EP2473657B1 - Fibres cellulosiques ignifugées, leur utilisation ainsi que leur procédé de fabrication - Google Patents

Fibres cellulosiques ignifugées, leur utilisation ainsi que leur procédé de fabrication Download PDF

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EP2473657B1
EP2473657B1 EP10754846.3A EP10754846A EP2473657B1 EP 2473657 B1 EP2473657 B1 EP 2473657B1 EP 10754846 A EP10754846 A EP 10754846A EP 2473657 B1 EP2473657 B1 EP 2473657B1
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flame
fiber
viscose
fibers
cellulose
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EP2473657A1 (fr
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Gert Kroner
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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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
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

  • the present invention provides flame-retarded cellulosic regenerated fibers having improved performance properties for textile applications which, for example, also satisfy the requirements of industrial laundry, their use for the production of yarns and fabrics, and a process for producing these fibers.
  • Fibers by the viscose process are mainly known today as cellulosic regenerated fibers and are produced worldwide for standard applications in the textile and nonwovens sector with a single fiber titer of between 0.8 and 16 dtex.
  • flame-retardant finish of viscose fibers various chemicals are described in the literature. Above all, flame retardants based on halogens, silicon and phosphorus are used.
  • Viscose fibers whose flame-retardant effect is based on the use of silicates described, for example, in the patents WO9313249 or CN1847476- are ecologically safe, but far from meeting the requirements of the modern textile industry in terms of mechanical fiber properties and wash resistance. According to the current state of knowledge, only completely water-insoluble solid phosphorus-containing flame retardants which do not contain halogens can fulfill all desired requirements with regard to ecology, flame-retardant behavior, textile data and other functional properties.
  • EP1882760 describes the preparation of flame-retarded viscose fibers using flame retardant dispersions based on a 2,2'-oxybis [5,5-dimethyl-1,3,2-dioxaphosphorinane] 2,2'-disulfide.
  • the particle size may be a maximum of 10 microns and that the spinning mass must therefore be cleaned before spinning through filters with a maximum mesh size of 10 microns.
  • this criterion is not sufficient to produce fibers that meet the requirements described here.
  • maximum particle size of 10 microns is perhaps sufficient for viscose filaments, ie continuous filaments, but does not meet the requirements of a modern staple fiber production with fiber fineness of about 1 to 4 dtex; a 1.3 dtex fiber has a diameter of about 10 ⁇ m.
  • WO 97/02315 discloses both the preparation of flame-retarded fibers by the viscose process (Example 2) and by the lyocell process (Examples 3 and 4). While for the obtained lyocell fibers Phosphorgehalte and Bisfa modules are given disclosed WO 97/02315 such values for the viscose fibers not.
  • Standard viscose fibers are now widely used in light-weight fashion textiles.
  • the low strength, especially when wet, the high elongation and the high surface shrinkage put the use of viscose but limits.
  • these textile properties do not permit use in segments which require frequent washing (especially in industrial washes) of the textiles.
  • a measure of the washability is the area shrinkage.
  • BISFA wet modulus In order to be able to grasp the area shrinkage easily quantitatively, its relationship with the wet modulus, measured according to the regulations of the BISFA and therefore hereinafter referred to as BISFA wet modulus, is exploited (BISFA, testing methods viscose, modal, lyocell and acetate staple fibers and tows, 2004 Edition).
  • the fibers described in the prior art, or commercially available are all made by standard viscose methods. Although they show comparatively good mechanical fiber data for flame-retardant viscose fibers, since the phosphorus contents are very low. Investigations with various flame retardants on the basis of phosphorus have shown, however, that only from a phosphorus content of about 2.8%, a sufficient flame retardant effect is achieved. The flame retardancy correlates very well with the content of flame retardant converted to pure phosphorus.
  • flame-retardant fibers could be used to particular advantage in products that are also exposed to heavy mechanical loads, for example in workwear for particularly dangerous activities such as fire departments, foundries, military, petroleum and chemical industries.
  • Synthetic high performance fibers such as (aromatic) polyamides, aramids, polyimides and the like are already commonly used for such products.
  • these fibers have a low wearing comfort, since they are not able to absorb moisture sufficiently.
  • the object was to provide a flame-retardant cellulosic fiber available, which meets the current requirements for an economically and ecologically responsible manufacturing process and the increased textile mechanical requirements, such as occur in an industrial cleaning of the garments made therefrom.
  • the object was to provide a suitable manufacturing method for these fibers.
  • this object could be achieved by a flame-retardant Regeneratcellulosemaschine for textile applications, which contains a spun, partlkelförmlge, phosphorus compound, preferably an organophosphorus compound as a flame retardant substance and has a use value between 10 and 35 and was prepared by a viscose process.
  • a flame-retardant Regeneratcellulosemaschine for textile applications which contains a spun, partlkelförmlge, phosphorus compound, preferably an organophosphorus compound as a flame retardant substance and has a use value between 10 and 35 and was prepared by a viscose process.
  • Such a fiber could be produced for the first time by a modified viscose process according to the invention.
  • This flame-retardant substance preferably has a particle size distribution with x 50 smaller than 1.0 ⁇ m and x 99 smaller than 5.0 ⁇ m.
  • organophosphorus compound 2,2'-oxybis [5,5-dimethyl-1,3,2-dioxaphosphorinan] 2,2'-disulfide (Formula I) is preferably used.
  • This substance is available under the trade names Exolit and Sandoflam in sufficient quantities and is not washed out of the fibers during the manufacturing process and also in the subsequent application:
  • the present invention also relates to the use of the fiber according to the invention for producing a yarn.
  • a yarn is characterized by yarns made of fibers, which were previously available, by a significantly higher strength.
  • a yarn according to the invention can also contain fibers of other origin in addition to the fibers according to the invention, for example wool, flame-retardant wool, para- and meta-aramides, polybenzimidazole (PBI), p-phenyl-2,6 Benzobisoxazole (PBO), polyimide (P84®), polyamideimide (Kermel®), modacrylic, polyamides, flame retarded polyamides, flame retarded acrylic fibers, melamine fibers, polyesters, flame retarded polyesters, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk , Carbon fibers, oxidized thermally stabilized polyacrylonitrile (PANOX®) fibers
  • PBI polybenzimid
  • this fabric may also contain other fibers, for example and in particular wool, flame-retardant wool, para and meta-aramides, polybenzimidazole (PBI), p-phenyl-2,6-benzobisoxazole (PBO), polyimide (P84®) , Polyamideimide (Kermel®), modacrylic, polyamides, flame retarded polyamides, flame retarded acrylic fibers, melamine fibers, polyesters, flame retardant polyesters, 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.
  • PBI polybenzimidazole
  • PBO p-phenyl-2,6-benzobisoxazole
  • P84® polyimide
  • Polyamideimide (Kermel®) Polyamideimide
  • the sheet is preferably a woven, knitted or knitted fabric, but may in principle also be a nonwoven. Also for high quality nonwovens is the use of fibers with high BISFA wet modulus and high strength crucial. 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 fiber according to the invention can be produced by a modified viscose process according to the invention, which is also the subject of the present invention.
  • Viscose processes for staple fibers and continuous filaments have been known in principle for many years and, for example, at length K. Götze, man-made fibers by the viscose process, 1967 , described.
  • the textile properties of the resulting fibers and filaments are significantly affected by many parameters.
  • limits are set for many influencing factors by the design of the existing production plants, which can not be exceeded for technical or economic reasons, so that any variations of the parameters are often not possible and therefore the expert would not have caused this.
  • the invention therefore also provides a process for producing a flame-retarded regenerated cellulose fiber for textile applications by spinning a viscose with a content of 4 to 7% cellulose, 5 to 10% NaOH, 36 to 42% (based on cellulose) carbon disulfide and 1 to 5% (based on cellulose) of a modifier in a spin bath, stripping off the coagulated filaments, using a viscose whose spin gamma value is 50 to 68, preferably 55 to 58, and whose
  • a viscose is used, to which the modifier is added only shortly before the spinning of the viscose.
  • Spinning gamma is the proportion of carbon disulfide molecules bound to 100 cellulose molecules. The spin gamma value is determined according to Zellcheming leaflet draft by R. Stahn [1958] and leaflet III / F 2.
  • the term "ball drop” is understood to mean the viscosity determined by the falling ball method; it is expressed in terms of bullet seconds. The provision is in K. Götze, Chemiefasern [1951], p. 175 specified.
  • the flame retardant phosphorus compound prepared as a pigment is added to the viscose spinning solution in the form of a pigment dispersion according to the invention.
  • the flame retardant Spun substance that the finished fiber contains at least 2.6%, preferably between 3.2% and 6.0%, more preferably between 3.5% and 6.0% phosphorus, based on cellulose.
  • a flame retardant organophosphorus compound particularly suitable for the purposes of the present invention is 2,2'-oxybis [5,5-dimethyl-1,3,2-dioxaphosphorinane] 2,2'-disulfide.
  • the quality of the pigment dispersion has a significant influence on the fiber properties. This is determined by the average and maximum particle size of the pigments, the concentration of the dispersion in use, d. H. during the addition to the viscose spinning solution, as well as the type and amount of the dispersing aids.
  • Fig. 2 shows a size distribution of a still suitable pigment dispersion.
  • the pigment dispersion should contain between 10 and 50% of the flame retardant.
  • the influence of the dispersant is not described as fully as it would be appropriate.
  • many chemicals that provide a highly stabilized flame retardant dispersion have negative effects on the spinning process, as they also have a modifying effect in the viscose, but do not positively affect the fiber strength, in contrast to the modifiers used.
  • As ideal dispersants for the flame retardant dispersion for the production of the fibers according to the invention which do not adversely affect the fiber strength, in particular those have been found which belong to the group containing modified polycarboxylates, water-soluble polyesters, alkyl ether phosphates, end-capped nonylphenol ethoxylates, castor oil alkoxyl esters and carboxymethylated alcohol polyglycol ethers.
  • the pigment dispersion should contain between 1.5 and 13% of the dispersing aid.
  • the alkali cellulose nonwoven was fiberized, aged and sulfided.
  • the xanthate was dissolved with a dilute sodium hydroxide solution to a viscose with 5.6% cellulose, 6.8% NaOH and 39% CS 2 , based on cellulose.
  • the viscose was filtered 4 times and vented. The viscose was dosed 1 hour before spinning 3%, based on cellulose, ethoxylated amine, a modifier causing a shell structure.
  • the viscose was ripened to a spinning gamma value of 57.
  • the viscosity during spinning was 80 falling seconds.
  • the finished flame retardant dispersion is added to this ready-to-spin viscose.
  • the nozzles used have a nozzle hole diameter of 60 ⁇ m.
  • the spin bath contains 72 g / l sulfuric acid, 120 g / l sodium sulfate and 60 g / l zinc sulfate.
  • the spinning bath temperature was 38 ° C.
  • the coagulated and partially regenerated plastic thread strand of pale yellow color was over a Galette (G 1) in a second bath, whose temperature was 95 ° C, out and stretched there between G 1 and a second galette (G 2) by 120%.
  • the final discharge was 42 m / min.
  • the tow was cut into stacks 40 mm in length, which was completely regenerated in dilute sulfuric acid, then acid washed with hot water, desulfurized with dilute sodium hydroxide solution, rinsed again, bleached with dilute sodium hypochlorite solution, rinsed again, rinsed, pressed and dried.
  • Example 1 6 parts by weight of 2,2'-oxybis [5,5-dimethyl-1,3,2-dioxaphosphorinan] 2,2'disulfide, 6 parts by weight of water and 1.1 parts by weight of ethoxylated phthalic acid are processed as in Example 1 to a ready-to-spiny viscose (composition: cellulose 5.8%, NaOH 6.5%, 40% CS 2 , based on cellulose, as modifier a mixture of 2% DMA + 1% PEG 2000, each based on cellulose) and in a spun aqueous spin bath.
  • the nozzles used have a nozzle hole diameter of 50 microns.
  • the spin bath contains 73 g / l sulfuric acid, 120 g / l sodium sulfate and 58 g / l zinc sulfate.
  • a fiber was made according to the teachings of CN101037812 produced. Since no information is given on the wet modulus in this publication, the conditions of the example with the highest wet strength (Example 2, 1.52 cN / tex) of the obtained fiber were selected and the following process conditions were set accordingly: cellulose 8.86%, NaOH 6 , 24%, 31% CS 2 , based on cellulose. A modifier was not added. The viscose was spun at a viscosity of 42 falling ball seconds. The high levels of phosphorus reported in this publication could not be reconstructed. In order to achieve acceptable strengths, several optimization experiments with different levels of flame retardant were carried out under the given conditions.
  • the nozzles used have a nozzle hole diameter of 60 microns.
  • the spin bath contains 115 g / l sulfuric acid, 330 g / l sodium sulfate and 45 g / l zinc sulfate.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Claims (13)

  1. Fibre de cellulose régénérée ignifugée pour applications textiles, caractérisée en ce que, en sa qualité de substance ignifuge, elle contient un composé phosphoré particulaire intégré, en ce qu'elle présente une valeur d'usage - définie comme le produit de la teneur en phosphore et du module humide, le module humide étant mesuré selon le règlement BISFA (BISFA, Testing methods viscose, modal, lyocell and acetate staple fibres and tows, 2004 Edition) - entre 10 et 35, et en ce qu'elle a été fabriquée selon un procédé viscose.
  2. Fibre ignifugée selon la revendication 1 qui contient au moins 2,8 % de phosphore, de préférence entre 3,2 % et 6,0 %, ou mieux encore entre 3,5 % et 6,0 %, rapporté à la cellulose.
  3. Fibre ignifugée selon la revendication 1 ou 2, le composé phosphore étant du disulfure de (diméthyle-5,5 dioxaphosphorinane-1,3,2)-oxybis-2,2' (1).
  4. Fibre ignifugée selon les revendications 1 à 3 qui présente un module humide BISFA (Bm) ≥0,5·(√T)·10/T pour un allongement de 5 % à l'état humide.
  5. Fibre ignifugée selon les revendications 1 à 4, caractérisée en ce que la substance ignifuge présente une distribution granulométrique avec x50 inférieur à 1,0 µm et x99 inférieur à 5,0 µm.
  6. Fibre ignifugée selon les revendications 1 à 5, caractérisée en ce que la dispersion du retardateur de flamme contient un agent dispersant choisi dans le groupe comprenant des polycarboxylates modifiés, des polyesters solubles dans l'eau, des phosphates d'alkyléther, des éthoxylates de nonylphénol à groupe terminal fermé, des esters alkoxylés d'huile de ricin et des polyglycoléthers d'alcools carboxymethylés.
  7. Utilisation des fibres selon les revendications 1 à 6 pour la production d'un fil.
  8. Utilisation des fibres selon les revendications 1 à 6 pour la fabrication d'un produit textile.
  9. Procédé de fabrication d'une fibre de cellulose régénérée ignifugée pour applications textiles par filage, dans un bain de coagulation, d'une viscose ayant une teneur de 4 à 7 % de cellulose, de 5 à 10 % de NaOH, de 36 à 42 % (rapportée à la cellulose) de sulfure de carbone, et de 1 à 5 % (rapportée à la cellulose) d'un agent de modification, et extraction des fils coagulés, la viscose utilisée ayant une valeur de filage gamma de 50 à 68, et une viscosité de filage de 50 à 120 secondes de chute de bille, et la température du bain de coagulation étant de 34 à 48°C ; caractérisé en ce que
    a. le rapport alcalin (= concentration en cellulose / teneur en alcalin) de la viscose prête à filer est de 0,7 à 1,5,
    b. les concentrations utilisées pour le bain de coagulation sont les suivantes :
    • H2SO4    68 - 90 g/l
    • Na2SO4    90 - 160 g/l
    • ZnSO4    30 - 65 g/l
    c. l'extraction finale du bain de coagulation se fait à une vitesse comprise entre 15 et 60 m/mn, et
    d. un composé phosphore sous forme de pigment est intégré, comme substance ignifuge, sous la forme d'une dispersion de pigment.
  10. Procédé selon la revendication 9, seule une quantité de substance ignifuge y étant intégrée de manière à ce que la fibre finie contienne au moins 2,8 % de phosphore, de préférence entre 3,2 % et 6,0 %, ou mieux encore entre 3,5 % et 6,0 %, rapporté à la cellulose.
  11. Procédé selon la revendication 9, le composé organophosphoré étant du disulfure de (diméthyle-5,5 dioxaphosphorinane-1,3,2)-oxybis-2,2' (I).
  12. Procédé selon la revendication 9, le pigment de dispersion contenant entre 10 et 50 % de ladite substance ignifuge, avec une dimension moyenne des particules (x90) inférieure à 1,0 µm et une dimension maximum des particules (x99) inférieure à 5,0 µm, et entre 1,5 et 20 % dudit agent dispersant.
  13. Procédé selon la revendication 12, en utilisant, pour la dispersion du retardateur de flamme, un agent dispersant choisi dans le groupe comprenant des polycarboxylates modifiés, des polyesters solubles dans l'eau, des phosphates d'alkyléther, des éthoxylates de nonylphénol à groupe terminal fermé, des esters alkoxylés d'huile de ricin et des polyglycoléthers d'alcools carboxymethylés.
EP10754846.3A 2009-09-01 2010-07-27 Fibres cellulosiques ignifugées, leur utilisation ainsi que leur procédé de fabrication Active EP2473657B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0137109A AT508687A1 (de) 2009-09-01 2009-09-01 Flammgehemmte cellulosische faser, deren verwendung sowie verfahren zu deren herstellung
PCT/AT2010/000273 WO2011026159A1 (fr) 2009-09-01 2010-07-27 Fibres cellulosiques ignifugées, leur utilisation ainsi que leur procédé de fabrication

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Publication Number Publication Date
EP2473657A1 EP2473657A1 (fr) 2012-07-11
EP2473657B1 true EP2473657B1 (fr) 2014-04-30

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US (1) US20120177919A1 (fr)
EP (1) EP2473657B1 (fr)
CN (1) CN102482800B (fr)
AT (1) AT508687A1 (fr)
ES (1) ES2487494T3 (fr)
TW (1) TWI476309B (fr)
WO (1) WO2011026159A1 (fr)

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AT511746B1 (de) * 2011-08-10 2013-12-15 Chemiefaser Lenzing Ag Aktivkohle-enthaltende cellulosische man-made faser sowie verfahren zu deren herstellung und verwendung
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AT513426A1 (de) * 2012-09-17 2014-04-15 Chemiefaser Lenzing Ag Spinngefärbte Modalfaser, deren Verwendung sowie Verfahren zu deren Herstellung
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AT516414B1 (de) 2014-10-28 2017-07-15 Chemiefaser Lenzing Ag Flüssigkeitsgetränkter Vliesstoff, enthaltend Zinkoxid-haltige Cellulosefasern
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CN105040207A (zh) * 2015-05-29 2015-11-11 安徽省含山县顺天纺织有限公司 一种工业用具有阻燃效果的聚丙烯纤维再生棉混纺纱及其制备方法
CN105586679A (zh) * 2016-01-26 2016-05-18 安徽省无为天成纺织有限公司 一种防护服用复合阻燃耐高温混纺纱线
DE102016001910B4 (de) * 2016-02-18 2019-10-10 Viscose Faser Gmbh Verfahren zum Bereitstellen einer Pigmentmenge und Verwendung der damit bereitgestellten Pigmentmenge
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EP3260595B1 (fr) 2016-06-20 2018-05-09 Viscose Faser GmbH Procédé d'extraction de fibres synthétiques difficilement inflammables à partir de déchets textiles
AU2018346452B2 (en) * 2017-10-06 2020-10-15 Lenzing Aktiengesellschaft Flame retardant Lyocell filament
EP3476985A1 (fr) 2017-10-27 2019-05-01 Lenzing Aktiengesellschaft Fibres synthétiques cellulosiques ignifugées
US11905630B2 (en) 2019-02-22 2024-02-20 Jess Black Inc. Fire-resistant double-faced fabric of knitted construction
EP3754053A1 (fr) 2020-05-04 2020-12-23 Lenzing Aktiengesellschaft Fibre cellulosique teinte dans la masse
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ATE494406T1 (de) 2006-07-28 2011-01-15 Chemiefaser Lenzing Ag Verfahren zur herstellung von flammhemmenden viskosefasern
CN1904156A (zh) 2006-07-31 2007-01-31 唐山三友集团化纤有限公司 阻燃粘胶短纤维及其生产工艺
CN101037812A (zh) 2007-04-06 2007-09-19 山东海龙股份有限公司 抗融阻燃粘胶纤维及其制备方法
CN101215726A (zh) 2007-12-27 2008-07-09 山东海龙股份有限公司 阻燃粘胶纤维制造方法

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US20120177919A1 (en) 2012-07-12
TW201129744A (en) 2011-09-01
TWI476309B (zh) 2015-03-11
AT508687A1 (de) 2011-03-15
EP2473657A1 (fr) 2012-07-11
CN102482800B (zh) 2015-04-22
CN102482800A (zh) 2012-05-30
WO2011026159A1 (fr) 2011-03-10

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