cation active agents within medical applications is possible.
• Such fibres may bind agents, like nicotine.
• Said fibres may be manufactured into band-aids and used for transdermal, therapeutic systems.
• Advantageously loading of said functional fibres may proceed by dipping the fibres into a solution of appropriate ions. Said dipping may be carried out continuously or in batch mode. When dipping in continuous mode it is preferred to load the cut fibre in a separate bath during subsequent treatment.
• Powdery weakly cross-linked cation exchanger based on a cross-linked copolymerisate of acrylic acid and sodium acrylate, having a grain size ⁇ 10 ⁇ m, is added to 12 weight-% cellulose solution in N-methylmorpholine-N-oxide monohydrate, in a weight proportion of 15 weight-%, based on the cellulose proportion.
• This spinning solution was homogenised in a kneader and spun with a spinning nozzle with 480 holes and a spinning hole diameter of 80 ⁇ m at a temperature of about 90° C. The draw off speed was about 30 m/min.
• the multifile fibre was led through several washing baths to wash out the residual N-methylmorpholine-N-oxides.
• the fibres were skidded and loaded in 10 L of 0.1 M silver nitrate solution per kg fibre. After loading the fibres were skidded and washed to remove residual silver nitrate. Finally the fibres are dried at a temperature of about 80° C. TABLE 2 yarn-count dtex 0.7 yarn-count related tensile tear resistance (dry) cN/tex 22.5 elongation (dry) % 14.8 yarn-count-related tear resistance of interwoven loops cN/tex 7.5 Silver content g/kg fiber 80
• Table 2 shows the parameters of the fibres as well as the silver content per fibre.
• a highly loaded fibre offers the advantage, that by blending this fibre with other textile fibres, e. g. cotton, silver loaded yarns can be economically obtained.
• the silver-fiber constitutes only a sixteenth of the yarn.
• Fibres are produced according to example 1 with a titre of 0.17 tex and a content of weakly cross-linked cation exchanger of 6 weight-%, based on the content of cellulose. These fibres are loaded with silver according to example 1. The fibre-parameters are given in table 3.
• Fibres are made according to Example 1 with a titre of 0.5 tex and a content of weakly cross-linked cation exchanger of 0.5 weight-%, based on the cellulosic content.
• the loading with silver ions is carried out according to Example 1.
• the parameters of the fibres are shown in table 3. Further, in table 3 a fibre without weakly cross-linked cation exchanger is shown for comparison.
• example 4 yarn-count dtex 0.5 0.5 yarn-count related tensile tear cN/tex 31.2 30.9 resistance (dry) elongation (dry) % 14.2 13.5 yarn-count-related tear cN/tex 9.1 8.5 resistance of loops silver content g/kg fiber 17.5 13.6
• Example 5 Working corresponding to Example 4 and adding to the slurry 6 weight-% of a weakly acid macroporous cation exchanger, based on cross-linked polyacrylate in its sodium-form, so that the spun fibre contains 6 weight-% ion exchanger based on the cellulose content, washing said fibre and loading it with silver ions according to Example 1, one obtains fibres with 13.6 g Ag/kg per fibre.
• Example 5 surprisingly shows that the ion exchanger on the basis of polyacrylate binds about half the amount of silver ions compared to the weakly cross-linked cation exchanger based on polyacrylates.
• the rise of the binding capacity of more than 100% leads to technical and economical advantages in that on one hand small amounts of the weakly cross-linked cation exchanger in the fibre barely influence the textile physical parameters, while on the other hand, based on the high incorporation of silver ions, an economical production by blending with other fibres is possible.
• Fibres with weakly cross-linked cation exchangers as well as common ion exchangers of the prior art, made according to Examples 1 to 5 are loaded with silver, copper (II) and zinc ions. The results are shown in Table 5.
• Table 5 metal content g/kg fiber fiber incorporated with copper silver silver/zinc 20 weight-% ion exchanger according to 23.7 57.1 23.9/27.5 example 4 (comparative example) 20 weight-% ion exchanger according to 11.5 41.7 36.4/24.5 example 5 (comparative example) 15 weight-% weakly linked cation 25.5 85.5 59.3/30.5 exchanger as in example 1 to 3
• Fibres loaded with copper ions, silver ions or a combination of silver ions and zinc ions may be used as bactericide fibres.
• the spinning solution is spun according to Example 1 with a titre of 0.5 tex.
• the fibres show a strength of 26.3 cN/tex, an elongation of 12.1% and a yarn-count related tear-resistance of loops of 8.6 cN/tex.
• the silver load is at 52.4 g silver/kg fibre and the load with benzoate at 16.6 g benzoate/kg fibre. These fibres possess a very strong bactericide effect.
• the example shows the appliccability of fibres according to the invention in combination with loaded fibres with anion exchangers and cation exchangers known from the prior art.
• Ion-exchanging fibres or foils according to the invention with incorporated cation exchangers, produced corresponding to example 2 are loaded with nicotine.
• the loaded fibres or foils are washed and dried.
• These fibres or foils can be processed into textile depots and can be applied as transdermal, therapeutic system.
• the bactericide properties of fibres, produced according to example 1, were determined following the European Pharmacopaeia (EP 2002), ‘Bioburden determination’.
• Papers were examined, which contain fibres according to example 1 in such an amount, that gradually altered silver contents in the paper of 190 mg Ag/kg paper, 760 mg Ag/kg paper and 3800 mg Ag/kg paper resulted.
• the examination was carried out with the following micro-organisms (Tables 6-9):
• the comparative sample was a paper without silver-containing fibres.
• the bacillus subtilis spores showed the highest resistance as expected. But also with these micro-organisms a decrease in microbial count could be achieved.
• Fibres produced according to example 1 were spun in combination with cotton to stocking-yarn with a titre of Nm 68/1 and a silver content of 1300 mg Ag/kg yarn. With this yarn a hose was knitted and examined on its bactericide effect (sample 31444083). The examination was carried out according to SN195924.
• the test-organism was lactobacillus brevis DSM 20054. As test sample a not anti-microbially equipped cotton fabric was used (Table 10). Five measurements were carried out on each sample as well as the test sample.
• the 24-hours-value of the growth-control (control, i. e. standard-fabric) has to be larger than the initial value by at least two orders of magnitude (AE ⁇ 2).

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• 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)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Artificial Filaments (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Nonwoven Fabrics (AREA)
• Paper (AREA)
• Knitting Of Fabric (AREA)

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• 2003
  • 2003-04-04 DE DE10315749A patent/DE10315749A1/de not_active Withdrawn
• 2004
  • 2004-04-01 RU RU2005134210/04A patent/RU2340710C2/ru not_active IP Right Cessation
  • 2004-04-01 US US10/552,086 patent/US20060283567A1/en not_active Abandoned
  • 2004-04-01 CN CNB2004800091522A patent/CN100545325C/zh not_active Expired - Lifetime
  • 2004-04-01 DE DE502004009966T patent/DE502004009966D1/de not_active Expired - Lifetime
  • 2004-04-01 EP EP04725036A patent/EP1611272B1/de not_active Expired - Lifetime
  • 2004-04-01 AT AT04725036T patent/ATE440981T1/de active
  • 2004-04-01 PL PL04725036T patent/PL1611272T3/pl unknown
  • 2004-04-01 JP JP2006504948A patent/JP2006522232A/ja active Pending
  • 2004-04-01 WO PCT/EP2004/003466 patent/WO2004088009A1/de active Application Filing

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