EP0918894A1

EP0918894A1 - Method for producing cellulose fibres

Info

Publication number: EP0918894A1
Application number: EP98927999A
Authority: EP
Inventors: Eduard Mülleder; Christoph Schrempf; Hartmut Rüf; Wilhelm Feilmair
Original assignee: Lenzing AG; Chemiefaser Lenzing AG
Current assignee: Lenzing AG
Priority date: 1997-06-17
Filing date: 1998-06-17
Publication date: 1999-06-02
Anticipated expiration: 2018-06-17
Also published as: SI0918894T1; ID21230A; CN1236403A; ATA105397A; KR20000068155A; EP0918894B1; ZA985246B; AU740994B2; JP3849062B2; WO1998058103A1; CA2263183C; NO315949B1; HK1023152A1; JP2000517009A; US6241927B1; NO990731D0; CA2263183A1; AU8002598A; CN1111617C; TW544476B

Abstract

The invention relates to a method of producing lyocell-type cellulose fibers by processing a spinnable solution of cellulose in an aqueous tertiary amine oxide according to the dry/wet-spinning process, which method is characterized in that a solution having a content of between 0.05% and 0.70% by mass, based on the mass of the solution, of cellulose with a molecular weight of at least 5x105 is used for spinning. The method of the invention allows the use of a spinnerette having more than 10,000 spinning holes for the spinning operation, which holes are arranged in such a manner that neighboring spinning holes are spaced maximally 3 mm apart and that the linear density of the spinning holes it at least 20.

Description

Process for the production of cellulosic fibers

The present invention relates to a process for the production of cellulosic fibers of the Lyocell type by processing a spinnable solution of cellulose in an aqueous tertiary amine oxide by the dry / wet spinning process.

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 ade 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.

To date, however, only one process for the production of a cellulose fiber of the Lyocell genus has become established until industrial implementation, namely the amine oxide process. In this process, N-methylmorpholine-N-oxide (NMMO) is preferably used as the solvent. For the purposes of the present description, the abbreviation "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 US Pat. No. 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. In the US PSen 3,447,939, 3,447,956 and 3,508,941 further processes for the production of cellulosic solutions are described, cyclic amine oxides being preferably 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. When the suspension is transported over the heating surface, water is evaporated off and the cellulose can be brought into solution, so that a spinnable cellulose solution is discharged from the film spinner.

A method for spinning cellulose solutions is e.g. known from US-A-4 246 221. According to this method, the spinning solution is extruded through a spinneret into filaments or threads, which are passed through an air gap into a precipitation bath in which the cellulose is precipitated. The filaments are stretched in the air gap, which gives the fiber favorable physical properties, e.g. a higher strength, can be given. By precipitating the cellulose in the precipitation bath, these physical properties are fixed, so that no further stretching is necessary. This process is commonly known as dry / wet spinning.

According to US-A-4 144 080, the freshly spun filaments can be cooled with air in the air gap. It is also proposed to wet the surface of the filaments with a precipitant in order to reduce the risk that the filaments will stick together. However, such wetting has the disadvantage that the cellulose is precipitated on the filament surface, which makes it more difficult to adjust the fiber properties by stretching. 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.

Applicant's WO 93/19230 improves the dry / wet spinning process and increases its productivity. This is brought about by a specific blowing with an inert cooling gas, the cooling being provided directly below the spinneret. In this way it is possible to greatly reduce the stickiness of the freshly extruded threads and thus to spin denser thread curtains, ie to use a spinneret with a high hole density, namely up to 1.4 holes / mm ² , which naturally increases the productivity of the dry / Wet spinning process can be increased considerably. Air with a temperature between -6 ° C and + 24 ° C is used to cool the freshly extruded threads.

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 0 per kilogram.

WO 95/01470 and WO 95/04173 by the applicant describe spinning processes in which a spinneret with a hole density of 1.59 holes / mm ² or a spinneret with a total of 15048 holes is used. The cooling air has a temperature of 21 ° C.

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 expert can do this The literature shows that the humidity is between 5.5 g H 0 and 7.5 g H 0 per kilogram of air. This creates a relatively dry climate in the air gap.

WO 96/17118 also deals with the climate in the air gap, it being established that the climate should be as dry as possible, namely 0.1 g H 0 to 7 g H 0 per kg air, with a relative humidity of less than 85%. 6 ° C to 40 ° C is suggested as the temperature for the cooling air. The specialist therefore takes from this literature to keep the climate as dry as possible during spinning.

This can also be found in WO 96/18760, which has an air gap temperature between 10 ° C. and 37 ° C. and a relative humidity of 8.2% to 19.3%, which means 1 g HO to 7.5 g HO per kilogram of air , suggests.

The applicant's WO 96/20300 describes, inter alia, the use of a spinneret with 28392 spinning holes. The air in the air gap has a temperature of 12 ° C and a humidity of 5 g H "0 per kilogram of air. This literature also shows the tendency, particularly when using a nozzle with a greatly increased number of spinning holes, that is to say when spinning a relatively dense thread curtain, to keep the climate in the air gap rather dry and cool.

WO 96/21758 also deals with the climate to be set in the air gap, two-stage blowing with different cooling air being proposed and blowing in the upper region of the air gap with less humid and cooler air.

A disadvantage of using less humid air is that such air can only be conditioned in a complex manner. The technical effort to provide cooling air with low humidity in large quantities for the amine oxide process is considerable. Furthermore, it has been shown that the cooling air becomes increasingly warmer and more humid as it passes through the thread curtain, since the freshly extruded fibers which leave the spinneret have a temperature of more than 100 ° C. and a water content of about 10% and on the cooling air gives off heat and moisture. The applicant has now found that this increasing water absorption with very thick thread curtains can lead to the fact that the required climate can only be adjusted by means of technically complex blowing devices and that the thread density cannot be increased further without these devices.

The object of the invention is therefore to eliminate these disadvantages and to provide a process for the production of cellulosic fibers of the Lyocell type by processing a spinnable solution of cellulose in an aqueous tertiary amine oxide by the dry / wet spinning process, it being possible for a dense thread curtain to be spun and the blowing air does not have to be dry anyway. Despite these requirements, the process should be able to be carried out with good spinnability, the spinnability being regarded as better the smaller the minimum achievable titer (see below).

This object is achieved in a method of the type defined in the introduction in that a solution is used for spinning which contains between 0.05% by mass and 0.70% by mass, in particular between 0.10 and 0.55% by mass. and preferably between 0.15 and 0.45 mass%, based on the mass of the solution, cellulose and / or another polymer having a molecular weight of at least 5x10 (= 500,000).

The molecular weight is determined in accordance with below-described, chroma ^¬ tographischem method. For the purposes of the present description, cellulose molecules or other polymer molecules which are produced according to the chroma-

In the process according to the invention, preference is given to using cellulose mixtures which have the stated content of long-chain molecules in the spinning solution.

In this connection, it is also surprisingly found that spinning a spinning solution containing such a cellulose mixture results in fibers with a lower tendency to fibrillation. This effect is even increased with an increasing moisture content of the air in the air gap.

N-methyl-morpholine-N-oxide has proven itself best as a tertiary amine oxide.

The invention further relates to the use of a spinnable solution of cellulose in an aqueous tertiary amine oxide, which solution between 0.05 mass% and 0.70 mass%, in particular between 0.10 and 0.55 mass%, and preferably between

0.15 and 0.45 mass%, based on the mass of the solution,

5 has cellulose with a molecular weight of at least 5x10, for the production of cellulosic fibers with a

Titers of up to 1 dtex. Such Lyocell fibers are new.

The invention also relates to a cellulosic fiber of the Lyocell genus, which is characterized in that it is obtainable by the process according to the invention.

The invention also relates to a cellulosic fiber of the Lyocell genus, which is characterized in that it has a titer of at most 1 dtex.

A preferred embodiment of the fiber according to the invention has between 0.25 and 7.0 mass%, in particular between 1.0 and 3.0 mass%, based on the mass of the cellulosic fiber, cellulose with a molecular weight of at least ⁵ × 10 ⁵ . TJ SH Cn GG

G G G = 0 0 G SH Φ

Φ Φ P Φ _^ SH XI ε φ = 0 P

C3 SH xi SH XI ε ε TJ G P. υ φ Φ XI Xl XI Φ Φ

= rö P u B Φ υ τs .. G G SH τs G tn ε rö φ u U cn SH ε SH Φ> G Φ Φ SH G P G G G - tn Φ = 0 G

H Φ P G G P cn cn Φ 0. G SH τs rö = rö Φ X. P = rö

• <tn G TJ G 5 in 0 υ τ) Φ G Φ X. φ φ GP m tn φ Φ o ^ Φ G SH _^ Φ υ CQ rö τs PG tn SH 0. P 5 Φ φ rö SH φ rö G tn τs = rö τs Φ Φ Φ

PM G Xl G Φ - o 5 G G Φ TJ &. P Φ 0 rö ε TJ P.

P rö Φ P TJ τs G P. fa 0 SH XI SH PG xl τ) υ cώ TJ TJ φ rö _^ SH Φ Φ SH X. cn> Φ φ Φ Φ

G SH 0 Φ rö G G U TJ O c φ ε Φ Cn CJ Φ Φ τs Cn> • ε φ. .3 - ». Φ P in SH Φ 0 G τs G φ XI Φ G rö G

> P 0 TJ X! - o -H Cn> X. <P n τs P = ü τs XI SH ε Φ -— ^

SH G SH υ in cn 5 G υ φ P Φ τs G υ P τs

Φ G tn P Φ cn G X rö ε SH X! ro X) xl X. P SH t i SH t TJ

G. ^< = _^ P in ε P Φ rö CJ τs X! P φ ro

SH Φ P U <£ 5 o Φ 0 TJ N X. X! SH Φ = rö G υ φ τ! Φ 5 Φ X.

Φ φ O rö tsi = 0 TJ cn cn Φ G Φ υ P τs SH X. rö τs cn τ) X U SH τs G P G G SH G t. m τi 3 τ) SH = P P rö H Φ Φ Φ Φ φ rö O ε Φ τi φ -H G TJ SH = rö ε 0 Ü G -. Φ SH X SH S rö Φ> Φ SH Φ = 0 X. SH φ 5 Φ - ^ • PM

SH G 0 ε Φ υ Φ SH τs ε G Φ ε SH τi cn υ

0 SH> Φ Φ τs τS φ Φ Φ τs τs üQ = P φ G G τs Φ Φ τs Φ cn

Φ Tj cn G τs> .. X G P Tj cn xi P Φ G P G rö

P TJ tn G 0 ^< : φ G rö GGG υ ε τi G 5 X SH X τs tn rö G xi tsi cn Φ ε φ Φ XI 0 SH P. , -. rö G rö SH υ υ

G G G P υ φ Φ φ cn ε> φ Φ ε P P. Φ Φ X G

P SH cn rö G X. rö = P SH τs Cn τ! ε> Φ Φ co SH X. Φ = 0 G X. cn Cn 2 G τi cn Φ Φ X SH φ SH Cr. Φ φ xl SH cn P υ G G P 0 G φ Xl QQ τs υ SH Φ φ G cn m Φ ro Φ

= P Φ rö TJ P tsi Φ> G X. υ rö G τ ⁾ Φ -HP XI Φ = PG XI Φ

X) £ -. G φ SH = o τi • = P P X. Tj 0 - - TJ 2 • Φ -

= P Φ X = 0 .. 0 TJ α SH Φ U -H. τ) XI G rö cn Φ -

3 SH SH SH 0 G P> X. φ G J φ G φ = 0> TJ rö υ G G rö

-. SH rö Φ rö G G Φ U X. G G X. QQ rö SH SH X.. -. &. X. Φ = PJ

Φ τs XI XI φ φ Φ X. P Φ CJ -HP = o rö G TJ ^• HG rö φ P.

Φ U ε υ ε

G ε G rö s G = 0 J SH Cn Φ G 5 G P. SH co ε Φ rö rö G *. φ τi φ _* . P Ü GG _^ - _^ cn SH cn Cn rö GG Cn Φ G τ) rö, P. Φ SH G tn ε P

3 cn P. G 2 P Φ SH G φ G Φ φ XI ε SH tΛ Φ = P rö P

Φ 0 Φ XI G n rö G G SH XI SH ε Φ 3 cn TJ

SH ε

P. SH SH CJ Φ o »o Φ P. SH Φ rö 0 Φ SH • H SH P Φ Φ Φ φ φ

0 rö P = rö SH G r o \ ° tsi P G rö Φ> G tsi P = Cn Cn X! Φ

> Φ φ P G - Φ X G X.G G P τ) -H tsi G cn Φ G υ τs τs

Φ X. G τs o Φ X! Φ. Φ Φ Φ - φ SH xi = rö Φ cn

X. Φ SH rö Qx P. o U τs TJ τs • P. τi Φ X. G Φ G φ Cn U Φ Φ τs τi 0 o rö G G = SH rö G X. Φ Φ Φ Φ Φ

Φ G SH G rö o \ ° 2 SH • G rö X Cn Φ rö X! . xl SH ε φ tn X. SH

SH τ) P cn G co Φ P 2 Φ o Φ G υ Xl 'rö u rö Φ

Φ TJ ε τs J c Φ G rö> φ ε> XI Φ SH SH: rö P SH rö υ TJ Φ P.

G P Φ TJ in in cn X. SH Φ Φ c ε ε £ P 0 Φ φ tn ε o in n G ε rö Φ SH SH: s rö τs P O 5 ω

Φ Φ - P ~ -. rö P rö Φ x. tn Φ Φ ε. -. G rö P cn rö

5 SH Φ X) SH G o o 2 Φ rö TJ XI ü φ ε Φ = o ε Φ Φ tn rö P o.

SH ω SH Φ Φ PQ G ε O SH ε xl G Φ SH P P o Φ φ cn rö cn SH = o Xl υ Cn Φ TJ P rö X.

G Φ SH SH X., - _-- SH SH Φ G υ G tn G SH Cn cn J rö φ Φ = rö rö Φ Φ G Φ Φ P ^• H _. φ rö w £ -. PX>3;"-" - P TJ 2 τs - - 'SH 5 SH PSP. r. τs G

shown) a. In Fig. 3 the filaments are drawn only visible in the air gap.

The inflow area is the mathematical product of the length of the air gap "1" and the width "b" of the first row of filaments. The linear density is given by the following mathematical relationship:

Spinning holes of the nozzle linear density = x air gap (mm)

Inflow area mm ²

The invention is described in more detail below.

1. General method for determining the molecular weight profile of pulps

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].

The size "differential weight fraction" describes the percentage frequency fraction of the molecular weight fraction.

For testing by means of GPC, the pulp is dissolved in dimethyl acetamide / LiCl and chromatographed. Detection is carried out by means of refractive index measurement and so-called "MALLS" (= Multi Angle Laser Light Scattering) measurement (HPLC pump: Kontron; sample collector: HP 1050, Hewlett Packard; solvent: 9 g LiCl / L DMAC; RI 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 μ - Mixed - A, Polymer Laboratories; Sample concentration: 1 g / 1 solvent; Injection volume: 40 μl, flow rate: 1 ml / min.

The measuring apparatus is calibrated using measures familiar to the person skilled in the art.

The signals are evaluated according to Zimm, whereby the Zimm formula may have to be set in the evaluation software.

1.1. Molecular weight profile of pulps

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 (about 0.2%) with a molecular weight of more than 500,000. A 15% cellulose solution of only this pulp (see below for production) in an aqueous amine oxide (= spinning mass) therefore does not correspond to that used according to the invention.

For comparison, 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 spinning mass _ausschließlich containing such pulp to 15 mass, having about 4% (based on the mass of the ^• solution; degradation during preparation of the solution not considered) cellulose molecules having a molecular weight greater than 500,000 and corresponds therefore not those which is used according to the invention. ,

.

0.

0

calmly. 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.

3. Spinning the solution and determining the maximum

Take-off speed or the minimum titer (spinnability)

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. By means of 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 μm.

For the experiments, 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. The maximum take-off speed (m / min) is determined by increasing the take-off speed 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 or the spinnability.

The titer that is given at the maximum withdrawal speed is calculated using the following general formula: 1, 21 XK x A x 100

Titer (dtex) = G x L

where 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, and L is the number of spinning holes in the spinneret. For the examples below, the concentration of cellulose is 15%, A = 0.030 g / minute, and L = 1.

4. Blowing in the air gap

The filaments in the air gap were blown over their entire length and at right angles to them. The humidity of the air was adjusted using a thermostat.

5. Spinning behavior of cellulose solutions

5.1. Cellulose solutions, which are too small a proportion

(<0.05 mass%) of long-chain molecules

According to the procedure described above, a pulp was produced with the pulp Viscokraft LV (manufacturer: International Paper Corp.), the molecular weight profile of which is shown in Fig. La, and spun in the air gap at different humidities, while the maximum take-off speed or the minimum spinnable Titer determined. The results are shown in Table 1.

In table 1 is "Temp." for the temperature of the spinning mass in ° C, "humidity" for the air humidity in the air gap in g of water / kg of air, and "max. take-off speed" stands for the maximum take-off speed in m / minute. The titer was calculated according to the above formula and has the unit dtex. Table 1

Pulp Temp. Moisture max. Less titer

Visco Force LV

II 115 0 176 0, 31

II 115 20 99 0, 55

II 115 48 63 0, 86

II 120 0 170 0.32

II 120 22 83 0.66

II 120 47 52 1, 05

The results shown in Table 1 show that the maximum withdrawal speed and the minimum titer decrease or increase with increasing moisture in the air gap. This means that the spinnability of a solution of this pulp, which has practically no long-chain components, deteriorates with increasing moisture in the air gap.

5.2. Cellulose solutions that have too high a proportion (> 0.70% by mass) of long-chain molecules

In accordance with the procedure described above, a pulp was produced with the pulp Alistaple LD 9.2 (manufacturer: Western Pulp), whose molecular weight profile is shown in FIG determined. An opposite result was obtained: the spinnability was somewhat better at higher humidities in the air gap than at lower humidities. However, the spinnability of such spinning masses, as can be seen from the minimal titer, is significantly worse overall, since it already contains too high a proportion of high molecular weight constituents. H

- <υ 0.

.-. os o

>

The tendency of the fibers produced to fibrillate even further with increasing moisture in the air gap.

2 shows the spinning behavior of cellulose solutions with varying proportions of long-chain molecules, the ordinate being the minimum titer (dtex) and the abscissa the concentration of the respective cellulose solution being applied to cellulose molecules with a molecular weight of at least 500,000. 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").

2 can be seen:

that there is a connection between spinnability and concentration of long-chain molecules;

that in dry air in the air gap (straight line "b") the spinnability becomes almost linearly better as the concentration of long-chain molecules decreases;

that in moist air in the air gap (curve "a") the spinnability initially becomes better and better with decreasing concentration of long-chain molecules, but deteriorates again from a concentration of about 0.25 mass%, this deterioration starting from 0.05 mass% % is particularly pronounced. FIG. 2 shows the range according to the invention (0.05 to 0.70 mass.). In this range, the minimum titer fluctuates only between about 0.4 dtex and 0.75 dtex, regardless of the humidity in the air gap. This means that the spinnability in this area is practically independent of the moisture in the air gap and that spinning masses with long-chain molecules in the concentration range specified according to the invention can be spun in dense thread curtains in which the air humidity has practically no negative influence on the spinnability, so that one time-consuming air conditioning and conditioning of the blown air is no longer necessary.

By means of extensive tests, the applicant has found that in this way thread curtains with a high linear density, namely a linear density of at least 20, which are blown with normal air, can be spun.

6. Fibrillation behavior of fibers produced from cellulose spinning solutions according to the invention and not according to the invention

Cellulose spinning solutions with a total cellulose concentration of 15% by weight were produced according to the method given under 2.

The following cellulose or cellulose mixtures were used as the cellulosic material used:

1) Viscokraft LV (100%)

2) Viscokraft LV (85%), Alistaple LD 9.2 (15%)

The cellulose solution, which contained 100% Viscokraft LV as cellulosic material, did not correspond to a cellulose solution used according to the invention immediately before spinning. The cellulose solution, which contained 85% Viscokraft LV and 15% Alistaple LD 9.2, immediately corresponded to the spinning of a cellulose solution used according to the invention.

Fibers were produced from the cellulose solutions in accordance with the procedure given under 3. In the individual experiments, air with different humidity was used under otherwise constant conditions for blowing the filaments in the air gap (see 4.). Fibrillation of the fibers thus produced was measured according to the following test.

Fibrillation test:

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 with a length of 20 mm were placed in a 20 ml sample vial with 4 ml of water and were held in a laboratory shaker of the RO type for 9 hours. 10 from Gehardt, 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.

Results :

The following table shows the fibrillation determined according to the above regulation:

Used pulp titer moisture of the number of

(dtex) Blown air fibrils (g H ₂ 0 / kg air)

100% visco power LV 1.7 10> 50

15% Alistaple LD 9.2 / 85% visco power LV 1.7 10 24

15% Alistaple LD 9.2 /

85% visco power LV 1.7 20 12

The table clearly shows that the tendency to fibrillation of fibers produced from cellulose solutions with the composition according to the invention is lower than for fibers which are produced from cellulose solutions with a composition not according to the invention. Furthermore, it can be seen from the table that the tendency to fibrillation of fibers produced from cellulose solutions used according to the invention drops even further when air with higher humidity is used for blowing.

Claims

Claims:

Process for the production of cellulosic fibers of the Lyocell type by processing a spinnable solution of cellulose in an aqueous tertiary amine oxide using the dry / wet spinning process,

characterized,

that a solution is used for spinning, which is between 0.05% by mass and 0.70% by mass, based on the

Mass of the solution, cellulose and / or another polymer

5 having a molecular weight of at least 5x10.

A method according to claim 1, characterized in that a solution is used for spinning, which has between 0.10 and 0.55% by mass, based on the mass of the solution, of cellulose with a molecular weight of at least 5x10.

A method according to claim 2, characterized in that a solution is used for spinning, which between

0.15 and 0.45 mass%, based on the mass of the solution,

5 has cellulose with a molecular weight of at least 5x10.

Process according to one of claims 1 to 3, characterized in that N-methylmorpholine-N-oxide is used as the tertiary amine oxide.

Use of a spinnable solution of cellulose in an aqueous tertiary amine oxide, which solution between 0.05 and 0.70% by mass, based on the mass of the solution, of cellulose having a molecular weight of at least 5x10, for the production of cellulosic fibers with a titer of at most 1 dtex.

Cellulosic fiber of the Lyocell genus, characterized in that it has a titer of at most 1 dtex.

7. Cellulosic fiber of the Lyocell genus, obtainable by a process according to one of claims 1 to 4.

Cellulosic fiber according to one of claims 6 or 7, characterized in that it contains between 0.25 and 7.0% by mass, in particular between 1.0 and 3.0% by mass, based on the mass of the cellulosic fiber has a molecular weight of at least 5x10.

Cellulosic fiber according to one of claims 6 to 8, characterized in that it is present as a staple fiber.

10. Process for the production of cellulosic fibers

Genus Lyocell by processing a spinnable solution of cellulose in an aqueous tertiary amine oxide using the dry / wet spinning process,

characterized in that

(1) a solution is used for spinning, which is between 0.05 and 0.70 mass., Based on the

Mass of the solution, cellulose with a molecular

5 has a weight of at least 5x10, and (2) a spinneret is used for spinning, which has more than 10,000 spinning holes, which are arranged so that adjacent spinning holes are spaced apart by a maximum of 3 mm, and that the linear density of the spinning holes is at least 20.