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 invention relates to flexible cellulose fibers with a reduced modulus and a reduced degree of NMR order for a predominant use in such textile fields in which flexible molded articles, e.g. Textile fibers and filament yarns are produced and required, hereinafter referred to as fibers, which are produced by the N-methylmorpholine-N-oxide (NMMNO) spinning process, which is more environmentally friendly than the viscose process, and a process for their production.
• NMMNO N-methylmorpholine-N-oxide
• a special feature of this process is the instability of the solvent under certain conditions at temperatures just a little above the processing temperature of the spinning solutions, which can lead to an uncontrolled chain reaction. It is therefore part of the prior art that additives are added to the spinning solution with the aim of stabilizing the spinning solution, in particular preventing or at least limiting the breakdown of the cellulose and the decomposition of the NMMNO (DD 201 703, DD 229 708).
• additives are added to the spinning solution with the aim of stabilizing the spinning solution, in particular preventing or at least limiting the breakdown of the cellulose and the decomposition of the NMMNO (DD 201 703, DD 229 708).
• a number of substances such as amines, gallates, ascorbic acid, hydroquinone and urea are mentioned by various authors. Propyl gallate has proven to be particularly effective even at low concentrations.
• the amounts used for stabilization are in a range below 1% based on cellulose.
• additives are also recommended to prevent the threads from sticking during the spinning process (DD 218 121) e.g. Polyethylene glycol, or recognized as useful for increasing the tear strength and the modulus of the threads (Chanzy, H. et al .: Polymer 31 (1990), 400-405).
• the strengths and moduli are characteristic of the fibers produced by the NMMNO process.
• the tensile strengths are generally in an approximate range from approximately 20 to 50 cN / tex, where cN / tex means centi Newtons per tex, and the initial moduli are in a range above approximately 1500 cN / tex. This means that the strengths are pleasantly high, but often higher than required and the moduli are significantly too high for an advantageous application in the area of flexible fibers with good textile properties, e.g. the usual viscose fibers, proven for textile use in clothing, with initial moduli well below 1500 cN / tex are used.
• the fibers produced with it also have some other disadvantages compared to those which are produced using the conventional viscose process. Among other things, they show Brittleness and tendency to fibrillate. The values achieved for the elongation at break are also unsatisfactory, so that Kloisinin et al. (SU 1 224 362) a solution of NMMNO in isopropanol or amyl alcohol has been described in place of the mostly used precipitation bath from an aqueous NMMNO solution. It also proves to be disadvantageous that the range of variation of the textile physical characteristics is small when the production conditions change.
• the fibers have a relatively high degree of order, which can be seen in the high-resolution 13 C-NMR solid-state spectrum at C-1, C-4 and to a certain extent also at C-6.
• the ratio of the line heights (distance of the maximum of the respective line from the baseline of the spectrum) at C-4 at approx. 88 and 85 ppm, a relatively easily accessible measure, is e.g. recognizable that for flexible viscose fibers this ratio has a value ⁇ 1.0, while for NMMNO fibers it is over one, e.g. at 1.35.
• the object of the present invention is to provide such flexible cellulose fibers which do not have all the disadvantages of the prior art.
• a further procedural object of the invention is that this proposed method for producing the flexible cellulose fibers of the type mentioned requires lower investment costs and is less polluting than the viscose method.
• An additional object of the invention is that this method to be proposed, based on the NMMNO process, allows a great deal of latitude in terms of the range of variation of the textile-physical parameters over changes in the manufacturing conditions.
• the tasks on the cellulose fiber side are solved with a flexible cellulose fiber with a reduced module and a reduced degree of NMR order, especially for textile use, which is achieved by pressing solutions of cellulose in water-containing NMMNO (N-methylmorpholine-N-oxide) through spinnerets over an air gap in an NMMNO-containing aqueous and / or alcoholic precipitation bath, as well as by conventional rinsing, post-treatment and drying with strengths between 15 and 50 cN / tex.
• NMMNO N-methylmorpholine-N-oxide
• these flexible cellulose fibers which can be produced in this way are characterized in that they have an initial modulus of less than 1500 cN / tex and in the high-resolution 13 C-NMR solid-state spectrum the ratio of the heights of the lines at 88 ppm and 85 ppm (C-4 range) above the spectrum baseline ⁇ 1.
• These flexible cellulose fibers according to the invention according to claim 1 with reduced modulus and reduced degree of NMR ordering are process-side by pressing a solution of cellulose in water-containing NMMNO through a spinneret over an air gap into an NMMNO-containing, aqueous and / or alcoholic precipitation bath and subsequent, conventional washing, Aftertreatment and drying can be produced.
• amines, amides or other amino group-containing substances preferably those with oxygen-bearing groups (for example carbonyl groups)
• oxygen-bearing groups for example carbonyl groups
• those with one of the nitrogen groups neighboring carbonyl group are favorable, such as urea, caprolactam, aminopropanol and / or aminocarboxylic acid. If several additives are used at the same time, it is possible to incorporate them as individual components or as a mixture.
• the specific application determines whether it is more advantageous to use the additives as individual components or as a mixture.
• the concentration of the additives in the spinning solution, based on the cellulose content of the solution should advantageously be at least 1% by mass, at most 200% by mass, preferably at least 10% by mass, at most 100% by mass.
• concentration of the additives in the spinning solution, based on the cellulose content of the solution is at least 4% by mass, at most 75% by mass, preferably at least 10% by mass, at most 50% by mass.
• a proportion of the additives of at least 0.1% by mass and at most 20% by mass, preferably at least 1% by mass and at most 10% by mass, based on the amount of the total precipitation bath is favorable.
• the desired effect also occurs when the water in the precipitation bath is partially or completely, preferably completely, replaced by alcohols, in particular by isopropanol or amyl alcohol, the additives being able to be present in the precipitation bath at most up to their saturation concentration.
• the fibers spun in a conventional manner from a nozzle through an air gap into the precipitation bath and aftertreated and dried in the usual way have an initial modulus derived in a known manner from the force / elongation diagram of well below 1500 cN / tex, preferably even below 1200 cN / tex, and / or an NMR order of magnitude of ⁇ 1 characterized by the height ratio in the maximum of the lines at 88 ppm and 85 ppm above the baseline of the high-resolution 13 C-NMR solid-state spectrum in the C-4 range.
• a spinning solution of 9.5% cellulose in NMMNO monohydrate with 0.1% by mass, based on cellulose, propyl gallate as stabilizing agent was spun in a laboratory extruder with a 20-hole nozzle at a temperature of 90 ° C., being the spinning bath a 10% solution of NMMNO in water was used.
• the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 34.3 cN / tex wet: 23.2 cN / tex Elongation at break, dry: 5.1% wet: 8.1%
• the ratio of the heights of the NMR lines at 88 and 85 ppm is 1.35.
• the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 35.6 cN / tex wet: 10.5 cN / tex Elongation at break, dry: 10.0% wet: 18.1% Initial module, dry: 1922 cN / tex wet: 131 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 1.0.
• Example 2 using a spinning bath consisting of a 6% aqueous urea solution.
• the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 33.1 cN / tex wet: 12.2 cN / tex Elongation at break, dry: 11.5% wet: 17.0% Initial module, dry: 1430 cN / tex wet: 120 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 1.0.
• the fiber has the following parameters: Titer: 4.0 tex Tensile strength, dry: 28.0 cN / tex wet: 13.2 cN / tex Elongation at break, dry: 13.9% wet: 19.9% Initial module, dry: 446 cN / tex wet: 126 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.96.
• the fiber has the following parameters: Titer: 4.2 tex Tensile strength, dry: 31.7 cN / tex wet: 10.2 cN / tex Elongation at break, dry: 8.8% wet: 16.2% Initial module, dry: 1059 cN / tex wet: 165 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.97.
• the fiber has the following parameters: Titer: 3.9 tex Tensile strength, dry: 16.5 cN / tex wet: 4.0 cN / tex Elongation at break, dry: 5.6% wet: 27.0% Initial module, dry: 669 cN / tex wet: 49 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.95 (see Fig. 2).
• the fiber has the following parameters: Titer: 4.2 tex Tensile strength, dry: 25.4 cN / tex wet: 10.1 cN / tex Elongation at break, dry: 7.1% wet: 11.9% Initial module, dry: 1580 cN / tex wet: 278 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.98.
• Examples 8 but additionally using a spinning bath (precipitation bath) consisting of a 10% aqueous aminocaproic acid solution.
• the fiber has the following parameters: Titer: 3.9 tex Tensile strength, dry: 18.3 cN / tex wet: 5.7 cN / tex Elongation at break, dry: 6.1% wet: 23.4% Initial module, dry: 760 cN / tex wet: 63 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.96.
• the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 24.9 cN / tex wet: 10.5 cN / tex Elongation at break, dry: 8.2% wet: 13.4% Initial module, dry: 1126 cN / tex wet: 129 cN / tex The ratio of the heights of the NMR lines at 88 and 85 ppm is 0.99.

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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)
• Multicomponent Fibers (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1994
  • 1994-06-10 DE DE4420304A patent/DE4420304C1/de not_active Expired - Fee Related
• 1995
  • 1995-03-24 EP EP95104358A patent/EP0686712B1/fr not_active Expired - Lifetime
  • 1995-03-24 AT AT95104358T patent/ATE170938T1/de not_active IP Right Cessation
  • 1995-03-24 DE DE59503497T patent/DE59503497D1/de not_active Expired - Lifetime
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