US20190127888A1 - Modified viscose fiber - Google Patents

Modified viscose fiber Download PDF

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Publication number
US20190127888A1
US20190127888A1 US16/095,778 US201716095778A US2019127888A1 US 20190127888 A1 US20190127888 A1 US 20190127888A1 US 201716095778 A US201716095778 A US 201716095778A US 2019127888 A1 US2019127888 A1 US 2019127888A1
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Prior art keywords
fiber
weight
viscose
fibers
content
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Abandoned
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US16/095,778
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English (en)
Inventor
Heidrun Fuchs
Christoph Schönberger
Gert Kroner
Harald Schobesberger
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Lenzing AG
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Lenzing AG
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Publication of US20190127888A1 publication Critical patent/US20190127888A1/en
Assigned to LENZING AKTIENGESELLSCHAFT reassignment LENZING AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHÖNBERGER, Christoph, KRONER, GERT, FUCHS, HEIDRUN, SCHOBESBERGER, HARALD
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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
    • 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
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24—Viscose

Definitions

  • the present invention relates to a modified viscose fiber, a process for the production of the viscose fiber according to the present invention, and to its use.
  • the invention relates to a modified viscose fiber with an incorporated material from algae, with improved use properties for textile applications, particularly in the knitwear sector, which meet the consumer's expectations for unrestricted washability and, respectively, also the requirements of industrial washing, to its use in the manufacture of yarns and planar assemblies, and to a process for the production of those fibers.
  • EP 1 259 564 describes the production of fibers and molded bodies according to the NMMO process from a polymer solution which comprises a biodegradable polymer—usually cellulose—and a material from marine plants and/or shells of marine animals and, optionally, further additives.
  • molded bodies produced in this way have a lower tendency towards fibrillation as compared to corresponding molded bodies according to the NMMO process without additives. This conclusion was drawn on the basis of the changed fiber structure, which is visible in SEM images, more precisely on the basis of a reduced longitudinal orientation.
  • EP 1 259 564 discloses the production of fibers and molded bodies modified by the addition of a material from marine plants and/or shells of marine animals according to a viscose process.
  • a material from marine plants and/or shells of marine animals By way of example, 15% (Example 7) and 1.7% (Example 8) of a material from brown algae are added on cellulose.
  • Fibers and, respectively, molded bodies produced in this manner have similar or, respectively, slightly deteriorated physical fiber properties in comparison to a viscose fiber without additives (Comparative Example 3).
  • EP 1 259 564 describes in Examples 9 and 10 the production of fibers and molded bodies with the addition of a material from marine plants and/or shells of marine animals according to the carbamate process. According to said process, a very low fineness-related dry tear strength is achieved, which is reduced even further by the addition of algal material, depending on the incorporated amount.
  • the Lyocell-based types tend to fibrillate and, subsequently, after repeated washings, to form unsightly textile surfaces that have been scrubbed white, despite the somewhat lower longitudinal fiber orientation.
  • fiber types produced according to the viscose process exhibit an even slightly poorer stability in the wet state (wet strength and BISFA wet modulus) than conventional viscose fibers.
  • the types produced according to the carbamate process have a dry tensile strength which is too low for commercial yarn production. In addition, said process has no economic significance, to this day, there has been no industrial fiber production according to the carbamate process.
  • fiber is intended to encompass fibers of a defined, relatively short length (for example, so-called “staple fibers”) as well as fibers of a very large length, which, in linguistic usage, are also referred to as “filaments”.
  • FIG. 1 illustrates the fibrillation dynamics of cellulosic fibers as determined according to an adapted Canadian Standard Freeness test.
  • FIG. 2 shows the microscopic assessment of the fibrillation behavior of a fiber according to Example 3.
  • FIG. 3 shows the fibrillation behavior of a fiber according to Example 4.
  • FIG. 4 shows the fibrillation behavior of a SeaCellTM fiber.
  • the present invention solves the above-indicated problem by providing non-fibrillating regenerated cellulosic fibers with incorporated algal material, which are produced according to a viscose process modified in comparison to EP 1 259 564.
  • the fibers according to the invention are characterized by the particular softness of cellulose fibers with an incorporated material from algae, which per se is known, but exhibit a significantly reduced tendency towards wet fibrillation as compared to solvent-spun fibers based on the NMMO process.
  • the minor procedural modifications in comparison to the manufacturing process described in EP 1 259 564 B1 have had the result that the fibers according to the invention show significantly improved physical fiber properties, in particular a higher fineness-related tear strength and a higher wet modulus, as compared to the fibers of the viscose type having brown algae incorporated according to EP 1 259 564, Example 7 (comprising 15% brown algae) and Example 8: (comprising 1.67% brown algae on cellulose) and even in comparison to Comparative Example 3 of EP 1 259 564 (without admixture of algae).
  • the fibers according to the invention have a wet modulus at an elongation of 5% in the wet state which complies with the following formula:
  • T is the titer of the fiber in dtex.
  • This wet modulus corresponds to the wet modulus of a modal fiber as per the definition by BISFA (The International Bureau for the Standardization of Man-Made Fibers) and is hereinafter also referred to as “BISFA wet modulus” or “BISFA modulus”.
  • BISFA The International Bureau for the Standardization of Man-Made Fibers
  • the wet modulus and the other textile physical properties mentioned in the present application are measured according to the measuring methods as defined by BISFA.
  • the fiber according to the invention has a fiber strength in the conditioned state which complies with the following formula:
  • the fibers according to the invention may contain 0.5% by weight to 6% by weight, preferably 2% by weight to 6% by weight, particularly preferably 3% by weight to 4% by weight, of algal material, based on cellulose.
  • the algae can come from both salt and fresh water.
  • the algae used have an alginic acid content of 15% by weight to 50% by weight.
  • the fibers according to the invention contain algal material of the type Ascophyllum nodosum.
  • the fibers according to the invention have, even without complementary additions of metal ions, an increased content of zinc in comparison to Lyocell fibers and/or viscose fibers with the same addition of algae.
  • the content of zinc ions preferably amounts to at least 200 ppm, particularly preferably 200 ppm to 700 ppm.
  • the zinc content is significantly increased also in comparison to modal fibers and is present in the fiber according to the invention at least partially as a Zn alginate.
  • Zinc is an essential trace element with skin-caring qualities and is therefore used in skin care products.
  • Zinc alginates are used, among other things, in wound dressings. It is believed that the combined effect of alginate (as a moisturizer and a natural softener) and of zinc ions releasable from the alginate achieves even better skin care properties.
  • composition of the viscose refer to its state prior to the addition of the dispersion of the algal material.
  • the modifier which is used produces a sheath structure of the fiber according to the invention in a manner known per se.
  • the modifier can be an ethoxylated amine.
  • the material from algae which is used is preferably provided in a powdered and dried state, with a residual water content of ⁇ 15%, better ⁇ 10%, at a particle size of x99 ⁇ 20 ⁇ m, better ⁇ 15 ⁇ m. So as to achieve the desired fiber properties, the algal material should preferably have an alginic acid content of at least 15%.
  • the material is preferably dispersed in water, optionally with a dispersing aid being added, in order to yield a dispersion with a solids content preferably ranging from 2% by weight to 15% by weight.
  • the aqueous dispersion can be deaerated in vacuo as needed and, optionally, can be added to the viscose at the desired ratio upon a preceding filtration for removing undissolved particles, while, in doing so, intimate mixing should be ensured by means of conventional mixing units, homogenizers or the like.
  • a filtration by cartridge filters may occur prior to spinning.
  • Spinning may be effected through spinnerets with a hole diameter of 50 ⁇ m-100 ⁇ m, depending on the desired titer of the fibers.
  • the present invention also relates to the use of the viscose fiber according to the invention for the production of yarns and planar textile assemblies.
  • a 10% dispersion was prepared in demineralized water from a dried, powdered plant material of Ascophyllum nodosum and was deaerated for 6 hours.
  • a viscose fiber without or, respectively, with 2.5% or, respectively, 5% algal material on cellulose was produced through spinnerets with a hole diameter of 50 ⁇ m and with a draw-off of 30 m/min. The dosing of the algal dispersion took place directly before the homogenizer, with a residence time of ⁇ 1 min in front of the spinneret.
  • a 10%, a 5% and a 2.5% dispersion was prepared in demineralized water from a dried, powdered plant material of Ascophyllum nodosum, and the dispersions were not deaerated.
  • a viscose fiber without or, respectively, with, in each case, 5% algal material on cellulose was produced through spinnerets with a hole diameter of 50 ⁇ m and with a draw-off of 30 m/min.
  • the alginic acid content of the algal material used and of the fibers thus spun was analyzed upon a total hydrolysis of the fiber via HPLC on the basis of the mannuronic acid and guluronic acid content against an alginic acid standard (Fluka).
  • the alginic acid content of the algal powder used was 25%, the alginic acid content of the fibers was between 0.95% and 1.2%, corresponding to a content of algae of 3.8% to 4.8%.
  • the fibers thus produced also have a significantly increased water retention capacity (WRV) compared with a modified viscose fiber without addition of algae. This shows the moisture retention capacity of the algal additive.
  • a viscose fiber without or, respectively, with 4% algal material on cellulose was produced through spinnerets with a hole diameter of 60 ⁇ m and with a draw-off of 20 m/min.
  • Viscose fibers modified according to the invention comprising 4% algal material on cellulose were produced through spinnerets with a hole diameter of 60 ⁇ m and with a draw-off of 19 m/min for approx. 40 hours.
  • the alginic acid content of the fibers thus spun was 0.80% - 1.0%, corresponding to a content of algae of 3.2% - 4.0%; the algal powder used had an alginic acid content of 25%.
  • Zinc contents of the modified viscose fibers algae-incorporated according to the invention are Zinc contents of the modified viscose fibers algae-incorporated according to the invention:
  • the zinc content was determined after fiber pulping by means of ICP analysis on fiber samples from Example 3 and Example 4 in comparison to a standard viscose fiber (manufacturer: Lenzing AG), a modal fiber (manufacturer: Lenzing AG) as well as an algae-modified fiber produced according to the Lyocell process (SeaCellTM, manufacturer: Smartfiber AG).
  • modified viscose fibers algae-incorporated according to the invention have a zinc content of 330 ppm to 530 ppm, whereas standard viscose fibers and modal fibers exhibit significantly lower zinc contents.
  • This fiber is a Lyocell type produced according to EP 1 259 564 with 3%-5% incorporated material of Ascophyllum nodosum.
  • 20 single fibers are weighted down with a titer-dependent pretension weight and suspended from a metal roller with a diameter of 1 cm.
  • the roller is covered with a viscose filament yarn stocking and is continuously moistened.
  • the roller is rotated at a speed of 500 rpm.
  • the roller simultaneously performs a pendulum movement transversely to the fiber axis with a deflection of about 1 cm.
  • the number of rotations until the fibers are worn through is determined. The stronger the tendency towards fibrillation in the wet state, the lower is the number of achieved revolutions U, which indicate the value of the wet abrasion resistance based on the titer [dtex].
  • a mixer serves as a measure of the tendency towards fibrillation, wherein fiber samples cut to a length of 5 mm are beaten in water in said mixer until they start to fibrillate.
  • the CSF apparatus itself consists of a funnel with an overflow and a screen inserted therein. As the degree of fibrillation increases, the screen located in the CSF apparatus clogs, whereby more water gets into the overflow and less into the passage. In a standardized measuring cylinder, the water volume is determined in ml in the passage after various mixing times, whereby it is the higher, the less the fiber fibrillates.
  • FIG. 1 illustrates the fibrillation dynamics determined according to those experiments.
  • the abscissa indicates the mixing time in minutes, the ordinate indicates the water volume in the passage in ml.
  • the fiber types A to F examined according to FIG. 1 were the following fibers:
  • both Lyocell types the standard Lyocell fiber as well as SeaCellTM, fibrillate already after a mixing time of 10 minutes.
  • All fiber types based on a viscose process i.e., also the algae-incorporated fibers according to the process modified according to the invention, still show no signs of fibrillation in the CSF test even after a mixing time of 45 minutes.
  • the friction of the fibers among each other during washing and, respectively, finishing operations in the wet state is simulated by the following test: 8 fibers are placed in a 20 ml sample vial with 4 ml of water and shaken at level 12 for 3 hours in a laboratory shaker of type RO-10 from Gerhardt, Bonn (FRG). Thereupon, the fibrillation behavior of the fibers is evaluated under the microscope by counting the number of fibrils per 0.276 mm of fiber length and is indicated as a fibrillation value ranging from 0 (no fibrils) to 6 (strong fibrillation).
  • FIGS. 2 to 4 show the result of the microscopic examination of the fibers:
  • FIG. 2 shows the fibrillation behavior of the fiber according to Example 3.
  • FIG. 3 shows the fibrillation behavior of the fiber according to Example 4.
  • FIG. 4 shows the fibrillation behavior of the SeaCellTM fiber.
  • the wet modulus according to BISFA i.e., the tensile strength at 5% elongation in the wet state
  • the wet modulus does not exceed a value of 3.0 in the viscose types from EP 1 259 564.
  • the viscose fibers modified according to the invention having incorporated algae are not modal fibers in the true sense of the word, but it is still possible to infer significantly improved use values in comparison to EP 1 259 564, Examples 7 and 8, from the substantially improved physical fiber properties.
  • the connection between the wet modulus of fibers and the surface shrinkage of fabrics produced therefrom has long been known (Szegö, L., Faserforsch., Text. Techn. 21.10 (1970).
  • Puchegger has confirmed this connection for viscose and modal fibers (Puchegger, F Lenzinger Ber., 55, 32-36 (1983) and Puchegger, F., Lenzinger Ber. 58, 94-99 (1985)).
  • Viscose composition Cellulose concentration 5.8 5.8 5.6 5.4 [% by weight] R18 content [%] 97.5 95 96 97 NaOH concentration in the viscose 6.2 6.1 6.5 6.7 [%] by weight Alkali ratio 0.9 1.0 0.9 0.8 (cellulose:NaOH, both g/l) CS 2 in the viscose [% by weight on 37 39 36 38 cellulose] Modifier [% by weight] 3 3 4 4 Degree of ripeness (gamma value) 58 58 57 59 Spinning viscosity [falling-ball 96 80 95 82 seconds] Nozzle hole diameter 50 ⁇ m 50 ⁇ m 60 ⁇ m 60 ⁇ m Spinning bath composition: H 2 SO 4 [g/l]: 75 73 74 72 Na 2 SO 4 [g/l]: 128 123 125 120 ZnSO 4 [g/l]: 60 65 65 60 T spinning bath [° C.]: 38 38 37 37 T

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
US16/095,778 2016-04-28 2017-04-25 Modified viscose fiber Abandoned US20190127888A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ATA50381/2016 2016-04-28
ATA50381/2016A AT518061B1 (de) 2016-04-28 2016-04-28 Modifizierte Viskosefaser
PCT/EP2017/059813 WO2017186725A1 (de) 2016-04-28 2017-04-25 Modifizierte viskosefaser

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US20190127888A1 true US20190127888A1 (en) 2019-05-02

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US16/095,778 Abandoned US20190127888A1 (en) 2016-04-28 2017-04-25 Modified viscose fiber

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US (1) US20190127888A1 (de)
EP (1) EP3449047A1 (de)
JP (1) JP6688908B2 (de)
KR (1) KR20180136469A (de)
CN (1) CN109072486A (de)
AT (1) AT518061B1 (de)
DE (1) DE202017007095U1 (de)
ES (1) ES1239889Y (de)
TW (1) TW201835399A (de)
WO (1) WO2017186725A1 (de)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN114013133A (zh) * 2021-01-25 2022-02-08 顾译雯 一种发热复合面料
CN115161842A (zh) * 2022-08-15 2022-10-11 罗莱生活科技股份有限公司 一种海藻改性纤维混纺面料及其制备方法

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IL274692B2 (en) * 2017-11-15 2025-10-01 Algalife Ltd Fibers, yarns, fabrics and clothing containing microalgae
DE102019007165A1 (de) * 2019-10-15 2021-04-15 Smartfiber Ag Verfahren zur Herstellung einer cellulosischen Funktionsfaser mit hoher Ionenaustauschkapazität, und cellulosischer Funktionsfaser
JP6812039B1 (ja) * 2020-04-10 2021-01-13 竹本油脂株式会社 ビスコースレーヨン不織布用処理剤、ビスコースレーヨン不織布用処理剤の水性液、ビスコースレーヨン、及び不織布用のビスコースレーヨンの製造方法
JP6812038B1 (ja) * 2020-04-10 2021-01-13 竹本油脂株式会社 ビスコースレーヨン用処理剤、ビスコースレーヨン用処理剤の水性液、ビスコースレーヨン、及びビスコースレーヨンの製造方法

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WO2011026159A1 (de) * 2009-09-01 2011-03-10 Lenzing Ag Flammgehemmte cellulosische faser, deren verwendung sowie verfahren zu deren herstellung

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114013133A (zh) * 2021-01-25 2022-02-08 顾译雯 一种发热复合面料
CN115161842A (zh) * 2022-08-15 2022-10-11 罗莱生活科技股份有限公司 一种海藻改性纤维混纺面料及其制备方法

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CN109072486A (zh) 2018-12-21
JP2019515151A (ja) 2019-06-06
DE202017007095U1 (de) 2019-07-31
KR20180136469A (ko) 2018-12-24
ES1239889U (es) 2020-01-22
EP3449047A1 (de) 2019-03-06
TW201835399A (zh) 2018-10-01
JP6688908B2 (ja) 2020-04-28
AT518061A4 (de) 2017-07-15
AT518061B1 (de) 2017-07-15
ES1239889Y (es) 2020-07-02
WO2017186725A1 (de) 2017-11-02

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