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WO2011032191A1 - Fluorescent fiber, use thereof, and method for the production thereof - Google Patents

Fluorescent fiber, use thereof, and method for the production thereof Download PDF

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Publication number
WO2011032191A1
WO2011032191A1 PCT/AT2010/000285 AT2010000285W WO2011032191A1 WO 2011032191 A1 WO2011032191 A1 WO 2011032191A1 AT 2010000285 W AT2010000285 W AT 2010000285W WO 2011032191 A1 WO2011032191 A1 WO 2011032191A1
Authority
WO
WIPO (PCT)
Prior art keywords
fibers
cellulosic
fiber
regenerated fiber
over
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.)
Ceased
Application number
PCT/AT2010/000285
Other languages
German (de)
French (fr)
Inventor
Gabriele Emlinger
Ulf Mathes
Alexander Gstettner
Gert Kroner
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to IN2222DEN2012 priority Critical patent/IN2012DN02222A/en
Priority to EP20100760892 priority patent/EP2478138B1/en
Priority to RU2012115659/05A priority patent/RU2541062C2/en
Priority to CN2010800416125A priority patent/CN102597342A/en
Priority to US13/496,670 priority patent/US20120244335A1/en
Priority to ES10760892T priority patent/ES2440939T3/en
Publication of WO2011032191A1 publication Critical patent/WO2011032191A1/en
Anticipated expiration legal-status Critical
Priority to US15/002,053 priority patent/US20160138217A1/en
Ceased legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/07Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath
    • D01F2/12Addition of delustering agents to the spinning solution
    • D01F2/14Addition of pigments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath
    • D01F2/16Addition of dyes to the spinning solution
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004General aspects of dyeing
    • D06P1/0012Effecting dyeing to obtain luminescent or phosphorescent dyeings
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30Flame or heat resistance, fire retardancy properties
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component

Definitions

  • Fluorescent fiber its use and method for its
  • the present invention relates to regenerated cellulosic regenerated fibers for use in high-visibility clothing such as described in standard EN 471, their use for
  • EN 471 deals exclusively with the warning effect of personal protective equipment, in particular warning clothing.
  • Warning clothing usually consists of a fluorescent
  • fluorescent material is, for the purposes of the present invention as defined in EN 471, a material that emits rather than absorbs radiation at longer wavelengths; in the text below, the term high-vis material is also used.
  • the present invention relates to the fluorescent background material but not to
  • Synthetic fibers typical danger electrostatic charge.
  • Fibers by the viscose process and lyocell process are known today as cellulosic regenerated fibers. They are used worldwide for standard applications produced in the textile and nonwovens sector with a single fiber titer between 0.8 and 16 dtex.
  • cellulose regenerated fibers can be dyed by the conventional bath method with fluorescent dyes. But the fibers dyed in this way do not meet the requirements of light fastness (ISO 105-B02, method 2> 5). After the xenon irradiation they are significantly bleached and show a strong change in hue and a greatly reduced color depth, which can be represented as a shift of the coordinates of the color space, for example.
  • Warning clothing as described for example in EN 471 fulfilled, and on the other hand, wearing comfort and safety aspects of these clothes increased at a reasonable cost. It should therefore be possible to make the protective and warning clothing from such a fiber without admixture of other fiber types. It is particularly important that the textiles produced from these fibers meet the following requirements for background materials in accordance with EN 471:
  • the light fastness of the fibers was determined according to ISO 105-B02 method. Furthermore, the object was to provide a suitable manufacturing method for these fibers. Surprisingly, this task could be solved by cellulosic
  • Regeneratfasern containing a spun color pigment and a dye applied by over-dyeing fluorescent dye are dissolved. These fibers of the invention have, in addition to the improved comfort and increased safety due to the cellulosic
  • the fibers also comply with the other values required in EN 471 with regard to rub fastness, perspiration fastness, wash fastness,
  • Dry cleaning fastness dry cleaning fastness, hypochlorite bleaching fastness and ironing fastness.
  • the spun-dyed regenerated cellulosic fiber can after a
  • Viscose process a modified viscose process (e.g.
  • viscose modal or lyocell.
  • the cellulosic regenerate fiber may contain other additives.
  • the cellulosic regenerated fiber is additionally flame-retarded.
  • a preferred embodiment of the flame-retarded fiber is made by incorporation of a pigmented flame retardant. As pigmented flame retardants come along with other types
  • the cellulosic in a further preferred embodiment, the cellulosic
  • Regenerate fiber also antibacterial equipped In this case, the substances known to the expert can be used.
  • Subsequent high-vis bath dyeing can be performed with dyes suitable for cellulosic materials (e.g., reactive dyes, direct dyes,
  • the over-dyeing, d. H. the bath dyeing may be carried out either on the flake of the spun-dyed fiber, on a yarn containing the spun-dyed fiber or on a textile surface containing the spun-dyed fiber. In this case, it is possible to apply the continuous and discontinuous dyeing methods known in principle to those skilled in the art.
  • the present invention also relates to the use of the fiber according to the invention for producing a yarn.
  • a yarn according to the invention may, in addition to the fibers according to the invention, also contain fibers of other origin, for example
  • Polyamideimide (Kermel®), (flame-retardant) wool, polybenzimidazole (PBI), polyimide (P84®), polyamides, (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, Carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers; and mixtures of these fibers.
  • the mixing partners may also have high-vis equipment.
  • the fiber according to the invention for the production of a textile fabric.
  • this fabric may also contain other fibers, for example (flame-retardant) polyester, modacrylic, para and meta-aramides, polyamide-imide (Kermel®),
  • Polyamides (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers, as well
  • the further fibers may also have a high-vis finish.
  • the textile fabric is preferably a woven, knitted or knitted fabric, but may in principle also be a nonwoven. In the case of a woven or knitted fabric, it is possible to mix the fibers according to the invention with the further fibers either by mixing before yarn production, the so-called intimate mixing, or by jointly using respectively pure yarns of the different fiber types during weaving, knitting or knitting.
  • the above-mentioned yarns or textile fabrics occur as intermediates within the textile warp.
  • Other warning items to be understood for the purposes of this invention for example, pennants, flags, flags and warning tapes or other items that are particularly well visible by a particularly eye-catching color or generate attention. The use according to the invention thus goes beyond the pure warning effect. If the fabric already mentioned above is used as the fabric - for example for use in
  • subject of the present invention is a process for the preparation of the above-described inventive fluorescent; cellulosic regenerated fibers in which a color pigment is spun into the fibers and these fibers are over-dyed in a later process step with a fluorescent dye.
  • the spinning is usually carried out by adding the color pigments to the spinning solution.
  • Such addition methods are generally known to the person skilled in the art for both the viscose and modal and solvent spinning processes.
  • spun-dyed cellulosic fibers are usually not later over-dyed in a further step with another dye, as spin dyeing is generally considered to be a very effective method, with the high fastness properties, both rubbing and light, washing and perspiration fastness can be achieved!
  • the present invention which is in combination with a later over-dyeing step, satisfies the specific ones
  • the over-dyeing, d. H. the bath dyeing can be carried out either on the flake of the spun-dyed fiber or on a yarn or a textile surface containing the spun-dyed fiber.
  • the continuous and discontinuous dyeing processes which are likewise known in principle to the person skilled in the art.
  • a spun-dyed flame-retarded viscose fiber contains 1.25% by weight of Pigment Yellow 3 (eg Aquarine Yellow 10 G) and 22% by weight of 2,2'-oxybis [5,5-dimethyl-1S-dioxaphosphorinane-3'-disulfide ( Exolit 5060, Fa. Clariant) in each case based on cellulose.
  • This fiber is then over-dyed with Remazol Leuchtgelb FL (DyStar) according to the following recipe:
  • the flake is placed in a dyebath containing 2% Remazol Leuchtgelb FL (DyStar Co.) and 100 g / l sodium sulfate at a liquor ratio of 1:10 and an initial temperature of 25 ° C and a heating rate of 1 ° C min to 50 ° C heated. After 10 min at this temperature, 5 g / l of soda is added and after a further 30 min 1, 2 ml / l NaOH (50%). After a further 40 minutes, the dyebath is allowed to cool and includes an aftertreatment with the rinse - soaps - rinse - soaps known to the person skilled in the art.
  • Example 2 A commercially available viscose fiber (Lenzing FR), which was also flame-retarded with Exolit 5060 and contained no spun-in color pigment, was over-dyed by the same method as described in Example 1. Were however, 6% Remazol Leuchtgelb FL (DyStar Co.) instead of 2% as used in Example 1. The fiber showed the test results shown in Table 2.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Woven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to a cellulosic regenerated fiber, which contains a pigment that is spun in and a fluorescent dye that is applied by overdying, the use thereof to produce yarns and sheet materials, and a method for producing said fibers. Said fiber fulfills the requirements of EN 471 with regard to luminance, color space, and rubbing fastness and has a light fastness (ISO 105-B02, method 2) of more than 5.

Description

Fluoreszierende Faser, deren Verwendung sowie Verfahren zu deren  Fluorescent fiber, its use and method for its

Herstellung  manufacturing

Gegenstand der vorliegenden Erfindung sind fluoreszierend ausgerüstete cellulosische Regeneratfasern für Einsatzzwecke in Warnkleidung wie beispielsweise in Norm EN 471 beschrieben, deren Verwendung zur The present invention relates to regenerated cellulosic regenerated fibers for use in high-visibility clothing such as described in standard EN 471, their use for

Herstellung von Garnen und Flächengebilden, sowie ein Verfahren zur Herstellung dieser Fasern. Stand der Technik: Production of yarns and fabrics, and a process for producing these fibers. State of the art:

Die EN 471 beschäftigt sich ausschließlich mit der Warnwirkung von persönlicher Schutzausrüstung, insbesondere mit Warnkleidung.  EN 471 deals exclusively with the warning effect of personal protective equipment, in particular warning clothing.

Warnkleidung besteht in der Regel aus einem fluoreszierenden Warning clothing usually consists of a fluorescent

Hintergrundmaterial und einem retroreflektierenden Material. Als Background material and a retroreflective material. When

fluoreszierendes Material wird für die Zwecke der vorliegenden Erfindung gemäß der Definition in der EN 471 ein Material bezeichnet, das Strahlung bei längerer Wellenlänge emittiert als absorbiert; im weiteren Text wird dafür auch der Begriff High-Vis-Material verwendet. Die vorliegende Erfindung bezieht sich auf das fluoreszierende Hintergrundmaterial, nicht aber auf fluorescent material is, for the purposes of the present invention as defined in EN 471, a material that emits rather than absorbs radiation at longer wavelengths; in the text below, the term high-vis material is also used. The present invention relates to the fluorescent background material but not to

retroreflektierende Materialien. retroreflective materials.

Bisher werden High-Vis-Textilien lediglich auf Basis von Synthesefasern und hier insbesondere Polyester gefertigt, die jedoch Nachteile hinsichtlich So far, high-vis textiles are made only on the basis of synthetic fibers and in particular polyester, but the disadvantages in terms

Tragekomfort und Sicherheit bieten. Die Nachteile solcher Textilien liegen insbesondere in einem unangenehmen Hautklima und in der Provide comfort and safety. The disadvantages of such textiles are especially in an unpleasant skin climate and in the

Geruchsentwicklung nach längerem Tragen aufgrund unzureichender feuchtigkeitsregulierender Materialeigenschaften, sowie in der für  Odor development after prolonged wear due to insufficient moisture-regulating material properties, and in the for

Synthesefasern typischen Gefahr elektrostatischer Aufladung. Synthetic fibers typical danger electrostatic charge.

Eine Alternative stellen aufwendige textile Konstruktionen dar, deren An alternative represent complex textile structures whose

Außenseite die High-Vis-Komponente enthält und deren Innenseite Outside contains the high-vis component and the inside

hauptsächlich aus cellulosischen Fasern besteht um den Tragekomfort zu verbessern, wie z.B. in WO 2006/017709 beschrieben. Als cellulosische Regeneratfasern sind heute vor allem Fasern nach dem Viskoseverfahren und Lyocellverfahren bekannt. Sie werden weltweit für Standardanwendungen im Textil- und Nonwovens-Bereich mit einem Einzelfasertiter zwischen 0,8 und 16 dtex hergestellt. mainly consists of cellulosic fibers to improve the comfort, as described for example in WO 2006/017709. Fibers by the viscose process and lyocell process are known today as cellulosic regenerated fibers. They are used worldwide for standard applications produced in the textile and nonwovens sector with a single fiber titer between 0.8 and 16 dtex.

Cellulosische Regeneratfasern können zwar nach den herkömmlichen Bad- Verfahren mit fluoreszierenden Farbstoffen gefärbt werden. Aber die auf diese Weise gefärbten Fasern erreichen die Anforderungen an die Lichtechtheit (ISO 105-B02, Verfahren 2 >5) nicht. Nach der Xenonbestrahlung sind sie erheblich ausgebleicht und zeigen einen stark veränderten Farbton und eine stark verminderte Farbtiefe, was sich beispielsweise als Verschiebung der Koordinaten des Farbraums darstellen läßt. Although cellulose regenerated fibers can be dyed by the conventional bath method with fluorescent dyes. But the fibers dyed in this way do not meet the requirements of light fastness (ISO 105-B02, method 2> 5). After the xenon irradiation they are significantly bleached and show a strong change in hue and a greatly reduced color depth, which can be represented as a shift of the coordinates of the color space, for example.

Seit Jahrzehnten ist bekannt, Viskosefasern durch Einspinnen von For decades, it has been known to viscose fibers by spinning

Farbpigmenten dauerhaft zu färben. Entsprechende Fasern sind am Markt erhältlich. Bisher gibt es aber keine spinngefärbten Regeneratfasern, die den Anforderungen der EN 471 entsprechen. Coloring pigments permanently. Corresponding fibers are available on the market. So far, however, there are no spun-dyed regenerated fibers that meet the requirements of EN 471.

Aufgabenstellung: Task:

Gegenüber diesem Stand der Technik bestand die Aufgabe, eine Faser zur Verfügung zu stellen, die einerseits die Anforderungen an Schutz- und  Compared to this prior art, the task was to provide a fiber available, on the one hand the requirements for protection and

Warnkleidung, wie sie beispielsweise in EN 471 beschrieben sind, erfüllt und andererseits Tragekomfort und Sicherheitsäspekte dieser Kleidung bei vertretbarem wirtschaftlichen Aufwand erhöht. Es sollte daher möglich sein, die Schutz- und Warnkleidung aus einer solchen Faser ohne Beimischung weiterer Faserarten herzustellen. Besonders wichtig ist es dabei, dass die aus diesen Fasern hergestellten Textilien die folgenden Anforderungen für Hintergrundmaterialien gemäß EN 471 bestehen: Warning clothing, as described for example in EN 471 fulfilled, and on the other hand, wearing comfort and safety aspects of these clothes increased at a reasonable cost. It should therefore be possible to make the protective and warning clothing from such a fiber without admixture of other fiber types. It is particularly important that the textiles produced from these fibers meet the following requirements for background materials in accordance with EN 471:

• Mindestleuchtdichtefaktor (Normwerte gemäß CIE Publikation Nr. 152) und Farbraum  • Minimum luminance factor (CIE Publication No. 152 standard) and color space

• Farbe nach Xenonbestrahlung: die Belichtung der Probe erfolgt nach ISO 105-B02, Verfahren 3  • Color after xenon irradiation: the exposure of the sample is carried out according to ISO 105-B02, method 3

• Reibechtheit trocken und nass (ISO 105-A02)  • Dry and wet rubbing fastness (ISO 105-A02)

Zusätzlich wurde die Lichtechtheit der Fasern nach ISO 105-B02 Verfahrend bestimmt. Weiters bestand die Aufgabe, ein geeignetes Herstellungsverfahren für diese Fasern zur Verfügung zu stellen. Überraschenderweise konnte diese Aufgabe durch cellulosische In addition, the light fastness of the fibers was determined according to ISO 105-B02 method. Furthermore, the object was to provide a suitable manufacturing method for these fibers. Surprisingly, this task could be solved by cellulosic

Regeneratfasern, die ein eingesponnenes Farbpigment sowie einen durch Überfärben aufgebrachten fluoreszierenden Farbstoff enthalten, gelöst werden. Diese erfindungsgemäßen Fasern weisen neben dem verbesserten Tragekomfort und erhöhter Sicherheit aufgrund der cellulosischen  Regeneratfasern containing a spun color pigment and a dye applied by over-dyeing fluorescent dye are dissolved. These fibers of the invention have, in addition to the improved comfort and increased safety due to the cellulosic

Grundstruktur überraschenderweise eine Lichtechtheit - gemessen nach ISO 105-B02, Verfahren 2 - von mehr als 5 auf. Dies war mit bisher bekannten cellulosischen Fasern nicht erreichbar. Basic structure surprisingly a lightfastness - measured according to ISO 105-B02, method 2 - of more than 5 on. This was not achievable with previously known cellulosic fibers.

Die Fasern entsprechen auch den anderen in EN 471 geforderten Werten bezüglich Reibechtheit, Schweißechtheit, Waschechtheit, The fibers also comply with the other values required in EN 471 with regard to rub fastness, perspiration fastness, wash fastness,

Trockenreinigungsechtheit, Hypochloritbleichechtheit und Bügelechtheit.  Dry cleaning fastness, hypochlorite bleaching fastness and ironing fastness.

Die spinngefärbte cellulosische Regeneratfaser kann nach einem The spun-dyed regenerated cellulosic fiber can after a

Viskoseverfahren, einem modifizierten Viskoseverfahren (z.B. Viscose process, a modified viscose process (e.g.

Modalverfahren, zinkfreies Viskoseverfahren mit AI-Sulfat, ...), aber auch nach einem Lösungsmittelverfahren, das mit organischen Lösungsmitteln wie geschmolzenen wässrigen Aminoxiden oder auch sogenannten ionischen Flüssigkeiten arbeitet, hergestellt werden. Die Fasern können Modalverfahren, zinc-free viscose process with Al sulfate, ...), but also after a solvent process that works with organic solvents such as molten aqueous amine oxides or so-called ionic liquids produced. The fibers can

dementsprechend als Viskose, Modal bzw. Lyocell bezeichnet werden. accordingly be referred to as viscose, modal or lyocell.

Die cellulosische Regeneratfaser kann weitere Zusatzstoffe enthalten. In einer besonderen Ausführungsform ist die cellulosische Regeneratfaser zusätzlich flammgehemmt ausgerüstet. Eine bevorzugte Ausführungsform der flammgehemmten Faser wird durch Inkorporation eines pigmentförmigen Flammschutzmittels hergestellt. Als pigmentförmige Flammschutzmittel kommen neben anderen Typen The cellulosic regenerate fiber may contain other additives. In a particular embodiment, the cellulosic regenerated fiber is additionally flame-retarded. A preferred embodiment of the flame-retarded fiber is made by incorporation of a pigmented flame retardant. As pigmented flame retardants come along with other types

insbesondere Organophosphorverbindungen in Frage, für Viskose in particular organophosphorus compounds in question, for viscose

beispielsweise das gut geeignete und bekannte 2,2'-oxybis[5,5-dimethyl- 1.S^-dioxaphosphorinan^'disulfid, erhältlich unter den Handelsnamen Exolit bzw. Sandoflam, hergestellt. For example, the well-suited and known 2,2'-oxybis [5,5-dimethyl- 1.S ^ -Dioxaphosphorinan ^ 'disulfide, available under the trade names Exolit and Sandoflam produced.

In einer weiteren, bevorzugten Ausführungsform ist die cellulosische In a further preferred embodiment, the cellulosic

Regeneratfaser auch antibakteriell ausgerüstet. Dabei können die dem Fachmann bekannten Substanzen eingesetzt werden. Regenerate fiber also antibacterial equipped. In this case, the substances known to the expert can be used.

Die anschließende High-Vis-Badfärbung kann mit für cellulosische Materialien geeigneten Farbstoffen (z.B. Reaktivfarbstoffe, Direktfarbstoffe, Subsequent high-vis bath dyeing can be performed with dyes suitable for cellulosic materials (e.g., reactive dyes, direct dyes,

Küpenfarbstoffe, ...) durchgeführt werden. Vat dyes, ...).

Das Überfärben, d. h. die Badfärbung kann entweder an der Flocke der spinngefärbten Faser, einem Garn, das die spinngefärbte Faser enthält oder einer Textilen Fläche, die die spinngefärbte Faser enthält, erfolgen. Dabei können die dem Fachmann grundsätzlich bekannten kontinuierlichen und diskontinuierlichen Färbeverfahren angewendet werden. The over-dyeing, d. H. the bath dyeing may be carried out either on the flake of the spun-dyed fiber, on a yarn containing the spun-dyed fiber or on a textile surface containing the spun-dyed fiber. In this case, it is possible to apply the continuous and discontinuous dyeing methods known in principle to those skilled in the art.

Durch geeignete Auswahl des Pigments für die Spinnfärbung und des High- Vis-Farbstoffs für die Badfärbung können auch Farbtöne erzielt werden, für By suitable selection of the pigment for the spin dyeing and the high-vis dye for the bath dye also shades can be achieved, for

c  c

die es bisher keine Einzellösungen gibt. There are no individual solutions so far.

Gegenstand der vorliegenden Erfindung ist auch die Verwendung der erfindungsgemäßen Faser zur Herstellung eines Garnes. Um für den jeweiligen Anwendungszweck passende Eigenschaften aufzuweisen, kann ein solches erfindungsgemäßes Garn neben den erfindungsgemäßen Fasern auch noch Fasern anderer Herkunft enthalten, beispielsweise The present invention also relates to the use of the fiber according to the invention for producing a yarn. In order to have suitable properties for the particular application, such a yarn according to the invention may, in addition to the fibers according to the invention, also contain fibers of other origin, for example

(flammgehemmten) Polyester, Modacryl, para- und meta-Aramide, (flame-retardant) polyester, modacrylic, para and meta-aramid,

Polyamidimid (Kermel®), (flammgehemmte) Wolle, Polybenzimidazol (PBI), Polyimid (P84®), Polyamide, (flammgehemmte) Polyamide, flammgehemmte Acrylfasern, Melaminfasern, Polyphenylensulfid (PPS), Polytetrafluorethylen (PTFE), Glasfasern, Baumwolle, Seide, Carbonfasern, oxidierte thermisch stabilisierte Polyacrylnitrilfasern (PANOX®) und elektrisch leitfähige Fasern; sowie Mischungen dieser Fasern. In einer bevorzugten Ausführungsform können die Mischungspartner ebenfalls eine High-Vis-Ausrüstung aufweisen. Ebenfalls Gegenstand der vorliegenden Erfindung ist die Verwendung der erfindungsgemäßen Faser zur Herstellung eines textilen Flächengebildes. Neben den erfindungsgemäßen Fasern kann dieses Flächengebilde auch weitere Fasern enthalten, beispielsweise (flammgehemmten) Polyester, Modacryl, para- und meta-Aramide, Polyamidimid (Kermel®), Polyamideimide (Kermel®), (flame-retardant) wool, polybenzimidazole (PBI), polyimide (P84®), polyamides, (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, Carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers; and mixtures of these fibers. In a preferred embodiment, the mixing partners may also have high-vis equipment. Likewise provided by the present invention is the use of the fiber according to the invention for the production of a textile fabric. In addition to the fibers according to the invention, this fabric may also contain other fibers, for example (flame-retardant) polyester, modacrylic, para and meta-aramides, polyamide-imide (Kermel®),

(flammgehemmte) Wolle, Polybenzimidazol (PBI), Polyimid (P84®), (flame retarded) wool, polybenzimidazole (PBI), polyimide (P84®),

Polyamide, (flammgehemmte) Polyamide, flammgehemmte Acrylfasern, Melaminfasern, Polyphenylensulfid (PPS), Polytetrafluorethylen (PTFE), Glasfasern, Baumwolle, Seide, Carbonfasern, oxidierte thermisch stabilisierte Polyacrylnitrilfasern (PANOX®) und elektrisch leitfähige Fasern, sowie Polyamides, (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers, as well

Mischungen dieser Fasern. In einer bevorzugten Ausführungsform können die weiteren Fasern ebenfalls eine High-Vis-Ausrüstung aufweisen. Das textile Flächengebilde ist bevorzugt ein Gewebe, Gewirke oder Gestrick, kann aber grundsätzlich auch ein Vlies sein. Im Falle eines Gewebes oder Gestrickes ist die Mischung der erfindungsgemäßen Fasern mit den weiteren Fasern entweder durch das Mischen vor der Garnherstellung, die sogenannte Intimmischung, oder durch gemeinsame Verwendung jeweils reiner Garne der verschiedenen Faserarten beim Weben, Wirken bzw. Stricken möglich. Mixtures of these fibers. In a preferred embodiment, the further fibers may also have a high-vis finish. The textile fabric is preferably a woven, knitted or knitted fabric, but may in principle also be a nonwoven. In the case of a woven or knitted fabric, it is possible to mix the fibers according to the invention with the further fibers either by mixing before yarn production, the so-called intimate mixing, or by jointly using respectively pure yarns of the different fiber types during weaving, knitting or knitting.

In gleicher Weise ist Gegenstand der vorliegenden Erfindung auch die In the same way, the subject of the present invention is also the

Verwendung der erfindungsgemäßen Fasern zur Herstellung eines Use of the fibers according to the invention for the production of a

Warnbekleidungsstücks oder eines sonstigen Warnartikels, wobei Garment or other warning article, wherein

üblicherweise die oben genannten Garne bzw. textilen Flächengebilde als Zwischenstufen innerhalb der textilen Kette auftreten. Als sonstige Warnartikel sollen für die Zwecke dieser Erfindung beispielsweise Wimpel, Fahnen, Flaggen und Warnbänder oder sonstige Artikel, die durch eine besonders auffällige Farbe besonders gut sichtbar sind bzw. Aufmerksamkeit erzeugen, verstanden werden. Die erfindungsgemäße Verwendung geht damit über die reine Warnwirkung hinaus. Falls als Flächengebilde das oben bereits genannte Vlies eingesetzt wird - beispielsweise für die Verwendung in Usually, the above-mentioned yarns or textile fabrics occur as intermediates within the textile warp. Other warning items to be understood for the purposes of this invention, for example, pennants, flags, flags and warning tapes or other items that are particularly well visible by a particularly eye-catching color or generate attention. The use according to the invention thus goes beyond the pure warning effect. If the fabric already mentioned above is used as the fabric - for example for use in

Wimpeln, Fahnen, Flaggen und Warnbändern - entfällt natürlich die Pennants, flags, flags and warning tapes - of course that eliminates

Zwischenstufe des Garns. Verschiedene Ausführungen solcher Kleidungsstücke und sonstiger Warnartikel sind dem Fachmann wohlbekannt und müssen daher hier nicht weiter beschrieben werden. Intermediate stage of the yarn. Different versions of such Garments and other warning articles are well known to those skilled in the art and therefore need not be further described here.

Ebenso ist Gegenstand der vorliegenden Erfindung ein Verfahren zur Herstellung der oben beschriebenen erfindungsgemäßen, fluoreszierenden; cellulosischen Regeneratfasern, in dem ein Farbpigment in die Fasern eingesponnen wird und diese Fasern in einem späteren Verfahrensschritt mit einem fluoreszierenden Farbstoff überfärbt werden. Das Einspinnen erfolgt üblicherweise durch Zugabe der Farbpigmente zur Spinnlösung. Solche Zugabeverfahren sind dem Fachmann grundsätzlich sowohl für das Viskose- als auch für Modal- und Lösungsmittelspinnverfahren bekannt. Allerdings werden spinngefärbte cellulosische Fasern üblicherweise nicht später in einem weiteren Schritt mit einem weiteren Farbstoff überfärbt, da das Spinnfärben allgemein als ein sehr effektives Verfahren gilt, mit dem hohe Echtheiten, sowohl Reib- als auch Licht-, Wasch- und Schweißechtheit erzielt werden können! Die vorliegende Erfindung, die in der Kombination mit einem späteren Überfärbeschritt liegt, erfüllt jedoch die speziellen Likewise subject of the present invention is a process for the preparation of the above-described inventive fluorescent; cellulosic regenerated fibers in which a color pigment is spun into the fibers and these fibers are over-dyed in a later process step with a fluorescent dye. The spinning is usually carried out by adding the color pigments to the spinning solution. Such addition methods are generally known to the person skilled in the art for both the viscose and modal and solvent spinning processes. However, spun-dyed cellulosic fibers are usually not later over-dyed in a further step with another dye, as spin dyeing is generally considered to be a very effective method, with the high fastness properties, both rubbing and light, washing and perspiration fastness can be achieved! However, the present invention, which is in combination with a later over-dyeing step, satisfies the specific ones

Anforderungen an Fasern aus Cellulose für Warnbekleidung. Requirements for cellulose fibers for warning clothing.

Das Überfärben, d. h. die Badfärbung kann entweder an der Flocke der spinngefärbten Faser oder an einem Garn oder einer textilen Fläche, die die spinngefärbte Faser enthält, erfolgen. Dabei können die dem Fachmann ebenfalls grundsätzlich bekannten kontinuierlichen und diskontinuierlichen Färbeverfahren angewendet werden. The over-dyeing, d. H. the bath dyeing can be carried out either on the flake of the spun-dyed fiber or on a yarn or a textile surface containing the spun-dyed fiber. In this case, it is also possible to use the continuous and discontinuous dyeing processes which are likewise known in principle to the person skilled in the art.

Die Erfindung soll nun anhand von Beispielen erläutert werden. Diese sind ist als mögliche Ausführungsformen der Erfindung zu verstehen. Keineswegs ist die Erfindung auf den Umfang dieser Beispiele eingeschränkt. The invention will now be explained by way of examples. These are to be understood as possible embodiments of the invention. By no means is the invention limited to the scope of these examples.

Beispiel 1 : Example 1 :

Eine spinngefärbte flammgehemmte Viskosefaser enthält 1 ,25 Gew.-% Pigment Gelb 3 (z.B. Aquarine Yellow 10 G) und 22 Gew.-% 2,2'-oxybis[5,5 dimethyl-1.S^-dioxaphosphorinanß^'disulfid (Exolit 5060, Fa. Clariant) jeweils bezogen auf Cellulose. Diese Faser wird anschließend mit Remazol Leuchtgelb FL (Fa. DyStar) gemäß folgender Rezeptur überfärbt: A spun-dyed flame-retarded viscose fiber contains 1.25% by weight of Pigment Yellow 3 (eg Aquarine Yellow 10 G) and 22% by weight of 2,2'-oxybis [5,5-dimethyl-1S-dioxaphosphorinane-3'-disulfide ( Exolit 5060, Fa. Clariant) in each case based on cellulose. This fiber is then over-dyed with Remazol Leuchtgelb FL (DyStar) according to the following recipe:

Die Flocke wird in ein Färbebad, enthaltend 2 % Remazol Leuchtgelb FL (Fa. DyStar) und 100 g/l Natriumsulfat bei einem Flottenverhältnis: 1 :10 und einer Anfangstemperatur von 25°C gegeben und mit einer Heizrate von 1°CV min auf 50°C aufgeheizt. Nach 10 min bei dieser Temperatur wird 5 g/l Soda zugegeben und nach weiteren 30 min 1 ,2 ml/l NaOH (50%ig). Nach weiteren 40 min lässt man das Färbebad abkühlen und schließt eine Nachbehandlung mit der für den Fachmann bekannten Folge Spülen - Seifen - Spülen - Seifen an. The flake is placed in a dyebath containing 2% Remazol Leuchtgelb FL (DyStar Co.) and 100 g / l sodium sulfate at a liquor ratio of 1:10 and an initial temperature of 25 ° C and a heating rate of 1 ° C min to 50 ° C heated. After 10 min at this temperature, 5 g / l of soda is added and after a further 30 min 1, 2 ml / l NaOH (50%). After a further 40 minutes, the dyebath is allowed to cool and includes an aftertreatment with the rinse - soaps - rinse - soaps known to the person skilled in the art.

Die Faser wurde anschließend getrocknet und ein Gewebe daraus hergestellt. Dieses zeigte die in Tabelle 1 enthaltenen Prüfergebnisse. Diese Ergebnisse zeigen, dass die erfindungsgemäß hergestellten Fasern, Garne und Textilien hervorragend für die Verwendung in Warnkleidung geeignet sind und nicht ausbleichen. The fiber was then dried and a fabric made therefrom. This showed the test results shown in Table 1. These results show that the fibers, yarns and textiles produced according to the invention are outstandingly suitable for use in high-visibility clothing and do not fade.

Tabelle 1 : Prüfergebnisse (für Beispiel 1) Table 1: Test results (for Example 1)

Figure imgf000008_0001
Figure imgf000008_0001

Beispiel 2 (Vergleichsbeispiel): Example 2 (Comparative Example)

Eine handelsübliche, ebenfalls mit Exolit 5060 flammgehemmte Viskosefaser (Lenzing FR), die kein eingesponnenes Farbpigment enthielt, wurde nach der gleichen Methode wie in Beispiel 1 beschrieben, überfärbt. Dabei wurden jedoch 6% Remazol Leuchtgelb FL (Fa. DyStar) anstatt 2% wie in Beispiel 1 verwendet. Die Faser zeigte die in Tabelle 2 enthaltenen Prüfergebnisse. A commercially available viscose fiber (Lenzing FR), which was also flame-retarded with Exolit 5060 and contained no spun-in color pigment, was over-dyed by the same method as described in Example 1. Were however, 6% Remazol Leuchtgelb FL (DyStar Co.) instead of 2% as used in Example 1. The fiber showed the test results shown in Table 2.

Tabelle 2: Prüfergebnisse (für Beispiel 2) Table 2: Test results (for Example 2)

Figure imgf000009_0001
Figure imgf000009_0001

Farbton und Farbtiefe veränderten sich durch die Belichtung bei der Faser nach dem Stand der Technik in Beispiel 2 deutlich stärker als bei der erfindungsgemäßen Faser aus Beispiel 1 , was sich auch an der stärkeren Verschiebung der Koordinaten des Farbraums klar erkennen lässt. Auch die Leuchtdichte verschlechtert sich bei der nicht erfindungsgemäßen Faser durch die Belichtung erheblich stärker als bei der erfindungsgemäßen Faser. Besonders gravierend ist jedoch die erheblich schlechtere Lichtechtheit der Faser in Beispiel 2 gegenüber der erfindungsgemäßen Faser aus Beispiel 1. Hue and color depth changed significantly by the exposure in the fiber according to the prior art in Example 2 than in the inventive fiber of Example 1, which can be clearly seen in the stronger shift of the coordinates of the color space. The luminance also deteriorates considerably more in the case of the non-inventive fiber as a result of the exposure than in the case of the fiber according to the invention. Particularly serious, however, is the significantly poorer lightfastness of the fiber in Example 2 over the fiber of Example 1 according to the invention.

Claims

Patentansprüche: claims: 1. Cellulosische Regeneratfaser, die ein eingesponnenes Farbpigment sowie einen durch Überfärben aufgebrachten fluoreszierenden 1. Cellulosic regenerated fiber comprising a spun color pigment and a fluorescent dye applied by over-dyeing Farbstoff enthält.  Contains dye. 2. Cellulosische Regeneratfaser gemäß Anspruch 1 , die eine 2. Cellulosic regenerated fiber according to claim 1, which is a Lichtechtheit, gemessen nach ISO 105-B02, Verfahren 2, von mehr als 5 aufweist.  Light fastness, measured according to ISO 105-B02, method 2, of more than 5. 3. Cellulosische Regeneratfaser gemäß Anspruch 1 , die nach einem 3. Cellulosic regenerated fiber according to claim 1, which according to a Viskose-, Modal- oder Lyocellverfahren hergestellt wird.  Viscose, modal or lyocell method is produced. 4. Cellulosische Regeneratfaser gemäß Anspruch 1 , die zusätzlich 4. Cellulosic regenerated fiber according to claim 1, in addition flammgehemmt ausgerüstet ist.  equipped flame retardant. 5. Cellulosische Regeneratfaser gemäß Anspruch 4, wobei die The regenerated cellulose fiber according to claim 4, wherein the flammhemmende Ausrüstung eine eingesponnene  flame retardant equipment a braided Organophosphorverbindung (bevorzugt 2,2'-oxybis[5,5-dimethyl-1 ,3,2- dioxaphosphorinan]2,2'disulfid) ist.  Organophosphorus compound (preferably 2,2'-oxybis [5,5-dimethyl-1, 3,2-dioxaphosphorinan] 2,2'disulfide). 6. Cellulosische Regeneratfaser gemäß Anspruch 1 , die zusätzlich 6. Cellulosic regenerated fiber according to claim 1, in addition antibakteriell ausgerüstet ist.  is equipped antibacterial. 7. Verwendung der Fasern gemäß den Ansprüchen 1 bis 6 zur 7. Use of the fibers according to claims 1 to 6 for Herstellung eines Garnes.  Production of a yarn. 8. Verwendung der Fasern gemäß den Ansprüchen 1 bis 6 zur 8. Use of the fibers according to claims 1 to 6 for Herstellung eines textilen Flächengebildes.  Production of a textile fabric. 9. Verwendung der Fasern gemäß den Ansprüchen 1 bis 6 zur 9. Use of the fibers according to claims 1 to 6 for Herstellung eines Warnbekleidungsstücks oder eines sonstigen Warnartikels. Manufacture of a garment or other warning article. 10.Verfahren zur Herstellung fluoreszierender cellulosischer 10.A method for producing fluorescent cellulosic Regeneratfasern gemäß den Ansprüchen 1 bis 6, dadurch  Regenerate fibers according to claims 1 to 6, characterized gekennzeichnet, dass ein Farbpigment in die Fasern eingesponnen wird und diese Fasern in einem späteren Verfahrensschritt mit einem fluoreszierenden Farbstoff überfärbt werden.  characterized in that a color pigment is spun into the fibers and these fibers are over-dyed in a later process step with a fluorescent dye. 11.Verfahren gemäß Anspruch 10, wobei das Überfärben durch einen kontinuierlichen oder diskontinuierlichen Verfahrensschritt erfolgt. 11.A method according to claim 10, wherein the over-dyeing is carried out by a continuous or discontinuous process step. 12. Verfahren gemäß Anspruch 10 oder 11 , wobei das Überfärben an einem aus der cellulosischen Regeneratfaser hergestellten Garn oder textilen Flächengebilde erfolgt. 12. A method according to claim 10 or 11, wherein the over-dyeing is carried out on a yarn or fabric made of the cellulosic regenerated fiber.
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