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WO1998058102A1 - Microfibre de cellulose - Google Patents

Microfibre de cellulose Download PDF

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Publication number
WO1998058102A1
WO1998058102A1 PCT/AT1998/000150 AT9800150W WO9858102A1 WO 1998058102 A1 WO1998058102 A1 WO 1998058102A1 AT 9800150 W AT9800150 W AT 9800150W WO 9858102 A1 WO9858102 A1 WO 9858102A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
air
solution
dtex
mass
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/AT1998/000150
Other languages
German (de)
English (en)
Inventor
Eduard Mülleder
Christoph Schrempf
Hartmut Rüf
Wilhelm Feilmair
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 AT98925319T priority Critical patent/ATE251238T1/de
Priority to DE59809792T priority patent/DE59809792D1/de
Priority to EP98925319A priority patent/EP0918893B1/fr
Priority to AU77504/98A priority patent/AU7750498A/en
Publication of WO1998058102A1 publication Critical patent/WO1998058102A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the present invention relates to a cellulosic microfiber.
  • the invention further relates to a process for the production of cellulosic fibers, wherein pulp or cellulose is dissolved in an aqueous tertiary amine oxide to form a spinnable solution, this solution is spun into filaments using a spinneret, and the filaments are drawn into a precipitation bath by stretching through an air gap be introduced to precipitate the dissolved pulp.
  • N-methylmorpholine-N-oxide is preferably used as the solvent.
  • NMMO is used for the term “tertiary amine oxides”, NMMO additionally representing the N-methylmorpholine-N-oxide which is preferably used today.
  • Tertiary amine oxides have long been known as alternative solvents for cellulose. From U.S. Patent 2,179,181 it is known, for example, that tertiary amine oxides can dissolve high-quality chemical pulp without derivatization and that cellulosic moldings, such as fibers, can be obtained from these solutions by precipitation. US Pat. Nos. 3,447,939, 3,447,956 and 3,508,941 describe further processes for the preparation of cellulosic solutions, cyclic amine oxides preferably being used as solvents. In all of these processes, cellulose is physically dissolved at an elevated temperature.
  • EP-A-0 356 419 by the applicant describes a process which is preferably carried out in a thin-film treatment apparatus in which a suspension of the comminuted pulp in an aqueous tertiary amine oxide is transported in the form of a thin layer and transported over a heating surface, the surface of this thin layer being subjected to a vacuum.
  • a suspension of the comminuted pulp in an aqueous tertiary amine oxide is transported in the form of a thin layer and transported over a heating surface, the surface of this thin layer being subjected to a vacuum.
  • water is evaporated off and the cellulose can be brought into solution, so that a spinnable cellulose solution is discharged from the film spinner.
  • Methods for spinning cellulose solutions are e.g. known from EP-A-0 671 492 and EP-A-0 659 219 of the applicant.
  • the spinning solution is extruded through a spinneret into filaments which are passed through an air gap into a precipitation bath in which the cellulose precipitates.
  • the filaments are stretched in the air gap. This process is commonly known as dry / wet spinning.
  • Applicant's WO 95/02082 also describes a dry / wet spinning process. This method uses cooling air that has a temperature between 10 ° C and 60 ° C. The humidity of the cooling air supplied is between 20 g H 0 and 40 g H ⁇ O per kilogram.
  • WO 94/28218 generally proposes the use of spinnerets with 500 to 100,000 holes.
  • the temperature of the Cooling air is between 0 ° C and 50 ° C.
  • the person skilled in the art can see from this literature that the humidity is between 5.5 g H 2 0 and 7.5 g H_0 per kilogram of air. This creates a relatively dry climate in the air gap.
  • WO 96/17118 is also concerned with the climate in the air gap, it being determined that the climate should be as dry as possible, namely 0.1 g H_0 to 7 g H O per kilogram of air, with a relative humidity of less than 85%. 6 ° C to 40 ° C is suggested as the temperature for the cooling air.
  • WO 96/21758 also deals with the climate to be set in the air gap, a two-stage blowing with different cooling air being proposed and blowing with less humid and cooler air in the upper region of the air gap.
  • EP-A-0 648 808 describes a method for forming a cellulose solution, the cellulosic components of the solution comprising a first component made of a cellulose with an average degree of polymerization (DP) of 500 to 2000 and a second component made of a cellulose with a DP of contain less than 90% of the DP of the first component in the range of 350 to 900.
  • the weight ratio of the first to the second component should be 95: 5 to 50:50.
  • the object of the invention is therefore to provide a process for the production of cellulosic fibers, pulp being dissolved in an aqueous tertiary amine oxide to give a spinnable solution, this solution being spun into filaments using a spinneret, and the filaments being stretched an air gap is introduced into a precipitation bath in order to precipitate the dissolved pulp, which method allows fibers with a titer of maximum or less than 1 dtex to be produced.
  • microfibers These fibers are referred to as microfibers ("Lexikon der Textilveredelung”, HK Rouette, Volume 2, page 1250 ff; 1995; Laumann'sche Verlagsgesellschaft, ISBN 3-87466-228-4).
  • the invention has in particular the object to provide staple fibers of the Lyocell genus with a titer of maximum or less than 1 dtex.
  • a solution is used for spinning which contains less than 0.20% by mass, in particular less than 0.05% by mass, based on the mass of the solution, of cellulose with a
  • the air in the air gap has a moisture content of less than 5 g water / kg air.
  • microfibers with a titer of less than 1 dtex can be produced.
  • the moisture content obviously affects spinnability in that the lower the moisture content of the air in the air gap, the better it is. This is particularly evident when blowing the extruded filaments with dry air, i.e. air with a moisture content of 0%. Under these conditions, fibers with a titer of up to 0.30 dtex can even be produced. The same pulp cannot even be processed into fibers with a titer of 1.7 dtex when blown with moist air (more than 30 g H 0 / kg air).
  • a preferred embodiment of the method according to the invention is therefore characterized in that the filaments are blown with air immediately after they have left the spinneret and that this air has a moisture content of less than 5 g water / kg air.
  • the tertiary amine oxide used is preferably N-methylmorpholine-N-oxide.
  • the invention also relates to the use of a spinnable solution of cellulose in an aqueous tertiary amine oxide which is less than 0.20% by mass, in particular less than 0.05% by mass, based on the mass of the solution, of cellulose with a molecular weight of at least 5x10, for the production of cellulosic fibers with a maximum titer of 1 dtex.
  • N-methyl-morpholine-N-oxide has proven itself best as a tertiary amine oxide.
  • the invention also relates to a cellulosic fiber of the Lyocell genus, which is characterized in that it has a titer in the range from 1.0 dtex to 0.3 dtex, in particular in the range from 1.0 dtex and 0.5 dtex, and preferably in Has a range of 1.0 dtex and 0.8 dtex.
  • a preferred embodiment of the fiber according to the invention is in the form of a staple fiber with a length of in particular 1 cm to 10 cm.
  • the molecular weight profile of a pulp can be obtained by means of gel permeation chromatography (GPC), the "Differential Weight Fraction” in [%] as ordinate against the molecular weight [g / mol; logarithmic plot].
  • GPC gel permeation chromatography
  • the size "differential weight fraction” describes the percentage frequency fraction of the molecular weight fraction.
  • HPLC pump Kontron; sample collector: HP 1050, Hewlett Packard; eluent: 9 g LiCl / L DMAC; Rl detector: Type F511, ERC; laser wavelength: 488 nm; increment dn / dc: 1.36 ml / g; evaluation software; Astra 3d, version 4.2, Wyatt; column material: 4 columns, 300 mm x 7 , 5 mm, filling material: PL Gel 20 ⁇ .- Mixed - A, from Polymer-Laboratories; sample concentration: 1 g / 1 mobile solvent; injection volume: 40 ⁇ .1, flow rate: 1 ml / min.
  • MALLS Multi Angle Laser Light Scattering
  • the measuring apparatus is calibrated using measures familiar to the person skilled in the art.
  • the signal is evaluated according to Zimm, whereby the Zim formula may need to be set in the evaluation software.
  • the molecular weight profile for the pulp Viscokraft LV (manufacturer: International Paper) is shown as an example in FIG.
  • the diagram of Fig. La shows that this pulp consists largely of molecules with a molecular weight of about 100,000 and that this pulp has practically no proportions with a molecular weight of greater than 500,000.
  • FIG. 1b shows the molecular weight profile of the pulp Alistaple LD 9.2 (manufacturer: Western Pulp).
  • This pulp has a maximum molecular weight frequency of about 200,000 and the graph also shows that this pulp has a high proportion (about 25%) of molecules with a molecular weight greater than 500,000.
  • a dope containing only 15% by weight of such pulp has about 4% (based on the mass of the solution; degradation not taken into account during the preparation of the solution) cellulose molecules with a molecular weight of more than 500,000 and thus does not correspond to those which invented - used according to the intended purpose.
  • the crushed pulp is suspended in aqueous, 50% NMMO, placed in a kneader (Type: IKA laboratory kneader HKD-T; manufacturer: IKA-Labortechnik) and left to impregnate for one hour. Subsequently, by heating the kneader with a heating medium heated to 130 ° C. and by reducing the pressure, water is evaporated until the pulp has completely dissolved.
  • a kneader Type: IKA laboratory kneader HKD-T; manufacturer: IKA-Labortechnik
  • a melt index device from Davenport used in plastics processing is used as the spinning apparatus.
  • This device consists of a heatable, temperature-controllable steel cylinder, into which the spinning mass is filled.
  • a piston which is loaded with a weight, the spinning mass is extruded through the spinneret attached to the underside of the steel cylinder, which has a hole with a diameter of 100 ⁇ m.
  • the spinning mass (cellulose content: 15%) introduced into the spinning apparatus is extruded through the spinning hole and passed over an air gap with a length of 3 cm into an aqueous precipitation bath, deflected, drawn off via a godet which is provided behind the precipitation bath, and thereby stretched.
  • the spinning mass output through the nozzle is 0.030 g / min.
  • the spinning temperature is 80 ° C to 120 ° C.
  • the minimum spinnable titer is used to simulate the spinning behavior. To do this, the maximum take-off speed (m / min) is determined. The take-off speed is like this increased for a long time until the thread breaks. This speed is noted and used to calculate the titer using the formula below. The higher this value, the better the spinning behavior and the finer the fiber obtained.
  • the titer that is given at the maximum withdrawal speed is calculated using the following general formula:
  • K is the cellulose concentration in mass%
  • A is the spinning mass output in g / minute
  • G is the take-off speed in m / minute
  • L is the number of spinning holes in the spinneret.
  • concentration of cellulose is 15%
  • A 0.030 g / minute
  • L 1.
  • Table 1 show the relationship that the maximum withdrawal speed and the minimum titer increase or decrease with increasing moisture in the air gap. This means that with increasing moisture, a thread with a smaller titer can be spun. However, fibers with a titer of less than 1 dtex can only be produced with difficulty and with extremely high humidity.
  • Table 2 show the relationship according to the invention that when the spinning mass according to the invention is used, the maximum take-off speed can be increased if the moisture in the air gap is reduced. This makes it possible to produce finer fibers. It is also possible to produce fibers with a titer of up to 0.3 dtex.
  • FIG. 2 shows the spinning behavior of cellulose solutions with varying proportions of long-chain molecules, the minimum titer (dtex) being the ordinate and the concentration of the respective cellulose solution to cellulose molecules with a molecular weight of at least 500,000 being plotted as the abscissa.
  • the concentrations were determined immediately before spinning.
  • the proportion of long-chain molecules was adjusted by adding appropriate amounts of Alistaple LD 9.2 to Viscokraft LV.
  • the cellulose concentration of the solution was 15% by mass in all cases.
  • the spinning behavior was determined for each cellulose solution both at a humidity in the air gap of 30 g H-0 (curve “a") and at 0 g H “0 (dry) (straight line” b ").
  • FIG. 2 shows that two critical parameters have to be taken into account in the production of microfibers: the concentration of cellulose molecules with one molecule.

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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)

Abstract

L'invention concerne un procédé de production de fibres de cellulose. On dissout de la cellulose dans un oxyde d'amine tertiaire aqueux, de façon à obtenir une solution susceptible d'être filée, on file cette solution en filaments au moyen d'une filière, on fait passer les filaments à travers une fente, de façon à les étirer, et on les introduit dans un bain de précipitation afin d'amener la cellulose dissoute à se précipiter. Ce procédé se caractérise en ce que l'on utilise pour le filage une solution qui contient moins de 0,20 % en volume, notamment moins de 0,05 % en volume, par rapport au volume de la solution, de cellulose d'un poids moléculaire d'au moins 5x10<5>, et en ce que l'air dans la fente a une teneur en humidité inférieure à 5g d'eau par kilogramme d'air.
PCT/AT1998/000150 1997-06-17 1998-06-17 Microfibre de cellulose Ceased WO1998058102A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT98925319T ATE251238T1 (de) 1997-06-17 1998-06-17 Cellulosische mikrofaser
DE59809792T DE59809792D1 (de) 1997-06-17 1998-06-17 Cellulosische mikrofaser
EP98925319A EP0918893B1 (fr) 1997-06-17 1998-06-17 Microfibre de cellulose
AU77504/98A AU7750498A (en) 1997-06-17 1998-06-17 Cellulose microfibre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT105597A AT405532B (de) 1997-06-17 1997-06-17 Cellulosische mikrofaser
ATA1055/97 1997-06-17

Publications (1)

Publication Number Publication Date
WO1998058102A1 true WO1998058102A1 (fr) 1998-12-23

Family

ID=3505615

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1998/000150 Ceased WO1998058102A1 (fr) 1997-06-17 1998-06-17 Microfibre de cellulose

Country Status (7)

Country Link
EP (1) EP0918893B1 (fr)
AT (1) AT405532B (fr)
AU (1) AU7750498A (fr)
DE (1) DE59809792D1 (fr)
ES (1) ES2206936T3 (fr)
PT (1) PT918893E (fr)
WO (1) WO1998058102A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221487B1 (en) 1996-08-23 2001-04-24 The Weyerhauser Company Lyocell fibers having enhanced CV properties
US6511930B1 (en) 1996-08-23 2003-01-28 Weyerhaeuser Company Lyocell fibers having variability and process for making
US11932969B2 (en) 2008-01-11 2024-03-19 Lenzing Aktiengesellschaft Microfiber

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996013071A1 (fr) * 1994-10-21 1996-05-02 Courtaulds Plc Non-tisses pour separateurs d'accumulateurs comprenant un voile de fibres de cellulose filees avec solvant
WO1997008370A1 (fr) * 1995-08-29 1997-03-06 Asahi Kasei Kogyo Kabushiki Kaisha Fils de cellulose a filaments multiples et tissus en etant faits
WO1997035054A1 (fr) * 1996-03-15 1997-09-25 Courtaulds Plc Fabrication d'elements de forme allongee
WO1998007911A1 (fr) * 1996-08-23 1998-02-26 Weyerhaeuser Company Fibres lyocellulaires et procede de preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996013071A1 (fr) * 1994-10-21 1996-05-02 Courtaulds Plc Non-tisses pour separateurs d'accumulateurs comprenant un voile de fibres de cellulose filees avec solvant
WO1997008370A1 (fr) * 1995-08-29 1997-03-06 Asahi Kasei Kogyo Kabushiki Kaisha Fils de cellulose a filaments multiples et tissus en etant faits
EP0854215A1 (fr) * 1995-08-29 1998-07-22 Asahi Kasei Kogyo Kabushiki Kaisha Fils de cellulose a filaments multiples et tissus en etant faits
WO1997035054A1 (fr) * 1996-03-15 1997-09-25 Courtaulds Plc Fabrication d'elements de forme allongee
WO1998007911A1 (fr) * 1996-08-23 1998-02-26 Weyerhaeuser Company Fibres lyocellulaires et procede de preparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221487B1 (en) 1996-08-23 2001-04-24 The Weyerhauser Company Lyocell fibers having enhanced CV properties
US6511930B1 (en) 1996-08-23 2003-01-28 Weyerhaeuser Company Lyocell fibers having variability and process for making
US7067444B2 (en) 1996-08-23 2006-06-27 Weyerhaeuser Company Lyocell nonwoven fabric
US11932969B2 (en) 2008-01-11 2024-03-19 Lenzing Aktiengesellschaft Microfiber

Also Published As

Publication number Publication date
PT918893E (pt) 2004-02-27
AT405532B (de) 1999-09-27
EP0918893A1 (fr) 1999-06-02
EP0918893B1 (fr) 2003-10-01
ES2206936T3 (es) 2004-05-16
AU7750498A (en) 1999-01-04
DE59809792D1 (de) 2003-11-06
ATA105597A (de) 1999-01-15

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