EP0731856B1 - Process for the preparation of cellulose fibres - Google Patents

Abstract

The invention is concerned with a process for the production of cellulose fibres, wherein a solution of cellulose in an aqueous tertiary amine-oxide is extruded into filaments through spinning holes of a spinneret and the extruded filaments are conducted across an air gap into a substantially aqueous precipitation bath, characterized in that the extruded filaments, while being conducted across the air gap, are contacted with an aliphatic alcohol which is present exclusively in gaseous state. The process according to the invention produces cellulose fibres having a very reduced tendency to fibrillation.

Description

The present invention relates to a process for the production of cellulose fibers, wherein a solution of cellulose in an essentially aqueous tertiary amine oxide is extruded into filaments through spinning holes in a spinneret and the extruded filaments are passed through an air gap into a precipitation bath.

As an alternative to the viscose process, a number of processes have been described in recent years in which cellulose is dissolved in an organic solvent, a combination of an organic solvent with an inorganic salt or in aqueous salt solutions without the formation of a derivative. Cellulose fibers made from such solutions were given the generic name Lyocell by BISFA (The International Bureau for the Standardization of man made Fibers). BISFA defines a cellulose fiber as Lyocell, which is obtained from an organic solvent by a spinning process. BISFA understands "organic solvent" as a mixture of an organic chemical and water. "Solvent spinning" is intended to mean dissolving and spinning without derivatization.

To date, however, only a single process for the production of a cellulose fiber of the Lyocell type has prevailed until industrial implementation. In this process, N-methylmorpholine-N-oxide (NMMO) is used as the solvent. Such a method is described, for example, in US Pat. No. 4,246,221 and provides fibers which are distinguished by a high strength, a high wet modulus and by a high loop strength. A process for the industrial production of spinnable solutions by Cellulose in tertiary amine oxides is known from EP-A - 0 356 419.

The utility of fabrics, e.g. However, fabrics made from the fibers mentioned are severely restricted by the pronounced tendency of the fibers to fibrillate when wet. Fibrillation is understood to mean breaking open the fiber in the longitudinal direction under mechanical stress in the wet state, as a result of which the fiber is given a hairy, furry appearance. A fabric made and dyed from these fibers loses its color intensity over the course of a few washes. In addition, there are bright stripes on the scuffed and crease edges. The cause of the fibrillation is assumed to be that the fiber consists of fibrils arranged in the direction of the fibers, between which there is only a small amount of cross-connection.

WO 92/14871 describes a method for producing a fiber with a reduced tendency to fibrillation. This is achieved in that all baths with which the fiber comes into contact before the first drying have a pH of maximum 8.5.

WO 92/07124 also describes a method for producing a fiber with a reduced tendency to fibrillation, according to which the undried fiber is treated with a cationic polymer. A polymer with imidazole and azetidine groups is mentioned as such a polymer. In addition, treatment with an emulsifiable polymer, e.g. Polyethylene or polyvinyl acetate, or crosslinking with glyoxal.

In a lecture given by S. Mortimer at the 1993 CELLUCON conference in Lund, Sweden, it was mentioned that the tendency to fibrillation increased with increasing stretching.

It has been shown that the known cellulose fibers of the Lyocell genus still leave something to be desired with regard to the tendency to fibrillation, and the present invention therefore has the object of providing a cellulose fiber of the Genus Lyocell which has a further reduced tendency to fibrillation.

This aim is achieved in a method of the type described in the introduction in that the extruded filaments are brought into contact with an aliphatic alcohol which is present exclusively in gaseous form during the passage through the air gap.

The term "air gap" means the gas space which extends between the spinneret and the precipitation bath. However, the gas in this gas space does not necessarily have to be air, but rather can be any gas or gas mixture which does not impair the spinning process. The term "air gap" thus includes any such gas or gas mixture in addition to air.

As mentioned above, the aliphatic alcohol is said to be in "gaseous form". For the purposes of the present description and claims, this term is intended to express that the alcohol in the air gap is not present as a mist. It has been found that it is essential for the process according to the invention that the dew point for the alcohol used is not undercut in the air gap. This can be prevented with certainty that the alcohol is in the form of small, droplet-forming droplets.

In contrast to the method according to the invention, it is known from US Pat. No. 4,261,943 to pass the extruded filaments through a cloud chamber in which a non-solvent, for example water, is in the form of tiny droplets is present. This measure is intended to reduce the stickiness of the freshly extruded filaments, since the water droplets coagulate the surface of the filaments. Superficial coagulation is neither achieved nor aimed for in the process according to the invention, since this is disadvantageous for the fibers. The present invention is based on the discovery that cellulose fibers of the Lyocell genus have a considerably reduced tendency to fibrillate when the freshly extruded filaments are exposed to an aliphatic alcohol.

It has been shown that the following alcohols are particularly suitable for reducing the tendency to fibrillation: methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol and tert-butanol. A mixture of these alcohols can also be used.

In "Structure formation of cellulosic fibers from amine oxide solvents" (Weigel P .; Gensrich, J .; Fink, HP; Challenges in Cellulosic Man-Made Fibers, Viscose Chemistry Seminar, Stockholm 1994) it is mentioned that isopropanol is used as the precipitation bath allows the production of a fiber with a low tendency to fibrillation. Isopropanol as a precipitant is disadvantageous because the textile data are falling sharply. The investigation of the crystallization of the fiber when using methanol in the spin bath was carried out by Dube, M .; Blackwell, RH: 1983 TAPPI International Dissolving and Specialty Pulps, Proceedings pp. 111-119, and von Quenin, I .: "Precipitation de la cellulose a partir de solutions dans les oxydes d'amines tertiaires - application au filage", dissertation 1985 , examined. In contrast, the inventors of the present invention have found that even if an aqueous precipitation bath is used, a fiber with the desired reduced tendency to fibrillation can be produced if an aliphatic alcohol is provided in gaseous form in the air gap.

For an efficient production of fibers with a reduced tendency to fibrillation, it has proven to be advantageous if the extruded filaments are blown in the air gap with a gas stream which contains the aliphatic alcohol in gaseous form. The production of an alcohol-containing gas stream is known to the person skilled in the art and can e.g. simply by spraying the alcohol into the gas stream using an ultrasonic atomizer or by passing the gas stream through the alcohol.

A further advantageous variant of the process according to the invention is that the solution of cellulose in an aqueous tertiary amine oxide is extruded into filaments through ring-shaped spinning holes of a spinneret, so that a ring-shaped filament curtain is passed through the air gap, and that the gas stream is in the center of the Filament curtain formed ring supplied and the filament curtain is blown radially from the inside out. A suitable device with which an annular filament curtain can be blown in the manner described is known from WO 93/19230.

It has proven expedient to additionally blow the extruded filaments with a second gas stream, the ring-shaped filament curtain being blown radially from the outside inwards. Such a blowing process is also known in principle from WO 93/19230.

It has been shown that large air gap widths have a positive effect on the fibrillation behavior, but that this occurs relatively quickly with the small hole / hole spacings used in staple fiber nozzles Leads to spinning defects. An air gap width of less than 60 mm and greater than 20 mm is preferred.

The spinning holes preferably have a diameter between 80 and 100 microns.

It is best to extrude between 0.025 and 0.05 g of cellulose solution per minute per spinning hole.

The temperature in the air gap is selected so that on the one hand the dew point is not fallen below, i.e. that no alcohol condenses in the air gap and on the other hand that there are no difficulties in spinning due to the temperature being too high. Values between 10 and 60 ° C can be set, with temperatures between 20 and 40 ° C being preferred.

All known cellulosic spinning materials can be processed by the process according to the invention. So these spinning masses can contain between 5 and 25% cellulose. However, cellulose contents between 10 and 18% are preferred. Hard or softwood can be used as the raw material for pulp production, and the degrees of polymerization of the pulp (s) can be in the range of commercially available products. Mixtures of several pulps can also be used (Chanzy et al., TAPPI 5th International Dissolving Pulp Conference 1980, pp. 105-108). However, it has been shown that the spinning behavior is better with a higher molecular weight of the pulp. Depending on the degree of polymerization of the pulp or solution concentration, the spinning temperature can be between 75 and 140 ° C. and can be easily optimized for each pulp or concentration. The warping in the air gap depends on the diameter of the nozzle hole and the concentration of cellulose in the solution when the titer of the fibers is fixed. In the range of the preferred cellulose concentration, however, this could not be influenced the fibrillation obsolescence is determined as long as one is in the area of the optimal spinning temperature.

The test methods and preferred embodiments of the invention are described in more detail below.

Fibrillation assessment

The friction of the fibers against one another during washing processes or during finishing processes when wet was simulated by the following test: 8 fibers were placed in a 20 ml sample vial with 4 ml of water and in a laboratory shaker type RO-10 from Gerhardt for 9 hours, Bonn (FRG) shaken at level 12. The fibrillation behavior of the fibers was then assessed under the microscope by counting the number of fibrils per 0.276 mm fiber length.

Textile data

Strength and elongation were tested according to the BISFA regulation "Internationally agreed methods for testing viscose, modal, cupro, lyocell, acetate and triacetate staple fibers and tows", edition 1993.

Example 1-8

A 12% spinning solution of sulfite and sulfate pulp (12% water, 76% NNMO) was spun at a temperature of 115 ° C. A melt index device from Davenport used in plastics processing was used as the spinning apparatus. This device consists of a heated, temperature-controlled cylinder into which the spinning mass is poured. By means of a piston, which is loaded with a weight, the spinning mass is passed through the spinneret attached to the underside of the cylinder extruded. This process is referred to as the dry / wet spinning process since the extruded filament is immersed in a spinning bath after it has passed through an air gap.

A total of 9 extrusion tests were carried out, the alcohol used, its concentration, the spinning mass throughput and the width of the air gap being varied. A spinning over an air gap without alcohol (80% relative humidity; 28 ° C) served as a comparison. The column "Fibrils" shows the average number of fibrils over a fiber length of 276 µm. The results are shown in Table 1. Table 1 Example No. alcohol Alcohol conc. Through sentence gap Fibrils 1a (V) ----- ---- 0.025 60 8th 1b (V) ----- ---- 0.050 60 16 2nd Methanol 72 0.025 60 0.4 3rd Methanol 263 0.050 60 8.5 4th Ethanol 240 0.025 60 1.3 5 Ethanol 255 0.05 60 3.5 6 Ethanol 250 0.025 30th 2.3 7 i-propanol 344 0.025 60 4.5 8th n-butanol 247 0.025 60 0.4

In the table are the alcohol used, the alcohol concentration in the air gap (g / m ³ ), the Spinning mass throughput (g of spinning mass / hole / min), the length of the air gap (mm) and the number of fibrils per fiber length of 0.276 μm, which were obtained in the fibrillation test described above.

Examples 9-14

A spinneret with circularly arranged spinning holes was used for Examples 9 to 14, so that a circular filament curtain was passed through the air gap. For example 9, air (comparison) and for examples 10-14 gas containing methanol were fed into the center of the circle formed by the spinning holes and blown radially outward. A spinning device with which Examples 9 to 14 can be carried out is known from WO 93/19230 (FIG. 2), but the ring-shaped filament curtain was only blown radially from the inside to the outside. The rest of the procedure was analogous to the conditions of Examples 1-8.

The results are shown in Table 2. Table 2 Example No. alcohol Alcohol conc. Through sentence gap Fibrils 9 (V) ----- ---- 0.025 60 > 50 10th Methanol 60 0.025 35 15.5 11 Methanol 60 0.025 45 9.0 12th Methanol 60 0.025 60 5.5 13 Methanol 110 0.025 45 1.5 14 Methanol 140 0.025 45 1.0

Table 3 shows characteristic fiber data for the fibers shown in Table 2. Table 3 Example No. Fiber strength cond. cN / tex Fiber elongation cond. % Fiber strength wet cN / tex Fiber stretch wet% 9 (V) 28.4 14.1 24.4 26.3 10th 29.9 17.7 27.2 25.7 11 28.7 17.8 26.8 28.1 12th 27.2 17.3 25.1 24.8 13 26.2 19.2 22.1 24.7 14 29.1 16.9 23.4 23.4

The titers (dtex) of fibers 9, 10, 11, 12, 13 and 14 shown in Table 3 were 1.71, 1.56, 1.6, 1.62, 2.1 and 1.86, respectively.

Claims (8)

1. A process for the production of cellulose fibres, wherein a solution of cellulose in an aqueous tertiary amine-oxide is extruded through spinning holes of a spinneret into filaments and conducted across an air gap into a substantially aqueous precipitation bath, characterized in that said extruded filaments, while being conducted across the air gap, are contacted with an aliphatic alcohol, said alcohol being present exclusively in gaseous state.
2. A process according to Claim 1, characterized in that as said alcohol methanol, ethanol, n-propanol, i-propanol, n-butanol, sec.-butanol or tert.-butanol or a mixture of these alcohols is used.
3. A process according to one of the Claims 1 to 3, characterized in that said extruded filaments are contacted with said aliphatic alcohol by being exposed in the air gap to a gas stream containing said aliphatic alcohol in gaseous state.
4. A process according to Claim 3, characterized in that said solution of cellulose in an aqueous tertiary amine-oxide is extruded through spinning holes of a spinneret arranged in a ring-shape into filaments, a filament curtain arranged in a ring-shape being conducted across the air gap, and that said gas stream is introduced in the center of the ring formed by the filament curtain, said filament curtain being exposed radially to said gas stream from the inside towards the outside.
5. A process according to Claim 4, characterized in that said extruded filaments additionally are exposed to a second gas stream, said filament curtain arranged in a ring-shape being exposed to said gas stream radially from the outside towards the inside.
6. A process according to one of the Claims 1 to 5, characterized in that said air gap has a length of from 20 to 60 mm.
7. A process according to Claim 1, characterized in that said spinning holes have a diameter of from 80 to 100 µm.
8. A process according to Claim 7, characterized in that from 0,025 to 0,05 g of cellulose solution per minute are extruded at each spinning hole.