EP1967618A2 - Antimicrobial filaments, method for their manufacture and use thereof - Google Patents
Antimicrobial filaments, method for their manufacture and use thereof Download PDFInfo
- Publication number
- EP1967618A2 EP1967618A2 EP20080001369 EP08001369A EP1967618A2 EP 1967618 A2 EP1967618 A2 EP 1967618A2 EP 20080001369 EP20080001369 EP 20080001369 EP 08001369 A EP08001369 A EP 08001369A EP 1967618 A2 EP1967618 A2 EP 1967618A2
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- EP
- European Patent Office
- Prior art keywords
- component
- thread according
- thermoplastic
- thread
- elastomer
- 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.)
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Classifications
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- 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
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
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- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249932—Fiber embedded in a layer derived from a water-settable material [e.g., cement, gypsum, 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
- Y10T442/615—Strand or fiber material is blended with another chemically different microfiber in the same layer
Definitions
- the present invention relates to elastic threads, in particular monofilaments, having excellent antimicrobial activity. These are particularly suitable for the production of textile fabrics, which are used in applications in which sterility and sterility combined with elastic behavior are in demand.
- the antimicrobial finishing of threads is usually done by doping with heavy metal ions, such as silver ions, or by applying antimicrobial effective sizes to the thread surface. It has also been tried to introduce antimicrobial substances into the thread; However, this is usually limited to selected materials and the active substances are removed by washing comparatively quickly from the thread.
- Halogenated phenols are known as antimicrobial agents.
- An example of this is triclosan, 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether.
- antimicrobial finished threads are in CA-A-2,551,701 to find.
- a microbiocidally effective air filter is described, which has microbiocid-equipped threads.
- antibacterial agent for example triclosan is called;
- polyvinyl chloride is proposed.
- the equipment is made by superficially applying triclosan or a derivative thereof to the thread or textile surface.
- the specification states that coextrusion of triclosan with filament-forming materials is only possible with selected polymers and does not work with polyester, polyamide, cotton and lycra textiles.
- US-A-6,299,651 discloses textiles finished with etherified triclosan derivatives.
- the active substance is applied by contact with the surface of the thread or the textile in the heat by diffusing.
- DE-T-689 09 268 describes a method for modifying the surface of a solid plastic in which a surface is contacted with a basic swelling agent. Due to the modified surface, active substances can be introduced into the plastic.
- the object of the present invention is therefore to provide elastic and antimicrobially finished threads and textiles which retain the antimicrobial effect even after several washes.
- the invention relates to a yarn containing a) thermoplastic elastomer, b) polymer having a melting point of at least 10 ° C below the melting point of the thermoplastic elastomer and c) halogenated phenol.
- threads are generally understood to mean fibers of finite length (staple fibers), fibers of infinite length (filaments) and multifilaments composed thereof or secondary-spun yarns of staple fibers. Preference is given to melt-spun threads in the form of monofilaments.
- thermoplastic elastomers of component a) can be of very different types. Such polymers are usually elastomeric block copolymers and are known to those skilled in the art.
- components a) are thermoplastic and elastomeric polyurethanes (TPE-U), thermoplastic and elastomeric polyesters (TPE-E), thermoplastic and elastomeric polyamides (TPE-A), thermoplastic and elastomeric polyolefins (TPE-O) and thermoplastic and elastomeric styrene Block copolymers (TPE-S).
- TPE-U thermoplastic and elastomeric polyurethanes
- TPE-E thermoplastic and elastomeric polyesters
- TPE-A thermoplastic and elastomeric polyamides
- TPE-O thermoplastic and elastomeric polyolefins
- TPE-S thermoplastic and elastomeric styrene Block copolymers
- thermoplastic and elastomeric block copolymers a) can be made up of a wide variety of monomer combinations. As a rule, these are blocks of so-called hard and soft segments.
- the soft segments are typically derived from polyalkylene glycol ethers in TPE-U, TPE-E and TPE-A.
- the hard segments are typically derived from short chain diols or diamines in TPE-U, TPE-E and TPE-A. In addition to the diols or diamines, the hard and soft segments of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or diisocyanates are built up.
- thermoplastic polyolefins are block copolymers comprising blocks of ethylene-propylene-butadiene and of polypropylene (EPDM / PP) or of nitrile-butadiene and of polypropylene (NBR / PP).
- thermoplastic and elastomeric polyurethanes and in particular thermoplastic and elastomeric polyether esters.
- block copolymers comprising blocks of polyethylene terephthalate and / or of polybutylene terephthalate and blocks of polyalkylene glycol terephthalate; or the blocks derived from aromatic and / or cycloaliphatic diisocyanate and alkylene and / or arylenediamine and blocks derived from aromatic and / or cycloaliphatic diisocyanate and ⁇ , ⁇ -diamino-polyalkylene ether.
- thermoplastic and elastomeric polymers are to be understood as meaning block copolymers which behave at room temperature comparable to the conventional elastomers, but can be plastically deformed under heat supply and thus exhibit a thermoplastic behavior.
- thermoplastic and elastomeric block copolymers have in some areas physical crosslinking points (e.g., minor valence forces or crystallites) that dissolve on heat without the polymer molecules decomposing.
- component b) selected polymers are used. This is the polymer component of the masterbatch used in the production of the threads according to the invention.
- the melting point of the polymer of component b) should be at least 10 ° C below the melting point of the polymer of component a).
- Suitable polymers of component b) are polyesters, polycarbonates, polyamides, or in particular polyolefins.
- component b) it is possible to use preferably polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, thermoplastic and elastomeric polyether esters (TPE-E) other than component a), polycarbonate, aliphatic polyamides such as nylon 6 or nylon 6.6, and in particular halogen-free polyolefins.
- TPE-E thermoplastic and elastomeric polyether esters
- those polymers are selected whose melting point is in the range from 140 to 220.degree.
- Particularly preferred polybutylene terephthalate and polyethylene and especially polypropylene as component b) are used.
- halogenated phenols are used. These may be mono- or polynuclear phenols. These may have one or more phenolic hydroxyl groups. Suitable halogen substituents are fluorine, chlorine, bromine and iodine; Bromine and especially chlorine are particularly preferred.
- phenols with a diphenyl ether base in particular those types having a phenolic hydroxyl group and two to four halogen substituents; most preferably those types having a phenolic hydroxyl group ortho to the ether oxygen.
- Very particularly preferred component c) is 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether (triclosan).
- the amounts of components a), b) and c) in the threads according to the invention can be selected within wide limits.
- the filaments contain 20 to 99.89% by weight of component a), 0.01 to 55% by weight of component b) and 0.1 to 25% by weight of component c), in each case based on the total mass of the filament ,
- the components a), b) and c) required for producing the threads according to the invention are known per se, some are commercially available or can be prepared by processes known per se.
- the threads according to the invention may contain, in addition to components a), b) and c), further auxiliaries d).
- hydrolysis stabilizers examples include hydrolysis stabilizers, processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers, crystallization accelerators or dyes.
- hydrolysis stabilizers examples are carbodiimides.
- processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
- antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
- pigments or matting agents examples include organic dye pigments or titanium dioxide.
- viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
- the proportion of the auxiliaries d) can amount to up to 20% by weight of the total mass of the thread.
- the threads of the invention are preferably monofilaments.
- the titer of the threads according to the invention can vary within wide limits. Examples are 30 to 45,000 dtex, more preferably between 100 and 1,000 dtex.
- the cross-sectional shape of the threads according to the invention may be arbitrary, for example round, oval or n-cornered, where n is greater than or equal to 3.
- monofilaments having a round or n-shaped cross section whose titre is between 30 and 45,000 dtex;
- these monofilaments contain at least one dye which is used in medically sterile areas.
- the threads of the invention can be prepared by methods known per se.
- the production of the threads according to the invention can be carried out by conventional Melt spinning process, combined with one or more times stretching and optionally fixing the threads obtained.
- the threads according to the invention are distinguished by a particularly good combination of elasticity and lasting antimicrobial properties.
- the halogenated phenol in combination with a polymer in the form of a masterbatch, can be easily incorporated into the thermoplastic elastomer and mixed. There are no agglomerates of the masterbatch in the polymer matrix and the material is finely dispersed. In the mixture of chemically differently structured polymers, usually islands of the added polymer often form in the matrix of the base polymer. This can be seen from the large diameter fluctuations of the thread or at numerous thick points. These negative phenomena were surprisingly not observed here.
- the threads of the invention are preferably used for the production of textile fabrics, in particular of woven, laid, knitted, braided or knitted fabrics.
- the fabrics are preferably used in areas where sterility and sterility are in demand.
- the antimicrobial property is permanently attached to the product since the masterbatch is evenly distributed throughout the cross section of the thread. Even after several washes, this property is retained without the need for post-preparation.
- Examples of uses of the threads according to the invention are the use in mattresses, which are to be used preferably in hospitals, retirement and nursing homes, in upholstery, such as hospital chairs, in treadmills, in elastic straps, especially in the fitness area in trim equipment and sunbeds be used, in conveyor belts, in particular for hygiene and cosmetic articles, in filter cloths, in particular for rotary filters, such as chamber filter presses, or in textiles for the interior decoration of buildings or vehicles, especially for the interior of automobiles or aircraft or as seat covers or seat supports for office - or school furniture.
- Textile fabrics containing the threads according to the invention are also the subject of this invention.
- the invention also relates to the use of the described threads for the purposes stated above.
- thermoplastic, elastomeric polyetherester (Heraflex, Riteflex) and a Materbatch containing 20% by weight of triclosan and polypropylene (Sanitized MB P-96-61) were used.
- TPE-E was admixed with an amount of 1.0% by weight (Example 1) or 1.5% by weight (Example 2) of the masterbatch.
- the polymer was melt spun through a spinner, quenched the individual filaments in a water bath, and then repeatedly stretched, heat set, post-baked, and each filament individually in three stages, each of which was heatable wound.
- the process data and the obtained textile values of the monofilaments are listed in the table below.
Abstract
Description
Die vorliegende Erfindung betrifft elastische Fäden, insbesondere Monofilamente, mit ausgezeichneter antimikrobieller Wirkung. Diese eignen sich vorzüglich zur Herstellung textiler Flächengebilde, die in Einsatzgebieten zur Anwendung kommen, in denen Keimfreiheit und Sterilität kombiniert mit elastischem Verhalten gefragt sind.The present invention relates to elastic threads, in particular monofilaments, having excellent antimicrobial activity. These are particularly suitable for the production of textile fabrics, which are used in applications in which sterility and sterility combined with elastic behavior are in demand.
Die antimikrobielle Ausrüstung von Fäden erfolgt üblicherweise durch Dotierung mit Schwermetallionen, wie Silberionen, oder durch Aufbringen von antimikrobiell wirksamen Schlichten auf die Fadenoberfläche. Es ist auch schon versucht worden, antimikrobiell wirksame Substanzen in den Faden einzubringen; dieses ist jedoch in der Regel auf ausgewählte Materialien begrenzt und die Wirksubstanzen werden durch Waschen vergleichsweise rasch aus dem Faden entfernt.The antimicrobial finishing of threads is usually done by doping with heavy metal ions, such as silver ions, or by applying antimicrobial effective sizes to the thread surface. It has also been tried to introduce antimicrobial substances into the thread; However, this is usually limited to selected materials and the active substances are removed by washing comparatively quickly from the thread.
Halogenierte Phenole sind als antimikrobielle Mittel bekannt. Ein Beispiel dafür ist Triclosan, 2-Hydroxy-4,2',4'-trichlordiphenylether.Halogenated phenols are known as antimicrobial agents. An example of this is triclosan, 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether.
Beispiele für antimikrobiell ausgerüstete Fäden sind in
Die Ausrüstung erfolgt durch das oberflächliche Aufbringen von Triclosan oder einem Derivat davon auf die Faden- oder Textiloberfläche. In der Beschreibung wird ausgeführt, dass die Coextrusion von Triclosan mit fadenbildenden Materialien nur bei ausgewählten Polymeren möglich ist und nicht bei Polyester-, Polyamid-, Baumwoll- und Lycratextilen funktioniert.The equipment is made by superficially applying triclosan or a derivative thereof to the thread or textile surface. The specification states that coextrusion of triclosan with filament-forming materials is only possible with selected polymers and does not work with polyester, polyamide, cotton and lycra textiles.
Es wurde jetzt in überraschender Weise eine ausgewählte Gruppe von verspinnbaren Polymeren gefunden, die das Einbringen von großen Mengen an halogenierten Phenolen gestatten und welche die Herstellung von elastischen Fäden mit einem bislang nicht verfügbaren Eigenschaftsprofil gestatten. Es hat sich gezeigt, dass das Verspinnen von thermoplastischen Elastomeren mit Halogenphenolen in Form eines Masterbatches derartige Fäden ergibt.There has now surprisingly been found a select group of spinnable polymers which permit the incorporation of large quantities of halogenated phenols and which permit the production of elastic filaments with a hitherto unavailable property profile. It has been found that the spinning of thermoplastic elastomers with halophenols in the form of a masterbatch results in such threads.
Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung von elastischen und antimikrobiell ausgerüsteten Fäden und Textilen, welche die antimikrobielle Wirkung auch nach mehreren Wäschen beibehalten.The object of the present invention is therefore to provide elastic and antimicrobially finished threads and textiles which retain the antimicrobial effect even after several washes.
Die Erfindung betrifft einen Faden enthaltend a) thermoplastisches Elastomer, b) Polymer mit einem Schmelzpunkt von mindestens 10°C unterhalb des Schmelzpunkts des thermoplastischen Elastomeren und c) halogeniertes Phenol.The invention relates to a yarn containing a) thermoplastic elastomer, b) polymer having a melting point of at least 10 ° C below the melting point of the thermoplastic elastomer and c) halogenated phenol.
Unter Fäden werden im Rahmen dieser Beschreibung ganz allgemein Fasern endlicher Länge (Stapelfasern), Fasern unendlicher Länge (Filamente) sowie daraus zusammengesetzte Multifilamente oder aus Stapelfasern sekundär gesponnene Garne verstanden. Bevorzugt sind schmelzgesponnene Fäden in Form von Monofilamenten.In the context of this description, threads are generally understood to mean fibers of finite length (staple fibers), fibers of infinite length (filaments) and multifilaments composed thereof or secondary-spun yarns of staple fibers. Preference is given to melt-spun threads in the form of monofilaments.
Unter Monofilamenten werden im Rahmen dieser Beschreibung einzelne Fäden verstanden. Diese weisen typischerweise Durchmesser von 55 bis 5000 µm, vorzugsweise von 100 bis 300 µm, auf.Under monofilaments are understood in the context of this description individual threads. These typically have diameters of from 55 to 5000 .mu.m, preferably from 100 to 300 .mu.m.
Bei den thermoplastischen Elastomeren der Komponente a) kann es sich um unterschiedlichste Typen handeln. Solche Polymere sind üblicherweise elastomere Block-Copolymeren und sind dem Fachmann bekannt.The thermoplastic elastomers of component a) can be of very different types. Such polymers are usually elastomeric block copolymers and are known to those skilled in the art.
Beispiele für Komponenten a) sind thermoplastische und elastomere Polyurethane (TPE-U), thermoplastische und elastomere Polyester (TPE-E), thermoplastische und elastomere Polyamide (TPE-A), thermoplastische und elastomere Polyolefine (TPE-O) und thermoplastische und elastomere Styrol-Blockcopolymere (TPE-S).Examples of components a) are thermoplastic and elastomeric polyurethanes (TPE-U), thermoplastic and elastomeric polyesters (TPE-E), thermoplastic and elastomeric polyamides (TPE-A), thermoplastic and elastomeric polyolefins (TPE-O) and thermoplastic and elastomeric styrene Block copolymers (TPE-S).
Die thermoplastischen und elastomeren Block-Copolymeren a) können aus unterschiedlichsten Monomerkombinationen aufgebaut sein. In der Regel handelt es sich um Blöcke aus sogenannten Hart- und Weichsegmenten. Die Weichsegmente leiten sich bei den TPE-U, den TPE-E und den TPE-A typischerweise von Polyalkylenglykolethern ab. Die Hartsegmente leiten sich bei den TPE-U, den TPE-E und den TPE-A typischerweise von kurzkettigen Diolen oder Diaminen ab. Neben den Diolen bzw. Diaminen werden die Hart- und Weichsegmente von aliphatischen, cycloaliphatischen und/oder aromatischen Dicarbonsäuren oder Diisocyanaten aufgebaut.The thermoplastic and elastomeric block copolymers a) can be made up of a wide variety of monomer combinations. As a rule, these are blocks of so-called hard and soft segments. The soft segments are typically derived from polyalkylene glycol ethers in TPE-U, TPE-E and TPE-A. The hard segments are typically derived from short chain diols or diamines in TPE-U, TPE-E and TPE-A. In addition to the diols or diamines, the hard and soft segments of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or diisocyanates are built up.
Beispiele für thermoplastische Polyolefine sind Block-Copolymere, die Blöcke aus Ethylen-Propylen-Butadien und aus Polypropylen (EPDM/PP) oder aus Nitril-Butadien und aus Polypropylen (NBR/PP) aufweisen.Examples of thermoplastic polyolefins are block copolymers comprising blocks of ethylene-propylene-butadiene and of polypropylene (EPDM / PP) or of nitrile-butadiene and of polypropylene (NBR / PP).
Besonders bevorzugte Komponenten a) sind thermoplastische und elastomere Polyurethane und insbesondere thermoplastische und elastomere Polyetherester. Beispiele dafür sind Block-Copolymere, die Blöcke aus Polyethylenterephthalat und/oder aus Polybutylenterephthalat sowie Blöcke aus Polyalkylenglykolterephthalat aufweisen; oder die Blöcke abgeleitet von aromatischem und/oder cycloaliphatischem Diisocyanat und Alkylen- und/oder Arylendiamin sowie Blöcke abgeleitet von aromatischem und/oder cycloaliphatischem Diisocyanat und α, ω-Diamino-polyalkylenether aufweisen.Particularly preferred components a) are thermoplastic and elastomeric polyurethanes and in particular thermoplastic and elastomeric polyether esters. Examples of these are block copolymers comprising blocks of polyethylene terephthalate and / or of polybutylene terephthalate and blocks of polyalkylene glycol terephthalate; or the blocks derived from aromatic and / or cycloaliphatic diisocyanate and alkylene and / or arylenediamine and blocks derived from aromatic and / or cycloaliphatic diisocyanate and α, ω-diamino-polyalkylene ether.
Unter thermoplastischen und elastomeren Polymeren sind im Rahmen dieser Beschreibung Block-Copolymere zu verstehen, der sich bei Raumtemperatur vergleichbar den klassischen Elastomeren verhalten, sich jedoch unter Wärmezufuhr plastisch verformen lassen und somit ein thermoplastisches Verhalten zeigen. Diese thermoplastischen und elastomeren Block-Copolymeren haben in Teilbereichen physikalische Vernetzungspunkte (z.B. Nebenvalenzkräfte oder Kristallite), die sich bei Wärme auflösen, ohne dass sich die Polymermoleküle zersetzen.In the context of this description, thermoplastic and elastomeric polymers are to be understood as meaning block copolymers which behave at room temperature comparable to the conventional elastomers, but can be plastically deformed under heat supply and thus exhibit a thermoplastic behavior. These thermoplastic and elastomeric block copolymers have in some areas physical crosslinking points (e.g., minor valence forces or crystallites) that dissolve on heat without the polymer molecules decomposing.
Als Komponente b) kommen ausgewählte Polymere zum Einsatz. Dabei handelt es sich um die Polymerkomponente, des bei der Herstellung der erfindungsgemäßen Fäden eingesetzten Masterbatches. Um eine ausreichende Verspinnbarkeit und Vermischbarkeit im Extruder zu gewährleisten, sollte der Schmelzpunkt des Polymeren der Komponente b) mindestens 10 °C unterhalb des Schmelzpunktes des Polymeren der Komponente a) liegen.As component b) selected polymers are used. This is the polymer component of the masterbatch used in the production of the threads according to the invention. In order to ensure sufficient spinnability and miscibility in the extruder, the melting point of the polymer of component b) should be at least 10 ° C below the melting point of the polymer of component a).
Beispiele für geeignete Polymere der Komponente b) sind Polyester, Polycarbonate, Polyamide, oder insbesondere Polyolefine.Examples of suitable polymers of component b) are polyesters, polycarbonates, polyamides, or in particular polyolefins.
Als Komponente b) können vorzugsweise Polyethylenterephthalat, Polypropylenterephthalat, Polybutylenterephthalat, Polybutylennaphthalat, Polyethylennaphthalat, von Komponente a) unterschiedliche thermoplastische und elastomere Polyetherester (TPE-E), Polycarbonat, aliphatische Polyamide, wie Nylon 6 oder Nylon 6.6, sowie insbesondere halogenfreie Polyolefine eingesetzt werden.As component b) it is possible to use preferably polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, thermoplastic and elastomeric polyether esters (TPE-E) other than component a), polycarbonate, aliphatic polyamides such as nylon 6 or nylon 6.6, and in particular halogen-free polyolefins.
Bevorzugt werden als Komponente b) solche Polymere ausgewählt, deren Schmelzpunkt im Bereich von 140 und 220 °C liegt.Preferably, as component b), those polymers are selected whose melting point is in the range from 140 to 220.degree.
Besonders bevorzugt werden Polybutylenterephthalat und Polyethylen sowie ganz besonders Polypropylen als Komponente b) eingesetzt.Particularly preferred polybutylene terephthalate and polyethylene and especially polypropylene as component b) are used.
Als Komponente c) werden halogenierte Phenole eingesetzt. Dabei kann es sich um ein- oder um mehrkernige Phenole handeln. Diese können eine oder mehrere phenolische Hydroxylgruppen aufweisen. Als Halogensubstituenten kommen Fluor, Chlor, Brom und lod in Frage; Brom und insbesondere Chlor sind davon besonders bevorzugt.As component c) halogenated phenols are used. These may be mono- or polynuclear phenols. These may have one or more phenolic hydroxyl groups. Suitable halogen substituents are fluorine, chlorine, bromine and iodine; Bromine and especially chlorine are particularly preferred.
Ganz besonders bevorzugt sind Phenole mit Diphenylether-Grundkörper, insbesondere diejenigen Typen mit einer phenolischen Hydroxylgruppe und zwei bis vier Halogensubstituenten; ganz besonders bevorzugt diejenigen Typen, mit einer phenolischen Hydroxylgruppe in ortho-Position zum Ethersauerstoff.Very particular preference is given to phenols with a diphenyl ether base, in particular those types having a phenolic hydroxyl group and two to four halogen substituents; most preferably those types having a phenolic hydroxyl group ortho to the ether oxygen.
Ganz besonders bevorzugte Komponente c) ist 2-Hydroxy-4, 2', 4'-trichlordiphenylether (Triclosan).Very particularly preferred component c) is 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether (triclosan).
Die Mengen an Komponenten a), b) und c) in den erfindungsgemäßen Fäden können in weiten Bereichen gewählt werden. Typischerweise enthalten die Fäden 20 bis 99,89 Gew. % an Komponente a), 0,01 bis 55 Gew. % an Komponente b) und 0,1 bis 25 Gew. % an Komponente c), jeweils bezogen auf die Gesamtmasse des Fadens.The amounts of components a), b) and c) in the threads according to the invention can be selected within wide limits. Typically, the filaments contain 20 to 99.89% by weight of component a), 0.01 to 55% by weight of component b) and 0.1 to 25% by weight of component c), in each case based on the total mass of the filament ,
Die zur Herstellung der erfindungsgemäßen Fäden benötigten Komponenten a), b) und c) sind an sich bekannt, teilweise kommerziell erhältlich oder können nach an sich bekannten Verfahren hergestellt werden.The components a), b) and c) required for producing the threads according to the invention are known per se, some are commercially available or can be prepared by processes known per se.
Die erfindungsgemäßen Fäden können neben Komponenten a), b) und c) noch weitere Hilfsstoffe d) enthalten.The threads according to the invention may contain, in addition to components a), b) and c), further auxiliaries d).
Beispiele dafür sind Hydrolysestabilisatoren, Verarbeitungshilfsmittel, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer, Kristallisationbeschleuniger oder Farbstoffe.Examples of these are hydrolysis stabilizers, processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers, crystallization accelerators or dyes.
Beispiele für Hydrolysestabilisatoren sind Carbodiimide.Examples of hydrolysis stabilizers are carbodiimides.
Beispiele für Verarbeitungshilfsmittel sind Siloxane, Wachse oder längerkettige Carbonsäuren oder deren Salze, aliphatische, aromatische Ester oder Ether.Examples of processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
Beispiele für Antioxidantien sind Phosphorverbindungen, wie Phosphorsäureester oder sterisch gehinderte Phenole.Examples of antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
Beispiele für Pigmente oder Mattierungsmittel sind organische Farbstoffpigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Beispiele für Viskositätsmodifizierer sind mehrwertige Carbonsäuren und deren Ester oder mehrwertige Alkohole.Examples of viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
Der Anteil der Hilfsstoffe d) kann bis zu 20 Gew. % der Gesamtmasse des Fadens betragen.The proportion of the auxiliaries d) can amount to up to 20% by weight of the total mass of the thread.
Die erfindungsgemäßen Fäden sind vorzugsweise Monofilamente.The threads of the invention are preferably monofilaments.
Der Titer der erfindungsgemäßen Fäden kann in weiten Bereichen schwanken. Beispiele dafür sind 30 bis 45.000 dtex, besonders bevorzugt zwischen 100 und 1.000 dtex.The titer of the threads according to the invention can vary within wide limits. Examples are 30 to 45,000 dtex, more preferably between 100 and 1,000 dtex.
Die Querschnittsform der erfindungsgemäßen Fäden kann beliebig sein, beispielsweise rund, oval oder n-eckig, wobei n größer gleich 3 ist.The cross-sectional shape of the threads according to the invention may be arbitrary, for example round, oval or n-cornered, where n is greater than or equal to 3.
Ganz besonders bevorzugt sind Monofilamente mit einem runden oder n-eckigen Querschnitt, deren Titer zwischen 30 und 45.000 dtex liegt; insbesondere enthalten diese Monofilamente mindestens einen Farbstoff, der in medizinisch sterilen Bereichen verwendet wird.Very particular preference is given to monofilaments having a round or n-shaped cross section whose titre is between 30 and 45,000 dtex; In particular, these monofilaments contain at least one dye which is used in medically sterile areas.
Die erfindungsgemäßen Fäden können nach an sich bekannten Verfahren hergestellt werden.The threads of the invention can be prepared by methods known per se.
Ein typisches Herstellverfahren umfasst die Maßnahmen:
- i) Vermischen von Komponente a) und einem Masterbatch enthaltend Komponenten b) und c) in einem Extruder,
- ii) Extrudieren des Gemisches enthaltend Komponenten a), b) und c) durch eine Spinndüse,
- iii) Abziehen des gebildeten Filaments,
- iv) gegebenenfalls Verstrecken und/oder Relaxieren des gebildeten Filaments, und
- v) Aufspulen des gebildeten Filaments.
- i) mixing component a) and a masterbatch containing components b) and c) in an extruder,
- ii) extruding the mixture comprising components a), b) and c) through a spinneret,
- iii) stripping off the formed filament,
- iv) optionally stretching and / or relaxing the formed filament, and
- v) winding the formed filament.
Die Herstellung der erfindungsgemäßen Fäden kann durch herkömmliche Schmelzspinnverfahren erfolgen, kombiniert mit ein- oder mehrfachem Verstrecken und gegebenenfalls Fixieren der erhaltenen Fäden.The production of the threads according to the invention can be carried out by conventional Melt spinning process, combined with one or more times stretching and optionally fixing the threads obtained.
Die erfindungsgemäßen Fäden zeichnen sich durch eine besonders gute Kombination von Elastizität und dauerhaften antimikrobiellen Eigenschaften aus.The threads according to the invention are distinguished by a particularly good combination of elasticity and lasting antimicrobial properties.
Für den Fachmann ist es überraschend, dass sich das halogenierte Phenol in Kombination mit einem Polymeren in Form eines Masterbatches problemlos in das thermoplastische Elastomere einarbeiten und vermischen lässt. Es bilden sich keine Agglomerate des Masterbatch in der Polymermatrix und das Material wird fein verteilt. Bei der Mischung chemisch unterschiedlich aufgebauter Polymerer bilden sich in der Regel oft Inseln des zudosierten Polymers in der Matrix des Grundpolymers aus. Man erkennt dies an den großen Durchmesserschwankungen des Fadens bzw. an zahlreichen Dickstellen. Diese negativen Erscheinungen wurden hier überraschenderweise nicht beobachtet.It is surprising for the person skilled in the art that the halogenated phenol, in combination with a polymer in the form of a masterbatch, can be easily incorporated into the thermoplastic elastomer and mixed. There are no agglomerates of the masterbatch in the polymer matrix and the material is finely dispersed. In the mixture of chemically differently structured polymers, usually islands of the added polymer often form in the matrix of the base polymer. This can be seen from the large diameter fluctuations of the thread or at numerous thick points. These negative phenomena were surprisingly not observed here.
Bevorzugt werden die erfindungsgemäßen Fäden zur Herstellung von textilen Flächengebilden, insbesondere von Geweben, Gelegen, Gewirken, Geflechten oder Gestricken, eingesetzt.The threads of the invention are preferably used for the production of textile fabrics, in particular of woven, laid, knitted, braided or knitted fabrics.
Die textilen Flächengebilde werden vorzugsweise in Gebieten eingesetzt, in denen Keimfreiheit und Sterilität gefragt sind.The fabrics are preferably used in areas where sterility and sterility are in demand.
Besonders hervorzuheben ist die Tatsache, dass die antimikrobielle Eigenschaft permanent mit dem Erzeugnis verbunden ist, da das Masterbatch gleichmäßig über den Querschnitt des Fadens verteilt ist. Auch nach mehreren Wäschen bleibt diese Eigenschaft erhalten, ohne dass eine Nachpräparierung notwendig ist.Of particular note is the fact that the antimicrobial property is permanently attached to the product since the masterbatch is evenly distributed throughout the cross section of the thread. Even after several washes, this property is retained without the need for post-preparation.
Beispiele für Verwendungen der erfindungsgemäßen Fäden sind der Einsatz in Matratzen, welche vorzugsweise in Krankenhäusern, Alters- und Pflegeheimen eingesetzt werden sollen, in Polsterbezügen, wie für Krankenstühle, in Laufbändern, in elastischen Riemen, die insbesondere im Fitness-Bereich in Trimmgeräten sowie in Sonnenliegen eingesetzt werden, in Transportbändern, insbesondere für Hygiene- und Kosmetikartikel, in Filtertüchern, insbesondere für Rotationsfilter, wie Kammerfilterpressen, oder in Textilien für die Innenausstattung von Gebäuden oder Fahrzeugen, insbesondere für die Innenausstattung von Automobilen oder Flugzeugen oder als Sitzbezüge oder als Sitzunterstützungen für Büro- oder Schulmöbel.Examples of uses of the threads according to the invention are the use in mattresses, which are to be used preferably in hospitals, retirement and nursing homes, in upholstery, such as hospital chairs, in treadmills, in elastic straps, especially in the fitness area in trim equipment and sunbeds be used, in conveyor belts, in particular for hygiene and cosmetic articles, in filter cloths, in particular for rotary filters, such as chamber filter presses, or in textiles for the interior decoration of buildings or vehicles, especially for the interior of automobiles or aircraft or as seat covers or seat supports for office - or school furniture.
Textile Flächengebilde enthaltend die erfindungsgemäßen Fäden sind ebenfalls Gegenstand dieser Erfindung.Textile fabrics containing the threads according to the invention are also the subject of this invention.
Die Erfindung betrifft auch Verwendung der beschriebenen Fäden für die oben angegebenen Zwecke.The invention also relates to the use of the described threads for the purposes stated above.
Die nachfolgenden Beispiele erläutern die Erfindung ohne diese zu begrenzen.The following examples illustrate the invention without limiting it.
Eingesetzt wurden ein thermoplastischer, elastomerer Polyetherester ("TPE-E") (Heraflex, Riteflex) sowie ein 20 Gew. % Triclosan und Polypropylen enthaltender Materbatch (Sanitized MB P-96-61).A thermoplastic, elastomeric polyetherester ("TPE-E") (Heraflex, Riteflex) and a Materbatch containing 20% by weight of triclosan and polypropylene (Sanitized MB P-96-61) were used.
Unmittelbar vor der Einzugszone eines Extruders wurde dem TPE-E eine Menge von 1,0 Gew. % (Beispiel 1) bzw. von 1,5 Gew. % (Beispiel 2) des Masterbatches zugemischt. Nach Extrusion wurde das Polymer über einen Spinnkopf schmelzgesponnen, die einzelnen Filamente in einem Wasserbad abgeschreckt, und anschließend in drei Stufen, von denen jede beheizbar war, mehrfach verstreckt, thermofixiert, nachpräpariert und jedes Filament einzeln aufgespult. Die verfahrenstechnischen Daten und die erhaltenen Textilwerte der Monofilamente sind in der nachstehenden Tabelle aufgeführt.Immediately before the feed zone of an extruder, TPE-E was admixed with an amount of 1.0% by weight (Example 1) or 1.5% by weight (Example 2) of the masterbatch. After extrusion, the polymer was melt spun through a spinner, quenched the individual filaments in a water bath, and then repeatedly stretched, heat set, post-baked, and each filament individually in three stages, each of which was heatable wound. The process data and the obtained textile values of the monofilaments are listed in the table below.
Als Vergleich wurde ein Monofilament ohne Masterbatch Zusatz mitgesponnen.As a comparison, a monofilament without masterbatch additive was spun.
Die Proben wurden im Labor der Sanitized AG nach der Methode SN 195 920 Staphylococcus aureus ATCC 6538 untersucht. Bereits das Muster 1 zeigte keinen bakteriellen Bewuchs und eine gute Wirkung, im Gegensatz zum unbehandelten Standard.
Claims (15)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE102007011076A DE102007011076B4 (en) | 2007-03-07 | 2007-03-07 | Antimicrobially finished threads, process for their production and textile fabrics |
Publications (2)
Publication Number | Publication Date |
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EP1967618A2 true EP1967618A2 (en) | 2008-09-10 |
EP1967618A3 EP1967618A3 (en) | 2013-05-01 |
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EP20080001369 Withdrawn EP1967618A3 (en) | 2007-03-07 | 2008-01-25 | Antimicrobial filaments, method for their manufacture and use thereof |
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US (1) | US7824764B2 (en) |
EP (1) | EP1967618A3 (en) |
JP (1) | JP2008214848A (en) |
DE (1) | DE102007011076B4 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103757906A (en) * | 2014-02-18 | 2014-04-30 | 江南大学 | Preparation method of olefine halamine compound grafted antibacterial cotton fabric containing quaternary ammonium groups |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102007011076B4 (en) * | 2007-03-07 | 2011-06-01 | Teijin Monofilament Germany Gmbh | Antimicrobially finished threads, process for their production and textile fabrics |
JP6455534B2 (en) * | 2017-02-02 | 2019-01-23 | トヨタ紡織株式会社 | Thermoplastic resin fiber, production method thereof, and fabric |
TWI728745B (en) | 2020-03-13 | 2021-05-21 | 財團法人工業技術研究院 | Fiber |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE68909268T2 (en) | 1988-02-01 | 1994-04-14 | Dow Corning | Process for modifying the surface of a solid plastic. |
US6299651B1 (en) | 1998-02-20 | 2001-10-09 | Milliken & Company | Fabrics comprising fibers having esterified triclosan derivatives diffused therein |
CA2551701A1 (en) | 2005-06-30 | 2006-12-30 | Bolduc Leroux Inc. | Microbicidal air filter |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2972600A (en) * | 1957-09-27 | 1961-02-21 | Schenectady Varnish Company In | Substituted phenols |
NL291470A (en) * | 1961-11-24 | 1900-01-01 | ||
CH570470A5 (en) * | 1972-10-13 | 1975-12-15 | Sanitized Ag | Permanent anti-microbial treatment of synthetic fibres - by adding anti-microbial substances to spinning melt or dope before spinning |
JPS62544A (en) * | 1985-06-26 | 1987-01-06 | Teisan Seiyaku Kk | Polyester composition molding and production thereof |
JPH0816284B2 (en) * | 1991-07-23 | 1996-02-21 | 富士紡績株式会社 | Modified polyurethane elastic fiber |
AUPN851996A0 (en) * | 1996-03-07 | 1996-03-28 | John Patrick Gray | Improvements in wound care management |
US6207274B1 (en) * | 1999-12-21 | 2001-03-27 | International Flavors & Fragrances Inc. | Fragrance containing fiber |
US6939918B2 (en) * | 2000-03-24 | 2005-09-06 | Advanced Elastomer Systems L.P. | Thermoplastic elastomers having improved low temperature properties |
US6479144B2 (en) * | 2000-12-04 | 2002-11-12 | Milliken & Company | Anti-tack spandex fibers containing antimicrobial agents therein and fabrics made therefrom |
US6451915B1 (en) * | 2000-12-29 | 2002-09-17 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved processing and physical property balance |
US6433090B1 (en) * | 2001-01-26 | 2002-08-13 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved set foams made therefrom |
EP1615756A1 (en) * | 2003-04-23 | 2006-01-18 | Ciba SC Holding AG | Natural products composites |
US20060160448A1 (en) * | 2004-10-15 | 2006-07-20 | Advanced Fabrics (Saaf) | Antimicrobial fabric and method for maunfacture of antimicrobial fabric |
DE102007011076B4 (en) * | 2007-03-07 | 2011-06-01 | Teijin Monofilament Germany Gmbh | Antimicrobially finished threads, process for their production and textile fabrics |
US8513322B2 (en) * | 2007-05-31 | 2013-08-20 | 3M Innovative Properties Company | Polymeric beads and methods of making polymeric beads |
-
2007
- 2007-03-07 DE DE102007011076A patent/DE102007011076B4/en not_active Expired - Fee Related
-
2008
- 2008-01-25 EP EP20080001369 patent/EP1967618A3/en not_active Withdrawn
- 2008-02-21 US US12/070,797 patent/US7824764B2/en not_active Expired - Fee Related
- 2008-02-29 JP JP2008049891A patent/JP2008214848A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE68909268T2 (en) | 1988-02-01 | 1994-04-14 | Dow Corning | Process for modifying the surface of a solid plastic. |
US6299651B1 (en) | 1998-02-20 | 2001-10-09 | Milliken & Company | Fabrics comprising fibers having esterified triclosan derivatives diffused therein |
DE69908910T2 (en) | 1998-02-20 | 2004-05-19 | Milliken Research Corp. | METHOD FOR GIVING AN ANTIMICROBIAL PROPERTY OF LARGE LIFE; FIBERS, TEXTILES OR FABRIC MADE THIS |
CA2551701A1 (en) | 2005-06-30 | 2006-12-30 | Bolduc Leroux Inc. | Microbicidal air filter |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103757906A (en) * | 2014-02-18 | 2014-04-30 | 江南大学 | Preparation method of olefine halamine compound grafted antibacterial cotton fabric containing quaternary ammonium groups |
Also Published As
Publication number | Publication date |
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JP2008214848A (en) | 2008-09-18 |
EP1967618A3 (en) | 2013-05-01 |
US7824764B2 (en) | 2010-11-02 |
DE102007011076A1 (en) | 2008-09-11 |
DE102007011076B4 (en) | 2011-06-01 |
US20080220680A1 (en) | 2008-09-11 |
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