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WO1997036029A1 - Procede de production de fibres de cellulose et produits en fibres de cellulose - Google Patents

Procede de production de fibres de cellulose et produits en fibres de cellulose Download PDF

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Publication number
WO1997036029A1
WO1997036029A1 PCT/EP1997/001365 EP9701365W WO9736029A1 WO 1997036029 A1 WO1997036029 A1 WO 1997036029A1 EP 9701365 W EP9701365 W EP 9701365W WO 9736029 A1 WO9736029 A1 WO 9736029A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
zinc chloride
acid
fibers
fiber
Prior art date
Application number
PCT/EP1997/001365
Other languages
German (de)
English (en)
Inventor
Abdulmajid Hashemzadeh
Original Assignee
Akzo Nobel N.V.
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 Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to JP9534003A priority Critical patent/JP2000507315A/ja
Priority to EP97914266A priority patent/EP0889978A1/fr
Priority to AU21578/97A priority patent/AU2157897A/en
Publication of WO1997036029A1 publication Critical patent/WO1997036029A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • 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 invention relates to a method for reducing the tendency of cellulose fibers to fibrillate, which at the same time brings about a reduced formation of gray fog, improved dyeability and levelness and a softer feel of textile products which were produced from the fibers treated according to the invention.
  • NMMO N-methylrriorpholine-N-oxide
  • a disadvantage of this method is that the fibers obtained tend to fibrillate relatively strongly, which is perceived as very disruptive for very many applications. It has been shown that cellulosic fibers which are produced by the NMMO process, particularly when wet, have a great tendency to fibrillate, especially when mechanical forces act on the fibers. This occurs in particular when dyeing and washing yarns which have been produced from the fibers just mentioned.
  • Fibrils have a disturbing effect on dyed textiles in that along folds which arise when washing in the washing machine, as a result of the increased abrasion at these points, a gray haze which is undesirable for aesthetic reasons is formed, which increases with each washing cycle.
  • fabrics made of fibers which have been produced by the process mentioned have a lower dye absorption than viscose fibers and have an increasingly harder grip with each wash. Textiles made from fibers that tend to fibrillate therefore do not meet the expectations of the customer from the outset with regard to comfort, which also worsens with every wash.
  • the international patent application WO-Al-92/14871 describes a process in which an effort is made to control the pH value in the different wash baths to reduce the tendency of the threads to fibrillate.
  • WO-Al-95/16063 describes a method in which a surfactant is added to the precipitation bath and / or the washing baths.
  • Vulkanfiber a material which is produced by treating paper with an aqueous solution of zinc chloride with a concentration of 65 to 73% by weight of zinc chloride, the solution being 30 is warm up to 50 ° C.
  • the paper is vulcanized, i.e. the cellulose filaments are intensively glued together.
  • the object of the invention is therefore to provide a method which does not require changes to the known spinning, drawing and precipitation bath technology which is optimized at high cost and which eliminates or at least substantially reduces the disadvantages mentioned .
  • This object is achieved by a process for the production of cellulosic fibers by spinning a solution of cellulose in a tertiary amine oxide, possibly also containing water and possibly a stabilizer, precipitation, washing, squeezing and drying of the fibers, which is characterized in that is that the fibers are treated either after washing or after squeezing or after drying with a zinc chloride solution which may contain an acid at a temperature in the range from about 10 to 250 ° C., the Zinc chloride solution has a zinc chloride concentration in the range from about 30 to 70% by weight and an acid concentration in the range from 0 to about 10% by weight, after which the fibers are washed free of zinc chloride and, if appropriate, of acid, optionally squeezes and dries.
  • a zinc chloride solution which may contain an acid at a temperature in the range from about 10 to 250 ° C.
  • the Zinc chloride solution has a zinc chloride concentration in the range from about 30 to 70% by weight and an acid concentration in the
  • the zinc chloride and possibly an acid-containing solution is preferably aqueous.
  • Acetic acid has proven to be a preferred suitable acid.
  • the addition of acid leads to an accelerated occurrence of the desired effects, so that the acid is preferably used when, for example, very high spinning speeds are required or when a fiber with a high titer is to be treated.
  • One embodiment of the invention is that the fibers are treated in a single device with the zinc chloride and optionally an acid-containing solution.
  • any device is suitable for this which is capable of completely providing the fiber with the treatment solution and of allowing the necessary mass and heat transport processes to take place sufficiently quickly.
  • a bath is preferably used in which there is an acidic zinc chloride solution and in which the fibers are treated.
  • turbulence or pressure waves can be generated in the bath, for example by ultrasound.
  • a zinc chloride concentration in the range from approximately 40 to 65% by weight, in particular in the range from approximately 50 to 60% by weight, an acid concentration in the range from approximately 0 to 5% by weight is preferred.
  • the treatment times will move in the direction of the lower limit of the time ranges mentioned, the higher the treatment temperatures are selected, whereas the longer the treatment times, the lower the treatment temperatures.
  • the fibers require a longer treatment time the higher their average degree of polymerization.
  • a further embodiment of the invention is that the fibers are first completely provided with the zinc chloride and possibly an acid-containing solution in the device already described, preferably in a bath, the bath temperature being in the range from about 20 to 25 ° C. lies. The same applies to the zinc chloride and acid concentration said. The fibers are then heat-treated outside of the device mentioned.
  • any heat transfer medium that is capable of allowing the necessary mass and heat transport processes to run sufficiently quickly is suitable for the heat treatment.
  • a zone of warm or hot gas is preferably used, the fibers being blown with the gas.
  • gases or vapors can be used which are inert with cellulose, zinc chloride, water and possibly with the acid under the conditions according to the invention.
  • Air is preferably used.
  • a temperature in the range from approximately 40 to 250 ° C., in particular in the ranges from approximately 150 to 250 ° C. and 40 to 70 ° C. is preferred for the heat treatment Dwell time of the fiber in the bath in the range of about 0.1 to 5 seconds, in particular in the range of about 0.5 to 3 seconds, and a dwell time of the fiber in the heat treatment zone in the range of about 0.1 to 10 seconds, especially in the range of about 0.2 to 5 seconds.
  • the treatment according to the invention can be carried out not only as already described at various points in the spinning process, but also on cellulosic fiber products, the fibers of which are obtained by spinning a solution of cellulose in a tertiary amine oxide which may also contain water and possibly a stabilizer , Cases, washing, squeezing and drying were obtained, the washed and optionally dried or unwashed fiber products with an acidic zinc chloride solution at a temperature in the range from about 10 to 250 ° C.
  • the zinc chloride solution has a zinc chloride concentration in the range of about 30 to 70% by weight and an acid concentration in the Has a range from 0 to about 10% by weight, after which the fibers are washed free from zinc chloride and possibly from acid, if necessary squeezed and dried.
  • the invention is applicable to all linear and flat cellulosic fiber products.
  • textile fabrics such as e.g. Fabrics, knitwear, nonwovens or laid scrims or yarns, fiber sheets or tapes are treated.
  • Staple fibers, short cuts or flakes or mixed yarns made of cellulosic and synthetic fibers can also be treated.
  • the zinc chloride and possibly an acid-containing solution is preferably aqueous.
  • Acetic acid has proven to be a preferred suitable acid.
  • the addition of acid leads to an accelerated occurrence of the desired effects, so that the acid is preferably used when very high treatment speeds of the cellulosic fiber product are required or when a fiber product with a very dense structure is to be treated.
  • One embodiment of the invention consists in treating the cellulosic fiber products in a single device with the zinc chloride and possibly an acid-containing solution.
  • any device is suitable for this, which is capable of completely providing the treatment solution to the cellulosic fiber products and of allowing the necessary mass and heat transport processes to take place sufficiently quickly.
  • the cellulosic fiber products are preferably treated in a bath in which the zinc chloride solution, which may contain an acid, is present. To accelerate the necessary heat and mass transfer processes, turbulence or pressure waves can be generated in the bathroom, for example by ultrasound.
  • a further embodiment of the invention consists in first providing the cellulosic fiber products completely with the zinc chloride and possibly an acid-containing solution having a temperature in the range from approximately 20 to 25 ° C. in the device already described and then heat-treating outside the device .
  • the wet scrub test apparatus shown schematically in FIG. 1 is used to measure the tendency to fibrillation of individual threads.
  • the wet abrasion test is carried out with threads which have been removed from the products mentioned.
  • the wet abrasion test equipment essentially consists of the elements (1) to (6), which are explained in the following:
  • the thread (2) is fixed in a PVC block (1).
  • the scouring load is generated in that the thread (2) is guided over an arrangement rotating at 25 revolutions per minute, which consists of a 2.5 mm thick ceramic rod (4) attached to a glass rod (5) with a diameter of 6 mm Diameter exists.
  • the wet scrub test was run for 1 minute.
  • the defined and reproducible fibrillation produced with the described apartment was assessed on a scale with the marks 1 to 6 by microscopic evaluation of the scrubbed, approximately 3 mm long fiber area.
  • Primary fibrillation means that fibrils are only observed on the fiber surface.
  • Secondary fibrillation means that the fibrils are also observed in the deeper layers of the filaments. The more secondary fibrillation progresses, the longer and thicker the fibrils become.
  • a grade scale from 1 to 6 was defined using the terms just described. The means
  • Primary and secondary fibrillation such as those on untreated
  • the dyeing of the fabrics takes 1 hour and is carried out at 50 ° C and a liquor ratio of 1: 160.
  • a paddle serves as the coloring unit. This is followed by a 20 minute boiling soap with Perilan VF (4.0 g / 1) and the detergent Kieralon Jet B.
  • the brightness which is determined with the Minolta Chroma Meter, is used to measure the color depth.
  • the fibers or fiber products treated according to the invention show a significantly reduced tendency to fibrillation with notes between 2 and 3, have no gray haze before washing in the washing machine or after 10 washes, and are distinguished by a pleasantly soft handle, which itself does not become harder after washing 10 times in the washing machine.
  • the fiber products treated and dyed in accordance with the invention are surprising in that they have a higher level of levelness and a significantly deeper dyeability, the properties just mentioned not decreasing even after washing 10 times.
  • the invention is not restricted to the use of a certain average degree of polymerization DP of the cellulose raw material. Rather, cellulose or cotton linters with a DP in the range from about 400 to 7000 can be used individually or as a mixture of celluloses with a high and low degree of polymerization.
  • the invention is not restricted to a specific stabilizer in the spinning solution. Rather, all additives suitable as stabilizers can be used, e.g. Pyrrogallol, gallic acid or propyl gallate.
  • the invention is not restricted to a specific cellulosic fiber type, but encompasses all cellulosic fiber types such as e.g. Continuous filaments or fibers, and staple or short cut fibers, flakes or blended yarns made of cellulosic and synthetic fibers.
  • the invention is also not limited to the fact that the fibers or a textile fabric produced therefrom under a ner certain mechanical tension must stand. Rather, the fibers or the textile fabrics produced therefrom can be used without mechanical tension or in a state of mechanical tension.
  • the invention is not restricted to the use of a certain tertiary amine oxide, but preferably uses N-methylmorpholine-N-oxide (NMMO).
  • NMMO N-methylmorpholine-N-oxide
  • the invention is further illustrated by the following examples.
  • the zinc chloride used was purchased from Fluka and has a purity of 98%.
  • a desized and dried fabric made of fibers (75 dtex, f 50) spun from an NMMO-containing cellulose solution is treated for 8 minutes in a bath containing a solution of 55% by weight zinc chloride in water.
  • the bath has a temperature of 22 ⁇ 3 ° C.
  • the fabric is then squeezed, washed and dried in a known manner.
  • the fabric treated and dyed in this way shows no gray haze and is further characterized by a 25% deeper staining, a softer feel and a very high level of levelness in comparison to untreated fabric which has a clear gray haze and whose levelness is desirable leaves little.
  • the tendency to fribrillation of fibers taken from the treated tissue was given a rating of 2, while untreated fibers were rated 6.
  • the treated fabric shows no gray haze and is still characterized by a high level of levelness, an unchanged soft feel and a 25% deeper staining compared to the untreated fabric, the handle of which is significantly harder.
  • the tendency to fribrillation of fibers taken from the treated tissue was given a grade of 2-3, while untreated fibers were rated 6.
  • a fiber (75 dtex f 50) spun, precipitated, washed and squeezed from an NMMO / cellulose solution is treated in a bath which contains a solution of 60% by weight zinc chloride in water.
  • the solution has a temperature of 22 + 3 ° C.
  • the fiber speed and the dimensions of the treatment bath are adjusted so that a fiber residence time of about 1.5 ⁇ 0.5 seconds results.
  • the fiber is then drawn through a hot air zone and blown with hot air at 225 ⁇ 25 ° C.
  • the fiber speed and the dimensions of the hot air zone are adjusted so that a fiber residence time of about 2 seconds results.
  • the fiber is squeezed, washed and dried in a known manner. The tendency to fribrillation of fibers treated in this way was given a grade of 2-3, while untreated fibers were rated 6.
  • a fiber spun, precipitated, washed, squeezed and dried from an NMMO / cellulose solution (75 dtex f 50) is treated in a 22 + 3 ° C. bath containing a solution of 50% by weight zinc chloride in water.
  • the fiber speed and the dimensions of the treatment bath are set in such a way that a fiber residence time of about 1 + 0.5 seconds results.
  • the fiber is then placed in a warm air zone conducted and blown with 55 + 5 ° C warm air.
  • the fiber speed and the dimensions of the warm air zone are set such that a fiber dwell time of about 2 seconds results.
  • the fiber is then squeezed, washed and dried in a known manner. The tendency to fribrillation of fibers treated in this way was rated 2-3, while untreated fibers were rated 6.
  • a fiber spun, precipitated, washed, squeezed and dried from an NMMO / cellulose solution (75 dtex f 50) is treated in a 22 ⁇ 3 ° C. bath containing a solution of 55% by weight zinc chloride in water.
  • the fiber speed and the dimensions of the treatment bath are set so that a fiber residence time of about 2 minutes results.
  • the fiber is then squeezed, washed and dried in a known manner.
  • a fabric is produced from the fiber treated in this way, which shows the same properties as the treated fabric of Example 1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Selon l'invention, un traitement avec une solution de chlorure de zinc contenant éventuellement un acide, avec une concentration en chlorure de zinc comprise entre 30 et 70 % en poids et à une température comprise entre 10 et 250 °C, permet, comparativement à des fibres ou à des produits fibreux non traités, d'améliorer les propriétés de fibres de cellulose filées à partir de solutions d'amines tertiaires ou celles de produits en fibres de cellulose. Les améliorations portent sur les points suivants: la tendance à la fibrillation diminue, la formation de voile gris est évitée et n'apparaît même pas après plusieurs lavages, le toucher est plus doux et le produit conserve sa souplesse, même après plusieurs lavages. En outre, la profondeur du pouvoir tinctorial et l'uniformité des couleurs subsistent, même après plusieurs lavages.
PCT/EP1997/001365 1996-03-27 1997-03-19 Procede de production de fibres de cellulose et produits en fibres de cellulose WO1997036029A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9534003A JP2000507315A (ja) 1996-03-27 1997-03-19 セルロース繊維およびセルロース繊維の製造方法
EP97914266A EP0889978A1 (fr) 1996-03-27 1997-03-19 Procede de production de fibres de cellulose et produits en fibres de cellulose
AU21578/97A AU2157897A (en) 1996-03-27 1997-03-19 Process for producing cellulose fibres and cellulosic fibre products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19612145.0 1996-03-27
DE19612145 1996-03-27

Publications (1)

Publication Number Publication Date
WO1997036029A1 true WO1997036029A1 (fr) 1997-10-02

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PCT/EP1997/001365 WO1997036029A1 (fr) 1996-03-27 1997-03-19 Procede de production de fibres de cellulose et produits en fibres de cellulose

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EP (1) EP0889978A1 (fr)
JP (1) JP2000507315A (fr)
AU (1) AU2157897A (fr)
WO (1) WO1997036029A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015101543A1 (fr) 2014-01-03 2015-07-09 Lenzing Aktiengesellschaft Fibre cellulosique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1272445A (en) * 1968-08-29 1972-04-26 Budd Co Machine for continuously treating vulcanized fibre
DE2164385A1 (de) * 1971-01-05 1973-06-28 Johnson & Johnson Verfahren zum behandeln von fasermaterialien zum zugaenglichmachen dieser materialien gegenueber nachfolgenden textilverfahren mit waessrigen medien
DE2838799A1 (de) * 1978-09-06 1980-03-13 Dynamit Nobel Ag Vulkanfiber und verfahren zu ihrer herstellung
SU1158644A1 (ru) * 1984-03-29 1985-05-30 Всесоюзное Ордена Трудового Красного Знамени Научно-Производственное Объединение Целлюлозно-Бумажной Промышленности Способ получени фибры
JPH01156599A (ja) * 1987-12-08 1989-06-20 Hokuetsu Paper Mills Ltd バルカナイズド・フアイバーの製造方法
JPH07189019A (ja) * 1993-12-22 1995-07-25 Kohjin Co Ltd 再生セルロース成形品の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1272445A (en) * 1968-08-29 1972-04-26 Budd Co Machine for continuously treating vulcanized fibre
DE2164385A1 (de) * 1971-01-05 1973-06-28 Johnson & Johnson Verfahren zum behandeln von fasermaterialien zum zugaenglichmachen dieser materialien gegenueber nachfolgenden textilverfahren mit waessrigen medien
DE2838799A1 (de) * 1978-09-06 1980-03-13 Dynamit Nobel Ag Vulkanfiber und verfahren zu ihrer herstellung
SU1158644A1 (ru) * 1984-03-29 1985-05-30 Всесоюзное Ордена Трудового Красного Знамени Научно-Производственное Объединение Целлюлозно-Бумажной Промышленности Способ получени фибры
JPH01156599A (ja) * 1987-12-08 1989-06-20 Hokuetsu Paper Mills Ltd バルカナイズド・フアイバーの製造方法
JPH07189019A (ja) * 1993-12-22 1995-07-25 Kohjin Co Ltd 再生セルロース成形品の製造方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BETRABET S M ET AL: "Electron-Microscope Study of Cotton Treated with Inter- and Intracrystalline Swelling Agents", TEXTILE RESEARCH JOURNAL, vol. 40, no. 10, October 1970 (1970-10-01), pages 917 - 924, XP002034641 *
BETRABET S M ET AL: "Part I. INTRACRYSTALLINE SWELLING AND DECRYSTALLIZATION IN ZINC CHLORIDE-TREATED COTTON CELLULOSE", CELLULOSE CHEMISTRY AND TECHNOLOGY, vol. 3, February 1969 (1969-02-01), pages 309 - 323, XP002034642 *
DATABASE WPI Section Ch Week 8550, Derwent World Patents Index; Class F09, AN 85-315347, XP002034645 *
DATABASE WPI Section Ch Week 8930, Derwent World Patents Index; Class F09, AN 89-217702, XP002034644 *
DATABASE WPI Section Ch Week 9538, Derwent World Patents Index; Class A11, AN 95-290979, XP002034643 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015101543A1 (fr) 2014-01-03 2015-07-09 Lenzing Aktiengesellschaft Fibre cellulosique
US10883196B2 (en) 2014-01-03 2021-01-05 Lenzing Aktiengesellschaft Cellulose fiber

Also Published As

Publication number Publication date
EP0889978A1 (fr) 1999-01-13
JP2000507315A (ja) 2000-06-13
AU2157897A (en) 1997-10-17

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