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WO1997035054A1 - Fabrication d'elements de forme allongee - Google Patents

Fabrication d'elements de forme allongee Download PDF

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Publication number
WO1997035054A1
WO1997035054A1 PCT/GB1997/000677 GB9700677W WO9735054A1 WO 1997035054 A1 WO1997035054 A1 WO 1997035054A1 GB 9700677 W GB9700677 W GB 9700677W WO 9735054 A1 WO9735054 A1 WO 9735054A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
cellulose
solution
further characterised
die
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/GB1997/000677
Other languages
English (en)
Inventor
Stephen Byron Smith
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.)
Akzo Nobel UK PLC
Original Assignee
Courtaulds PLC
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 Courtaulds PLC filed Critical Courtaulds PLC
Priority to GB9818107A priority Critical patent/GB2328397B/en
Priority to DE19781649T priority patent/DE19781649T1/de
Priority to AU19332/97A priority patent/AU1933297A/en
Publication of WO1997035054A1 publication Critical patent/WO1997035054A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • This invention relates to a method for the manufacture of elongate lyocell members such as fibres and film, wherein a solution of cellulose in an aqueous tertiary amine N-oxide solvent is extruded through a die by way of a gaseous gap into an aqueous coagulating bath to form an elongate member which is thereafter washed and dried.
  • lyocell members such as fibres and film are known.
  • the manufacture of lyocell fibres is described for example in US-A-4,416 ,698, the contents of which are incorporated herein by way of reference.
  • Cellulose is dissolved in a solvent containing a tertiary amine N-oxide (which may also be called for brevity an amine oxide), for example N-methylmorpholine N-oxide (NMMO).
  • NMMO N-methylmorpholine N-oxide
  • the solvent generally also contains a proportion of a non-solvent for cellulose, for example water.
  • the resulting solution is extruded through a suitable die to produce fibres, which are coagulated, washed in water to remove the solvent, and dried.
  • solvent spinning This process of extrusion and coagulation is referred to as "solvent spinning", and the cellulose fibre produced thereby is referred to as "solvent-spun" cellulose fibre or as lyocell fibre.
  • elongate cellulose members can be made by extrusion of a solution of a cellulose derivative into a regenerating and coagulating bath.
  • a viscose process In which the cellulose derivative is cellulose xanthate .
  • Solvent spinning has a number of advantages over other known processes for the manufacture of elongate cellulose members such as the viscose process, for example reduced environmental emissions.
  • Elongate lyocell members are known to be prone to fibrillation. Fibrillation is a phenomenon which in the main occurs when the lyocell member is subjected to mechanical forces during wet-processing, and it results in the partial detachment of fine longitudinal fibrils from the elongate member. Efforts have been made to reduce or eliminate fibrillation tendency by chemical aftertreatments , such as those described in US-A-5,310,424, or by suitable choice of spinning parameters, as described for example in WO-A-95/02082. It is an object of the present invention to provide a method of manufacturing elongate lyocell members, particularly low-decitex fibres, in which spinning stability (i.e. freedom from breakdowns) is good and in which the elongate members thereby produced have a low fibrillation tendency.
  • spinning stability i.e. freedom from breakdowns
  • a method for the manufacture of an elongate lyocell member wherein a solution of cellulose in an aqueous tertiary amine N-oxide solvent is extruded through a die by way of a gaseous gap into an aqueous coagulating bath to form an elongate member which is thereafter washed and dried, characterised in that in combination (1) the concentration of cellulose in the solution is in the range from 2.0 to 4.5, preferably from
  • the ratio of the velocity of the elongate member as it is removed from the coagulating bath to the velocity of the solution as it is extruded through the die is in the range from 1.0 to 2.0, preferably from 1.0 to 1.5
  • the width of the die is in the range from 40 to 80, preferably from 60 to 80, further preferably from 70 to 80, micrometre.
  • the ratio of the velocity of the elongate member as it is removed from the coagulating bath to the velocity of the solution as it is extruded through the die may conveniently be referred to as the draw ratio.
  • the elongate member may take the form of fibre, for example the form of continuous filament yarn or of tow intended to be cut into staple fibre, or it may take the form of film in flat or tubular form.
  • the "width" of the die is defined as being the cross-sectional diameter of the individual holes in the die (which may also be called a spinnerette or jet).
  • the "width” of the die is defined as the width of the slot or lobes.
  • the "width" of the die is defined as being the narrow cross-sectional dimension of the generally rectangular or circular slot through which the solution is extruded. The width of the die is measured at the face thereof.
  • the tertiary amine N-oxide is preferably N- methylmorpholine N-oxide. Mixtures of tertiary amine N- oxides may be used.
  • the solution may also comprise one or more water-miscible non-solvents for cellulose in known manner. The concentration of tertiary amine N-oxide in the solution is preferably in the range from 83 to 90 percent by weight.
  • the solution may also comprise one or more dispersed substances, for example a pigment such as titanium dioxide, and one or more other dissolved substances, for example a stabiliser such as propyl gallate, in known manner.
  • the temperature of the solution supplied to the die is preferably in the range from 80 to 120 "C.
  • Any suitable dissolving-grade cellulose may be used to form the solution.
  • High D.P. (degree of polymerisation) cellulose for example cotton linters, may be preferred.
  • the D.P. of such cotton linters or other cellulose used may be in the range from 1500 to 5000. Mixtures of cellulose from different sources may be used.
  • the gas in the gaseous gap is preferably air, although other inert gases or gas mixtures may also be used.
  • the length of the gaseous gap i.e. the distance between the face of the die and the surface of the coagulating bath
  • the ability to use a relatively short gaseous gap is an advantage of the invention, in that the use of long gaps may result in spinning instability or (in the case of fibre) stuck filaments. Nevertheless, longer gaps may, if desired, be used in the spinning of continuous filament yarn.
  • gas e.g.
  • the velocity of the supplied gas (e.g. air) is preferably in the range from 1 to 10 m/s.
  • the temperature of the supplied gas is preferably in the range from 0 to 30 °C.
  • the relative humidity of the supplied gas is preferably in the range from 0 to 60 percent.
  • the absolute humidity of the gas (e.g. air) is preferably in the range from 0 to 20, more preferably from 6 to 15, g/kg.
  • the coagulating bath preferably comprises from 0 to 70, more preferably from 20 to 40, percent by weight of the same tertiary amine N-oxide as in the solution of cellulose that is extruded.
  • the velocity of the elongate member as it is removed from the coagulating bath (the take-up velocity) is preferably in the range from 20 to 150 m/min.
  • Washing and drying of the coagulated elongate member and optional operations such as bleaching and cutting fibre to staple length may be carried out in known manner.
  • the decitex of fibre produced by the method of the invention may be in the range from 0.5 to 10 dtex, often from 1 to 2.5 dtex.
  • the method of the invention is particularly suited to the manufacture of low-decitex fibres of the latter kind.
  • Fibrillation tendency of lyocell fibres can be assessed by the following Test Method.
  • a small tuft of fibre containing 100 to 200 filaments is cut to 5 mm length. These short fibres are placed in a
  • This operation can be carried out manually or by image analysis. Alternatively, a set of standard micrographs can be set up for comparison. Trained fibre technologists have been found to be consistent in their assessment with this method. In practice, it is impossible to measure a fibrillation index above about 30, owing to the difficulty in seeing the large number of fibrils. Data are measured on the middle of the 5 mm length of fibre and on the end. Experience shows that the result for the fibre end correlates best to fabric performance, and only this is the figure quoted herein as Fibrillation Index.
  • a solution comprising 3.5% cellulose (Buckeye M-155-07 1AY cotton linters of average DP 3970), 9% water and 87.5% N-methylmorpholine N-oxide (NMMO) (solution S.G. 1.25) was extruded at a rate of 240 mg/min through a spinnerette having a single hole 70 micrometre in diameter, corresponding to an extrusion velocity of 50 m/min.
  • the extruded filament was passed by way of an air gap 30 mm long into an aqueous coagulating bath at 20°C comprising 20% NMMO.
  • Air 24'C, 10% relative humidity, 1.9 g/kg absolute humidity
  • the filament was taken up from the coagulating bath by means of a reel with surface velocity 63 m/min, washed free of NMMO and dried. The ratio of take-up velocity to extrusion velocity was therefore 1.26.
  • the fibre had the following properties: titre 1.4 dtex, air-dry tenacity 26 cN/tex, air-dry extensibility 9.5%, wet tenacity 24 cN/tex, wet extensibility 14%, initial wet modulus (2% extension) 170 cN/tex.
  • Fibrillation was induced and assessed in a sample of this fibre and in a control sample of commercial lyocell fibre by the Sand Test. The Fibrillation Indexes of the two samples were 2.5 and 7 respectively, demonstrating that the fibre made according to the invention had a lower fibrillation tendency than the control.
  • Example 1 was repeated, except that the solution comprised 4.2% cellulose (2.0% HV woodpulp (D.P. approximately 850, available from International Paper Co.), 1.0% Buckeye MVE cotton linters of average DP 4550 and 1.2% 1AY Buckeye cotton linters of average DP 3970). Similar results were obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)

Abstract

Il est possible de produire des éléments lyocellulaires de forme allongée, des fibres à faible tendance à la fibrillation par exemple, en mettant en oeuvre un procédé grâce auquel on extrude une solution de cellulose dans un solvant aqueux contenant un oxyde d'amine tertiaire par une filière à travers un interstice de gaz dans un bain aqueux de coagulation afin de constituer un élément allongé qui est ensuite lavé et séché. Ce procédé, qui possède une stabilité élevée au filage, se caractérise par le fait que, en combinaison, 1), la teneur en cellulose de la solution se trouve comprise entre 2,0 et 4,5, de préférence, entre 2,0 et 4,0 % en poids, que 2), le rapport de la vélocité de l'élément allongé tel qu'il est retiré du bain de coagulation à la vélocité de la solution telle qu'elle est extrudée par la filière est compris entre 1,0 et 2,0, de préférence, entre 1,0 et 1,5 et que 3), la largeur de cette filière est comprise entre 40 et 80, de préférence, entre 60 et 80, et mieux encore, entre 70 et 80 micromètres.
PCT/GB1997/000677 1996-03-15 1997-03-12 Fabrication d'elements de forme allongee Ceased WO1997035054A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9818107A GB2328397B (en) 1996-03-15 1997-03-12 Manufacture of elongate members
DE19781649T DE19781649T1 (de) 1996-03-15 1997-03-12 Herstellung von länglichen Elementen
AU19332/97A AU1933297A (en) 1996-03-15 1997-03-12 Manufacture of elongate members

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9605504.1A GB9605504D0 (en) 1996-03-15 1996-03-15 Manufacture of elongate members
GB9605504.1 1996-03-15

Publications (1)

Publication Number Publication Date
WO1997035054A1 true WO1997035054A1 (fr) 1997-09-25

Family

ID=10790468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/000677 Ceased WO1997035054A1 (fr) 1996-03-15 1997-03-12 Fabrication d'elements de forme allongee

Country Status (6)

Country Link
AU (1) AU1933297A (fr)
DE (1) DE19781649T1 (fr)
GB (2) GB9605504D0 (fr)
ID (1) ID16355A (fr)
TW (1) TW380168B (fr)
WO (1) WO1997035054A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998058102A1 (fr) * 1997-06-17 1998-12-23 Lenzing Aktiengesellschaft Microfibre de cellulose
WO1998058103A1 (fr) * 1997-06-17 1998-12-23 Lenzing Aktiengesellschaft Procede de production de fibres de cellulose
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
EP2589689A4 (fr) * 2010-06-30 2014-01-22 Kolon Inc Dope pour le filage de fibre cellulosique à haute ténacité, procédé pour la préparation de fibre de filament cellulosique à haute ténacité utilisant un tel dope, et procédé pour la préparation de fibre courte de fibre cellulosique à haute ténacité
WO2015101543A1 (fr) 2014-01-03 2015-07-09 Lenzing Aktiengesellschaft Fibre cellulosique
EP3536853A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell à formation de bouloche réduite
CN118441367A (zh) * 2024-05-20 2024-08-06 雅思雅思拉普 抗原纤化的莱赛尔纤维及其制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494851A2 (fr) * 1991-01-09 1992-07-15 Lenzing Aktiengesellschaft Procédé pour la fabrication d'objets cellulosiques
EP0494852A2 (fr) * 1991-01-09 1992-07-15 Lenzing Aktiengesellschaft Procédé pour la fabrication d'objets cellulosiques
WO1995002082A1 (fr) * 1993-07-08 1995-01-19 Lenzing Aktiengesellschaft Fibres cellulosiques
WO1996017118A1 (fr) * 1994-12-02 1996-06-06 Akzo Nobel N.V. Procede de production de corps cellulosiques façonnes et fil realise a partir de filaments cellulosiques
WO1996021758A1 (fr) * 1995-01-10 1996-07-18 Courtaulds Fibres (Holdings) Limited Fabrication d'articles extrudes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494851A2 (fr) * 1991-01-09 1992-07-15 Lenzing Aktiengesellschaft Procédé pour la fabrication d'objets cellulosiques
EP0494852A2 (fr) * 1991-01-09 1992-07-15 Lenzing Aktiengesellschaft Procédé pour la fabrication d'objets cellulosiques
WO1995002082A1 (fr) * 1993-07-08 1995-01-19 Lenzing Aktiengesellschaft Fibres cellulosiques
WO1996017118A1 (fr) * 1994-12-02 1996-06-06 Akzo Nobel N.V. Procede de production de corps cellulosiques façonnes et fil realise a partir de filaments cellulosiques
WO1996021758A1 (fr) * 1995-01-10 1996-07-18 Courtaulds Fibres (Holdings) Limited Fabrication d'articles extrudes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6221487B1 (en) 1996-08-23 2001-04-24 The Weyerhauser Company Lyocell fibers having enhanced CV properties
US6241927B1 (en) 1997-06-17 2001-06-05 Lenzing Aktiengesellschaft Method of producing cellulose fibers
AU740994B2 (en) * 1997-06-17 2001-11-22 Lenzing Aktiengesellschaft Method for producing cellulose fibres
WO1998058102A1 (fr) * 1997-06-17 1998-12-23 Lenzing Aktiengesellschaft Microfibre de cellulose
WO1998058103A1 (fr) * 1997-06-17 1998-12-23 Lenzing Aktiengesellschaft Procede de production de fibres de cellulose
EP2589689A4 (fr) * 2010-06-30 2014-01-22 Kolon Inc Dope pour le filage de fibre cellulosique à haute ténacité, procédé pour la préparation de fibre de filament cellulosique à haute ténacité utilisant un tel dope, et procédé pour la préparation de fibre courte de fibre cellulosique à haute ténacité
WO2015101543A1 (fr) 2014-01-03 2015-07-09 Lenzing Aktiengesellschaft Fibre cellulosique
US10883196B2 (en) 2014-01-03 2021-01-05 Lenzing Aktiengesellschaft Cellulose fiber
EP3536853A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell à formation de bouloche réduite
WO2019170740A1 (fr) 2018-03-06 2019-09-12 Lenzing Aktiengesellschaft Fibre lyocell à formation réduite de bouloche
CN118441367A (zh) * 2024-05-20 2024-08-06 雅思雅思拉普 抗原纤化的莱赛尔纤维及其制备方法与应用

Also Published As

Publication number Publication date
GB9818107D0 (en) 1998-10-14
GB2328397A (en) 1999-02-24
GB2328397B (en) 1999-08-11
ID16355A (id) 1997-09-25
AU1933297A (en) 1997-10-10
DE19781649T1 (de) 1999-04-29
TW380168B (en) 2000-01-21
GB9605504D0 (en) 1996-05-15

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