Title of Invention	METHOD AND DEVICE FOR THE PRODUCTION OF MOLDED CELLULOSE BODIES
Abstract	The invention relates to a method for producing molded cellulose bodies by using ionic liquids, especially 1,3-dialkylimidazolium halides, as solvents. According to said method, the cellulose is dissolved, the solution is shaped into fibers or foils/membranes, the cellulose is regenerated with the aid of a precipitation process in aqueous solutions, the solvent is separated by washing, and the molded bodies are dried.

Title of Invention

METHOD AND DEVICE FOR THE PRODUCTION OF MOLDED CELLULOSE BODIES

Abstract

The invention relates to a method for producing molded cellulose bodies by using ionic liquids, especially 1,3-dialkylimidazolium halides, as solvents. According to said method, the cellulose is dissolved, the solution is shaped into fibers or foils/membranes, the cellulose is regenerated with the aid of a precipitation process in aqueous solutions, the solvent is separated by washing, and the molded bodies are dried.

Full Text	METHOD AND DEVICE FOR THE PRODUCTION OF MOLDED CELLULOSE BODIES This invention relates to a process for producing shaped articles of cellulose using ionic liquids, in particular 1,3-dialkylimidazolium halides, as a solvent, which process comprises dissolving the cellulose, forming the solution into fibers or films/membranes, regenerating the cellulose by coagulating in aqueous solutions, removing the solvent by washing and drying the formed articles. To form cellulose, which is an infusible polymer, into filaments, fibers or films/membranes under industrial conditions, three different solution spinning processes have been developed to a point of technical maturity, namely the spinning of stable derivatives, for example secondary acetate rayon, dissolved in acetone without regeneration (acetate process - Ullmann's Encyclopedia Weinheim: VCH-Verlagsgesellschaft 198 6 Vol. A5 pp. 438-448), the spinning of semistable derivatives, for example cellulose xanthate, dissolved in caustic soda with regeneration (Gotze K. "Chemiefasern nach dem Vis-koseverfahren" Berlin/Heidelberg/New York: Springer Verlag 1967), and the spinning of solutions of cellulose and amine oxide hydrates and regeneration by coagulating the cellulose in aqueous amine oxide solutions [Lyocell process - Woodings C. "Regenerated Cellulose Fibres" Woodhead Publishing Ltd. Cambridge 2001; DE-A 29 13 589 and 28 48 471, US-A 4 246 221]. It is further known to dissolve cellulose in "chelate"-forming metal complexes, for example in copper tetramine hydroxide (cuoxam), copper ethylenediamine (cuen) , nickel tris(2-aminoethyl)amine (nitren), zinc diethyltriamine; dime thylacetamide/lithium chloride [Klufers P. "Which metals form complexes with cellulose dianions" paper presented in German to a DFG meeting at Bad Herrenalb March 16, 1999] . These solvents have found broad analytical interest, but hitherto no industrial application apart from coppertetramine hydroxide for spinning cuprammonium rayon. Although ionic liquids have been known since 1914, it is only very recently that they achieved importance as a solvent or reaction medium for many syntheses. Of particular interest are compounds having a positive nitrogen atom such as the ammonium, pyridinium and imidazolium cation [Schilling G. "Ionische Flussigkeiten" GIT Labor-Fachzeitschrift 2004 (4) 372-373] . It is known from WO 03/02932 9 and US-A 2003/0157 351 that certain ionic liquids, consisting predominantly of cyclic nitrogen cations and halogen anions, dissolve cellulose in the absence of water and at elevated temperature and reprecipitate the cellulose on addition of water. The cellulose solution is produced by dissolving dry cellulose in substantially anhydrous ionic liquids by supply of energy, for example by heating with microwaves. Nothing is said about the properties of the starting and regenerated celluloses, of the cellulose solution and the possible conditions under which the cellulose solution might be formed into articles. Positive factors favoring the use of ionic liquids as a solvent for forming cellulose into filaments, fibers and films/membranes are a possible higher thermal stability compared with amine oxide hydrates and also a significantly better environmental compatibility compared with the viscose, acetate and copper process. Ionic liquids used as a solvent should permit operation in a closed-loop solvent cycle or circuit. It is an object of the present invention to provide a process whereby cellulose (chemical pulp, bleached elemental chlorine free ECF or total chlorine free TCF) is formed into filaments, fibers and films/membranes with substantial preservation of molecular parameters in a simple, consistent and environmentally friendly operation, and also corresponding apparatus. This process and apparatus shall make it possible to produce formed articles of cellulose having novel and/or improved properties. We have found that this object is achieved by a process for producing a formed article of cellulose by dissolving cellulose in an ionic liquid, forming the viscous solution into a formed article and regenerating the cellulose, which comprises a) cellulose or a cellulose mixture being dispersed in water by shearing to the individual fiber, pressed off and the press-moist cellulose or cellulose mixture being b) dispersed in the ionic liquid in the presence of basic substances and optionally further stabilizers, the water being removed under shearing, increasing temperature and decreasing pressure (from about 800 to 850 mbar to about 10 to 30 mbar) and converted into a homogeneous solution, c) feeding the solution through one or more temperature-controllable tubular lines and a pressure-equalizing apparatus to at least one spin pack, d) the solution in the spin pack passing through a filter, a distributor plate preferably configured as a heat exchanger and the spinning capillary or capillaries or the slot of the spinneret die or dies, e) leading the solution jets which have been formed into filaments or a film through a conditioned gap with drawing, f) the oriented jets of solution being coagulated by treatment with a temperature-controlled solution which is miscible with the ionic liquid but constitutes a coagulant for the cellulose and, at the end of the coagulation bath sector, being separated from the coagulation bath by diversion or deflection, and g) the formed article in the form of filament yarn, fiber tow or film/membrane being withdrawn, subjected to a single or multiple stage coagulant wash, optionally spin finished and dried or cut into staple fibers, spin finished and dried. Preferably, the spinning solution does not attain the spinning temperature until passing through the distributor plate configured as a heat exchanger. In a preferred embodiment of the process of the present invention, the spinning solution is formed in spinning capillaries 0.4 to 5 mm in overall length (1), having a cylindrical portion (L = 0.5 - 3 D) , a conical portion (1-L) and an outlet diameter (D) of 0.05 to 0.25 mm having a circularly round arrangement of the spinning capillaries for filament yarns and a rectangular arrangement of the spinning capillaries for fibers. The spinning solution is advantageously formed into a flat film using a broad slot die having a gap width of 0.1 to 2.0 mm in thickness. Blown films are suitably produced using annular slot dies having a gap width of about 0.1 to 1.5 mm. The dispersing and dissolving of dry cellulose, without prior inclusion of costly and inconvenient grinding processes, in anhydrous ionic liquids, for example in l-butyl-3-methylimidazolium chloride, does not lead to a nodule-free suspension nor, even after very long dissolving times, to a homogeneous solution that meets the requirements of a spinning operation. Finely ground cellulose is very bulky, does not flow freely, and is prone to deflagrations in the presence of air. It has further emerged that this way of dissolving the cellulose is associated with a significant degradation in molar mass. A spruce sulfite pulp having a cuoxam DP of 550 prior to dissolving by microwave heating was found to give a cellulose having a cuoxam DP of 172 after regeneration from the solution. Spinning such solutions into fibers is not possible. The process of the present invention is capable of utilizing chemical pulps from wood or cellulosic fibers from annual plants, in particular cotton 1inters, produced by the sulfite, sulfate/prehydrolysis sulfate or organosolve process using elemental chlorine free (ECF) and/or total chlorine free (TCF) bleaching. Preference is given to using mixtures of celluloses having a medium molar mass (cuoxam DP 400-800) in admixture with high molecular weight (cuoxam DP 800-3000) or low molecular weight (cuoxam DP 20-400) celluloses. Preferred ionic liquids are melts of 1,3-dialkyl-imidazolium halides. The ionic liquid has added to it for stabilization, before and/or during the dissolving, basic substances of low vapor pressure in such an amount that the suspension of cellulose/aqueous ionic liquid has a pH of 8 or more. The basic compound having a low vapor pressure is particularly preferably an alkali metal hydroxide, such as KOH or NaOH. In the process of the present invention, the pulp is beaten up to the individual fiber by vigorous shearing in water. After pressing off, there is a swollen cellulose containing about 50 % by mass of water. The press-moist cellulose can easily be converted, for example in aqueous 1-butyl-3-methylimidazolium chloride which concurrently contains sufficient alkali metal hydroxide as to produce a pH > 8, into a homogeneous suspension which by shearing, temperature increase and pressure reduction after distillative removal of the water transitions into a homogeneous spinning solution. Under these conditions, the dissolving time is only a fraction of that required to dissolve dry cellulose in anhydrous l-butyl-3-methylimidazolium chloride. Molar mass degradation is below 10 %. Spinning solution quality can be characterized similarly to the Lyocell process by determination of particle content cppm and the class width specific particle distribution [q3x = f (x)] by laser diffraction (see Kosan B. Michels Ch. Chemical Fibers International 48 (1999) 4 pp. 50-54] and also of zero shear viscosity Ή 9 and relaxation time XBm [see Michels Ch. Das Papier 52 (1998) 1 pp. 3-8]. In practice, these solutions have relaxation time spectra [H = f (A) ] , since the cellulose has a molar mass distribution. λ&m is then the relaxation time at the frequency maximum in the weighted relaxation time spectrum [HA = f(A) ] . In contradistinction to cellulose/amine oxide hydrate solutions, cellulose solvation in 1-butyl-3-methylimidazolium chloride or 1-ethyl-3-methylimidazolium chloride proceeds distinctly more slowly and the attainment of minimum zero shear viscosity (complete solvation) is significantly more dependent on dissolving temperature and dissolving time. The temperature function of zero shear viscosity and relaxation time is given by the relation (1) (1) Its knowledge is of significant importance for forming highly elastic solutions in the spinneret die channel and gap. Cellulose concentration and cellulose or cellulose mixture molar mass are advantageously so chosen that a zero shear viscosity of 1000 to 100 000 Pass and preferably of 10 000 to 80 000 Pa s becomes established at 85 °C for the spinning solution. Molar mass stability for a prolonged period at elevated temperature benefits from the addition of antioxidants as well as of bases. Antioxidants are in particular organic compounds having at least one conjugated double bond and two hydroxyl or amino groups, such as hydroquinone, p-phenylenediamine, gallic esters, tannins and the like. As is evident from DTA/DSC and reaction-calorimetrie measurements, thermal stability of spinning solutions according to the present invention is significantly higher than that of stabilized Lyocell spinning solutions. Whereas stabilized cellulose/amine oxide hydrate solutions represent a risk of explosive decomposition at above 130 °C, 1-butyl-3-methylimidazolium chloride is stable up to 250 °C at least and, in the stabilized spinning solution, cellulose starts to decompose at above 213 °C. The forming of the solution into filaments, fibers and films/membranes is effected in a modified dry-jet wet-spinning process by the solution being fed via a temperature-controllable tubular line and pressure-equalizing apparatus to the spin pack at dissolving temperature 9L , being forced therein to a safety spinning filter, adjusted in a temperature-controllable heat exchanger to the requisite spinning temperature 9sp, allowed to relax in accordance with the solution's relaxation time λ9m at the spinning temperature, formed through spinneret dies into filaments or films and being led through a gap to the coagulation bath while undergoing drawing. Between the heat exchanger outlet and the spinning capillaries there should remain a volume V in cm3 which is not less than the product of volume stream vL in cm3/s and relaxation time Km in s at the spinning temperature. (2) In the gap, which consists of a conditioned zone, the filament sheet is subjected - perpendicularly to its direction of transport and in a sheetlike manner - to a flow of conditioned air at preferably 15 to 25 °C and 20 to 80 % relative humidity. Filament formation can be represented as a two-stage operation. The solution jet undergoes, predominantly under the influence of the shearing stress rD, at constant temperature, a narrowing in the spinning capillary from the spinning capillary's entry cross section AE to the exit cross section AAr i.e., the draw in the die SVD follows from (3) DE and DA correspond respectively to the entry and exit filament consolidation in the gap should be associated with disruptions in the fiber sheath and has an adverse effect on the fibrillation characteristics of the fibers. In addition, the jets of solution are highly hygroscopic, take up water from the conditioned environment, and a partial coagulation of the cellulose takes place in the edge zones. It has been determined in relation to the process of the present invention that very good fiber properties are achieved when the surface area increase ∆Oa attains values Surface area increase normalized to the gap a = 1 is a further important parameter. surface area increase is a measure of the rate of surface area change and should be as small as possible. Good fiber properties are obtained at values van mm/min, and in particular at van The conditioning of the gap, preferably by means of air of defined temperature and humidity, as well as providing a cooling and stabilizing effect to the moving yarn, results in a partial precipitation of the cellulose, preferentially in the edge zones of the filaments. This enhances spinning consistency, in particular at high capillary densities, promotes the formation of a core-sheath structure, and improves fiber properties. As it passes through the conditioned drawing zone, the filament sheet is preferably additionally subj ected to a likewise conditioned stream of gas. In the process of the present invention, the oriented jets of solution are routed through an aqueous coagulation bath containing up to 50 % by mass or preferably up to 25 % by mass of the ionic liquid used for dissolving, to regenerate the cellulose. We have further found that when for example 1,3-dialkylimidazolium halides are used as a solvent, the slightly brown coagulation bath can be decolorized by treatment with alkaline hydrogen peroxide at 60 to 80 °C and the cations entrained by the pulp or other, ancillary products can be removed via cation exchangers. The coagulation bath thus cleaned or purified can be returned into the circuit as a solvent after it has been concentrated by distillation. The process of the present invention and the apparatus will now be elucidated by reference to drawings and by examples, where Figure 1 shows a graphical depiction of the particle size distribution of a typical cellulose/-1-butyl-3-methylimidazolium chloride spinning solution containing 11.5 % by mass of cotton linters pulp; Figure 2 shows a graphical depiction of the weighted relaxation time spectrum of a spinning solution containing 12.5 % by mass of eucalyptus prehydrolysis sulfate pulp at 85 °C; Figure 3 shows a graphical depiction of the temperature function of zero shear viscosity and relaxation time for the spinning solution according to Figure 2; Figure 4 shows the DSC-determined enthalpy as a function of the temperature for 1-butyl- 3-methylimidazolium chloride and for a spinning solution containing 12 % by mass of spruce sulfite pulp and 1-butyl-3-methylimidazolium chloride as solvent; Figure 5 shows the schematic depiction of an apparatus for carrying out the process for producing filament yarns and fibers; Figure 6 shows the schematic depiction of a preferred apparatus for producing fibers and films; Figure 7 shows a schematic depiction of the distributor plate configured as a heat exchanger. Figure 1 shows the density distribution q3(x) determined by laser distribution against the particle size in µm for a spinning solution stabilized with 0.22 % by mass of NaOH (based on the solvent), consisting of 11.5 % by mass of cotton linters pulp (cuoxam DP 650) and 88.5 % by mass of 1-butyl-3-imidazolium chloride and having a zero shear viscosity of 31 650 Pa s and a relaxation time of 5.3 s at 85 °C. The particle content of 20 ppm divides into 81 % Figure 2 shows the weighted relaxation time spectrum (HA) = f (A) for a spinning solution stabilized with 0.22 % by mass of NaOH and 0.04 % by mass of propyl gallate (based on the solvent), composed of 12.5 % by mass of a eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569) and 87.5 % by mass of 1-butyl-3-methylimidazolium chloride and having a zero shear viscosity of 27 010 Pa s and a relaxation time of 9.5 s at 85 °C. Particle content was 22 ppm with a 40 % fraction Figure 3 contains the temperature function of zero shear viscosity and relaxation time (at the frequency maximum) in the temperature range 70-130 °C for the spinning solution in Figure 2. Comparison of the spinning solutions in figures 1 to 3 illustrates the influence of pulp provenience, molar mass (cuoxam DP), cellulose concentration, stabilization and temperature on zero shear viscosity, relaxation time and solution state. Figure 4 shows the results relating the thermal analysis of the solvent 1-butyl-3-methylimidazolium chloride and of a stabilized spinning solution composed of 12 % by mass of eucalyptus prehydrolysis sulfate pulp and 88 % by mass of l-butyl-3-methylimidazolium chloride. While the solvent has no changes up to 250 °C besides the endothermic melting peak, the spinning solution curve contains an exothermic peak starting at 213 °C as well as the endothermic melting peak. The exothermic peak starting at 213 °C evidently marks the onset of the thermal degradation of the cellulose. Figure 5 shows a spinning appliance for carrying out the process of the present invention. The spinning appliance consists of a temperature-controllable tubular line (1) , pressure-equalizing apparatus (2) , spin pack (3), drawing zone (9), coagulation bath (11) and withdrawal godet roll (18) . The spin pack (3) comprises a distributor plate which is configured as a heat exchanger (5) and comprises a solution filter (4), an inflow chamber (6) and at least one spinneret die (7). Situated between the spin pack (3) and the coagulation bath (11) is the conditioned drawing zone (9) with gas supply/distribution (10), the length of which is adjustable through vertical movement of the coagulation bath (11) • The coagulation bath container (11) comprises the inflow chamber (12) for forming a laminar coagulation bath current, the overflow (13), the floor opening (14) confined by a yarn-routing element consisting of ceramic, the receiving trough (15) , coagulation bath pump (16) and thermostat (17) . The yarn-guiding element in the floor opening (14) and the withdrawal godet roll (18) are used to separate the filament bundle (19) from the coagulation bath (11) by withdrawing at an angle (3, which is preferably less than 70 °. Figure 6 shows a spinning apparatus which is preferably used for spinning fibers and films. The construction up to the spinneret die (7) substantially corresponds to that of figure 5. Here the spinneret die (7) forms a rectangle and contains rowed spinning capillaries or a slot for spinning films. The conditioned drawing zone (9) and the gas supply/distribution (10) are adapted to this rectangular shape. The length of the drawing zone (9) is adjusted by vertical displacement of coagulation bath (11). As indicated by the dotted line, the drawing zone (9) is substantially enclosed. Opposite the gas supply/distribution (10) , openings for conducting away the conditioned quench gas are arranged. The coagulation bath (11) is again formed from inflow or calming chamber (12), overflow (13), deflecting roller or roll (14), receiving trough (15), pump (16) and thermostat (17) . Yarn sheet (19) and coagulation bath (11) are separated by deflecting at an angle > 90 and withdrawal via the pair of godet rolls (18). When films are spun, a driven roll (14) performs the task of deflection and further guiding rollers become responsible for the transportation to the pair of godet rolls (18) . Figure 7 shows in schematic form the construction of the distributor plate configured as a heat exchanger (5) and comprising solution filter (4) , seals (8) and heaters (H) . The spinning solution at temperature Tl (9) passes through the solution filter (4), flows through a multiplicity of bores (R) while concurrently heating up to the spinning temperature T2 (9p) and passes at this temperature through the inflow chamber (6) and the die (7). The heat exchanger (5) preferably consists of nickelized or chromed aluminum, copper or brass. It further advantageously comprises a hollow, closed off by seals (8), for receiving the filter pack (4), a separate heating system (H) and flow channels (R) . Examples 1 to 7 A spruce sulfite pulp (cuoxam DP 550; ECF bleached) was beaten up in water at a liquor ratio of 20:1 and was dewatered by pressing off to 40 % by mass. Dispersion of 75 g of press-moist cellulose in 275 g of 1-butyl-3-methylimidazolium chloride (BMIMC1) with 20 % by mass of water and stabilizing additives as indicated in Table 1 gave 350 g of homogeneous suspension which after introduction into a vertical kneader was converted into a homogeneous solution under vigorous shearing, gradually rising temperature from 85 to 120 °C and decreasing pressure from 850 to 20 mbar by complete removal of water. The dissolving time was a uniform 60 minutes. The solution with 12 % by mass of cellulose and 88 % by mass of BMIMC1 (refractive index 1.5228 at 50 °C) was investigated immediately after dissolving and after spinning (corresponds to 2 0 hours at 85 °C). The results are given in Table 1. The addition of alkali led to a significant stabilization of the cellulose. Evidently, the BMIMC1 detaches traces of hydrochloric acid at high temperature and they led to cleavage of the 1,4-acetal bond of the cellulose. The addition of a small amount of radical scavengers as in Examples 5 to 7 provided a further improvement in the thermal long-term stability of the spinning solutions. Example 8 37 5 g of eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569; TCF bleached) were beaten up in water in a liquor ratio of 15:1 in a jet stream mixer, separated from the liquor via a centrifuge down to 50 % by mass, coarsely comminuted and dispersed press-moist in 3088 g of l-butyl-3-imidazolium chloride (BMIMC1) with 15 % by mass of water also containing 0.22 % by mass of sodium hydroxide and 0.036 % by mass of propyl gallate. Introducing the suspension into a vertical kneader, evaporating 838 g of water during 60 minutes under vigorous shearing, elevated temperature (85 to 130 °C) and vacuum (800 to 15 mbar) produced a homogeneous solution composed of 12.5 % by mass of cellulose and 87.5% by mass of BIMIMC1 and having a zero shear viscosity of 32 680 Pa s, a relaxation time of 9.8 s at 85 °C and a temperature function as per In ήo = 16.9874 + 9799 1/T Particle content of the solution was 18 ppm with 65 % The solution was spun in an experimental machine according to Figure 5. The requisite spinning solution amount mL was fed at 85 °C bulk temperature via a temperature-controlled tubular line at the same temperature to the spin pack by means of a spin pump (0.10 ml/revolution), filtered, heated in the heat exchanger to the spinning temperature 9 , relaxed in the inflow chamber with about 8 ml volume and pressed through dies containing 30 or in the case of trial # 7.12, 60 spinning capillaries having an L/DA ratio of 1 or, in the case of trial # 5.3, of 2 and an exit diameter of DA. The jets of solution passed while undergoing SVa drawing through the conditioned air gap of length a and were additionally quenched with 25 (fibers) or 100 1/min (filament yarn) of air at 25 °C and humidity according to table. The oriented sheet of yarn passed through the spin bath at a temperature of 20 °C while the cellulose was simultaneously coagulated, was separated from the coagulation bath at the withdrawal speed va at an angle (3 = 4 0 °, withdrawn via godet rolls and sent to the af tertreatment. The aftertreatment was carried out batchwise and tensionlessly for the fiber samples, whereas in the case of filament yarn (trial # 7.12) it was carried out continuously under minimal tension ( Spinning conditions and also fiber and filament yarn properties are recited hereinbelow in Tables 2 and 3. Table 2 also shows the computed surface area increase AOa and also the rate van of surface area increase. exhaustively described by Mieck K.P. et al. in Melliand Textilberichte 7 4 (1993) 945 and Lenzinger Berichte 74 (1994) 61-68. Cuoxam DP was 531 for the dissolved cellulose and 52 9 for the fiber. Fiber properties comprised high tenacities and moduli in the conditioned and wet states and also an elevated wet abrasion resistance compared with Lyocell fibers. Example 9 A cotton 1inters pulp (cuoxam DP 650) was converted similarly to Example 8 into a spinning solution having 11.5 % by mass of cellulose, a zero shear viscosity of 31 650 Pa s at 85 °C, a relaxation time of 5.3s at 85 °C, a particle content of 20 ppm, particles Pump rate Diameter DA Spinning temperature Draw ratio SVa Air gap Relative humidity Spin bath Withdrawal speed 1.35 g/min 100 Vim (30 capillaries) 100 °C 9.3 12 mm 7.5 g,0 20 °c 50.2 m/min Fibers were obtained having very high tenacities and moduli in the conditioned and wet states: Fineness Tenacity conditioned wet Elongation at break conditioned Initial modulus Wet abrasion resistance Fiber cuoxam DP wet conditioned wet 1.27 dtex 67.7 cN/tex 60.9 cN/tex 9.0 Q. 8.8 Q. 1366 cN/tex 511 cN/tex 43 cycles 624 Example 10 A mixture of 85 % by mass of beech prehydrolysis sulfate pulp (cuoxam DP 390; TCF bleached) and 15 % by mass of spruce sulfite pulp (cuoxam DP 780; ECF bleached) was conjointly beaten up in water to the individual fiber using a jet stream mixer and separated from the liquor via a screen belt press. 1020 g of the press-moist cellulose having a water content of 52 % by mass were intensively mixed in 3478 g of BMIMC1 with 15 % by mass of water which concurrently contained 0.22 % of sodium hydroxide and 0.036 % of propyl gallate, in a vertical kneader, and under shearing, elevated temperature (85/130 °C) and vacuum (700/20 mbar) 1044 g of water were distilled off during 60 minutes and subsequently dissolved for 60 minutes. The solution formed contained 14.0 % by mass of cellulose having a cuoxam DP of 465 for the dissolved cellulose. Zero shear viscosity at 85 °C was 13 100 Pa s, relaxation time was 5.5 s. Particle analysis revealed a 28 ppm content with a particle size distribution of 82 % 40 pm. A machine according to Figure 6 was 'used to spin the solution. A spin pump carried 19.1 g/min of spinning solution at 90 °C into the spin pack, which is filtered through a screen filter (mesh size 25 µm), heated up to 110 °C in the heat exchanger and pressed through a rectangular die containing 900 spinning capillaries (arranged over an area of 1 x 3 cm) having an exit diameter of 75 pm. The sheet of filament passed while being drawed to a ratio of 5.1 through the conditioned gap 2.8 cm in length, and was quenched over a width of 9 cm with 160 1/min of air at 23 °C and 70 % relative humidity. Surface area increase during drawing was 0.128 cm2/min + filament, its rate was 0.46 mm/min. After cellulose coagulation in the spin bath at 23 °C and deflection, the filament sheet arrived at a pair of godet rolls at a withdrawal speed of 22 m/min. Cutting of the tow of fiber into staple 40 mm in length, washing and finishing was followed by drying at 90 °C down to a residual moisture content of 10 % by mass. The following values were obtained for the mechanical fiber properties: 1.50 dtex 44.1 cN/tex 40.0 cN/tex 12.1 12.0 o 32.2 cN/tex 920 cN/tex 340 cN/tex 130 cycles Fineness Tenacity conditioned Tenacity wet Elongation at break conditioned Elongation at break wet Loop tenacity conditioned Modulus conditioned Modulus wet WAR Example 11 A mixture of cotton linters pulps (80 % by mass of cuoxam DP 4 65 and 20 % by mass of cuoxam DP 650) were prepared similarly to Example 9. The press-moist cellulose mixture had a water content of 45 % by mass. In a horizontal single screw mixing/kneading reactor of the type Diskotherm B (LIST AG ARISDORF Switzerland), in the first shearing zone, continuously, 819 g/min of preheated 1-ethyl-3-methylimidazolium chloride (EMIMC1), containing 10 % by mass of water, 0.28 % of sodium hydroxide and 0.04 % of tannin, at 90 °C were metered via a precision gear pump and 200 g/min of comminuted cellulose via a belt scale and valveless plunger metering pump, mixed and heated up to 120 °C under a vacuum of 30 mbar and 172 g/min of water were distilled off. The pale yellow homogeneous solution produced in the second shearing zone contained 13 % by mass of cellulose (zero shear viscosity 11 450 Pa s at 85 °C) and was cooled to 110 °C and fed by a vertical double screw conveyor to a wide film laboratory plant. It corresponded in construction to the arrangement in Figure 6. 847 g/min of spinning solution were fed via a pressure-equalizing apparatus and precision gear pump to the spin pack, filtered, homogenized to 110 °C in the heat exchanger and pressed through a film die 100 mm in slot width and 1.2 mm in slot thickness. The 100 mm in slot width and 1.2 mm in slot thickness. The solution formed into flat film was drawed to a ratio of 3.2 while passing through a conditioned air gap (20 °C; 55 % relative humidity) 15 mm in length, arriving in the coagulation bath (an EMIMCl-containing aqueous solution), deflected via a driven roll and attracted by the two rolls at 20 m/min. Washing, drying and finishing gave a conditioned film 40 µm in thickness and 61 g/m in mass per unit area. The longitudinal tensile strength of the film was 27.2 cN/tex, its longitudinal elongation was 16.8 %. Example 12 234 g of eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569; TCF bleached) were beaten up in water in a liquor ratio of 25:1 using an ultra-mixer, adjusted to pH 10 with sodium hydroxide, separated from the liquor by pressing off to 26.7 % by mass, coarsely comminuted and dispersed press-moist in 1520.5 g of 1-butyl-3-methylimidazolium chloride (BMIMC1) containing 22 % by mass of water, 1.4 g of sodium hydroxide and 1.2 g of propyl gallate. Introducing the suspension (2400 g) into a horizontal twin-screw kneader of the type CPR 2.5 batch (List-AG Arisdorf), evaporating 980 g of water during 90 minutes under intensive shearing (screw speed 30/24 to 90/72 rpm) , increased bulk temperature (85 to 145 °C) and vacuum (800 to 10 mbar) produced a homogeneous concentrated solution composed of 16.5% by mass of cellulose and 83.5 % by mass of BMIMC1 (cellulose :BMIMC1 molar ratio // 1:4.67) having a zero shear viscosity of 72 560 Pa s, a relaxation time of 4.8 s at 85 °C and a temperature function as per In ή = -15.35831 + 9505*1/T Particle content of the solution was 33 ppm with a 61 % fraction The solution was spun in an laboratory equipment according to Figure 5. The requisite spinning solution amount mL was fed at 95 °C bulk temperature via a temperature-controlled tubular line at the same temperature to the spin pack by means of a spin pump (0.10 ml/revolution), filtered, heated in the heat exchanger to the spinning temperature 9S , relaxed in the inflow chamber with about 8 ml volume and pressed through dies containing 60 spinning capillaries having an L/DA ratio of 1 and an exit diameter of DA. The jets of solution passed while undergoing SVa drawing through the conditioned air gap of length a and were additionally quenched with 85 1/min of air at 25 °C and 2.5 g/m of water. The oriented sheet of yarn passed through the spin bath at a temperature of 20 °C while the cellulose was simultaneously coagulated, was separated from the coagulation bath at the withdrawal speed va at an angle (3 = 40 °, withdrawn via godet rolls and sent to the discontinuous aftertreatment. Spinning conditions and fiber properties are to be found hereinbelow in Tables 4 and 5. We claim: 1. A process for producing a shaped article of cellulose by dissolving cellulose in an ionic liquid, forming the viscous solution into a shaped article and regenerating the cellulose, which comprises a) cellulose or a cellulose mixture being dispersed in water by shearing to the individual fiber, pressed off and the press-moist cellulose or cellulose mixture being b) dispersed in the ionic liquid in the presence of basic substances, the water being removed under shearing, increasing temperature and decreasing pressure and converted into a homogeneous solution, c) feeding the solution through one or more temperature-controllable tubular lines and a pressure-equalizing apparatus to at least one spin pack, d) the solution in the spin pack passing through a filter, a distributor plate configured as a heat exchanger and the spinning capillary or capillaries or the slot of the spinneret die or dies, e) leading the solution jets which have been formed into filaments or a film through a conditioned gap with drawing, f) the oriented jets of solution being coagulated by treatment with a temperature-controlled solution which is miscible with the ionic liquid but constitutes a coagulant for the cellulose and, at the end of the coagulation bath sector, being separated from the coagulation bath by diversion or deflection, and g) the formed article in the form of filament yarn, fiber tow or film/membrane being withdrawn, subjected to a single or multiple stage coagulant wash, spin finished and dried or cut into staple fibers, spin finished and dried. The process according to claim 1 that utilizes chemical pulps from wood or cellulosic fibers from annual plants, such as cotton 1inters, produced by the sulfite, sulfate/prehydrolysis sulfate or organosolve process using elemental chlorine free (ECF) and/or total chlorine free (TCF) bleaching. The process according to claim 1 that utilizes celluloses of medium molar masse (cuoxam DP 400-800) in admixture with high molecular weight (cuoxam DP 800-3000) or low molecular weight (cuoxam DP 20-400) celluloses. The process according to claim 1 that utilizes 1,3-dialkylimidazolium halides as ionic liquid. The process according to claim 1 wherein the ionic liquid has added to it for stabilization, before and/or during the dissolving, basic substances of low vapor pressure in such an amount that the suspension of cellulose/aqueous ionic liquid has a pH > 8. The process according to claims 1 and 5 wherein the basic substances of low vapor pressure are alkali metal hydroxides. The process according to claim 1 wherein the spinning solution contains further stabilizers in the form of organic compounds having at least one conjugated double bond and two hydroxyl or amino groups, preferably hydroquinone, phenylenediamine, gallic esters or tannins. The process according to claim 1 wherein the ionic liquid consists of a recycled coagulation bath. The process according to claim 1 wherein the aqueous coagulation bath is subjected to a hot treatment with alkaline hydrogen peroxide solution, metal ions entrained are removed by ion exchangers and the ionic liquid is concentrated by distillation. The process according to claim 1 wherein the cellulose concentration and the molar mass of the cellulose or cellulose mixture are chosen such that at 85 °C a zero shear viscosity in the range from 1000 to 100 000 Pa s and preferably in the range from 1000 to 80 000 Pa s for the spinning solution and a relaxation time in the range from 0.5 to 90 s becomes established. The process according to claim 1 wherein the spinning solution does not attain the spinning temperature until passing through the distributor plate configured as a heat exchanger. The process according to claim 1 wherein the spinning solution is formed in spinning capillaries 0.4 to 5 mm in overall length (1), having a cylindrical portion (L = 0.5 - 3 D), a conical portion (1-L) and an outlet diameter (D) of 0.05 to 0.25 mm having a circularly round arrangement of the spinning capillaries for filament yarns and a rectangular arrangement of the spinning capillaries for fibers. The process according to claim 1 wherein the spinning solution is formed in slot dies 0.1 to 2.0 mm in thickness to form flat film or in circular slot dies 0.1 to 1.5 mm in gap width to form blown film. The process according to claim 1 wherein the sheet of filaments passing through the conditioned drawing zone is additionally subjected to a conditioned stream of gas. The process according to claim 1 wherein the surface area increase per unit time DO in the course of forming the cellulose solution in gap a satisfies the relation where T10 is the fiber fineness in dtex, va is the withdrawal speed in m/min, DA is the outlet diameter of the spinning capillary in cm, pL is the density of the spinning solution in g/cm and cCelli. is the cellulose concentration in % by mass. The process according to claim 1 wherein the rate of surface area increase van in gap a satisfies the relation where DOa is the surface area increase in cm /min and a is the gap length in cm. The process according to claim 1 wherein the filament yarn sheet passes through the coagulation bath and through an opening, in the floor of the coagulation bath container, which is formed by a yarn-guiding element, is separated from the coagulation bath stream by being diverted at an angle β The process according to claim 1 wherein the fiber tow filament sheet passes through the coagulation bath, is separated from the coagulation bath by being deflected over a rod or roller at an angle > 90 and is transported over a pair of godet rolls, The process according to claim 1 wherein the flat film is led through the coagulation bath over a roll, is deflected at an angle of > 90 ° using that roll and is separated from the coagulation bath and transported over a second roll. Apparatus for producing cellulose fibers or filament yarns from chemical pulps and ionic liquids as a solvent (fig. 5), consisting of a temperature controllable tubular line (1) and pressure-equalizing apparatus (2) • a spin pack (3), solution filter (4), temperature controllable heat exchanger (5) with seals (8), inflow chamber (6) and spinneret die (7) • a drawing zone (9) with gas supply/distribution (10) • a coagulation bath (11) with inflow chamber (12) , overflow (13), yarn-guiding element/floor opening (14), receiving trough (15), pump (16) and thermostat (17) and • a withdrawal godet roll (18) . 21. Apparatus for producing cellulose fibers or films from chemical pulps and ionic liquids as a solvent (fig. 6), consisting of • a rectangular spinneret die (7), • a drawing zone (9) with gas supply/distribution (10) • a coagulation bath (11) with inflow chamber (12), overflow (13), deflecting roller (14), receiving trough (15), pump (16) and thermostat (17) and • two godet rolls (18) . 22. Apparatus according to claim 18 or 19 (fig. 7) wherein the heat exchanger (5) consists of • nickelized or chromed aluminum, copper or brass • a well, closed off by seals (8), for receiving the filter pack (4) • a separate heating system (H) • and the flow channels (R). 23. Apparatus according to claim 18 wherein the volume V in cm3 of the inflow chamber (6) between the heat exchanger (5) and the spinneret die (7) satisfies the relation v = vL-K (') where V^ is the volume stream of the cellulose solution in cm3/s and λm is the relaxation time at the frequency maximum of the relaxation time spectrum of the spinning solution. Dated this 26 day of December 2006

Full Text

METHOD AND DEVICE FOR THE PRODUCTION OF MOLDED
CELLULOSE BODIES
This invention relates to a process for producing shaped articles of cellulose using ionic liquids, in particular 1,3-dialkylimidazolium halides, as a solvent, which process comprises dissolving the cellulose, forming the solution into fibers or films/membranes, regenerating the cellulose by coagulating in aqueous solutions, removing the solvent by washing and drying the formed articles.
To form cellulose, which is an infusible polymer, into filaments, fibers or films/membranes under industrial conditions, three different solution spinning processes have been developed to a point of technical maturity, namely the spinning of stable derivatives, for example secondary acetate rayon, dissolved in acetone without regeneration (acetate process - Ullmann's Encyclopedia Weinheim: VCH-Verlagsgesellschaft 198 6 Vol. A5 pp. 438-448), the spinning of semistable derivatives, for example cellulose xanthate, dissolved in caustic soda with regeneration (Gotze K. "Chemiefasern nach dem Vis-koseverfahren" Berlin/Heidelberg/New York: Springer Verlag 1967), and the spinning of solutions of cellulose and amine oxide hydrates and regeneration by coagulating the cellulose in aqueous amine oxide solutions [Lyocell process - Woodings C. "Regenerated Cellulose Fibres" Woodhead Publishing Ltd. Cambridge 2001; DE-A 29 13 589 and 28 48 471, US-A 4 246 221].
It is further known to dissolve cellulose in "chelate"-forming metal complexes, for example in copper tetramine hydroxide (cuoxam), copper ethylenediamine (cuen) , nickel tris(2-aminoethyl)amine (nitren), zinc diethyltriamine; dime thylacetamide/lithium chloride

[Klufers P. "Which metals form complexes with cellulose dianions" paper presented in German to a DFG meeting at Bad Herrenalb March 16, 1999] . These solvents have found broad analytical interest, but hitherto no industrial application apart from coppertetramine hydroxide for spinning cuprammonium rayon.
Although ionic liquids have been known since 1914, it is only very recently that they achieved importance as a solvent or reaction medium for many syntheses. Of particular interest are compounds having a positive nitrogen atom such as the ammonium, pyridinium and imidazolium cation [Schilling G. "Ionische Flussigkeiten" GIT Labor-Fachzeitschrift 2004 (4) 372-373] .
It is known from WO 03/02932 9 and US-A 2003/0157 351 that certain ionic liquids, consisting predominantly of cyclic nitrogen cations and halogen anions, dissolve cellulose in the absence of water and at elevated temperature and reprecipitate the cellulose on addition of water. The cellulose solution is produced by dissolving dry cellulose in substantially anhydrous ionic liquids by supply of energy, for example by heating with microwaves. Nothing is said about the properties of the starting and regenerated celluloses, of the cellulose solution and the possible conditions under which the cellulose solution might be formed into articles.
Positive factors favoring the use of ionic liquids as a solvent for forming cellulose into filaments, fibers and films/membranes are a possible higher thermal stability compared with amine oxide hydrates and also a significantly better environmental compatibility compared with the viscose, acetate and copper process.

Ionic liquids used as a solvent should permit operation in a closed-loop solvent cycle or circuit.
It is an object of the present invention to provide a process whereby cellulose (chemical pulp, bleached elemental chlorine free ECF or total chlorine free TCF) is formed into filaments, fibers and films/membranes with substantial preservation of molecular parameters in a simple, consistent and environmentally friendly operation, and also corresponding apparatus. This process and apparatus shall make it possible to produce formed articles of cellulose having novel and/or improved properties.
We have found that this object is achieved by a process for producing a formed article of cellulose by dissolving cellulose in an ionic liquid, forming the viscous solution into a formed article and regenerating the cellulose, which comprises
a) cellulose or a cellulose mixture being dispersed in water by shearing to the individual fiber, pressed off and the press-moist cellulose or cellulose mixture being
b) dispersed in the ionic liquid in the presence of basic substances and optionally further stabilizers, the water being removed under shearing, increasing temperature and decreasing pressure (from about 800 to 850 mbar to about 10 to 30 mbar) and converted into a homogeneous solution,
c) feeding the solution through one or more temperature-controllable tubular lines and a pressure-equalizing apparatus to at least one spin pack,
d) the solution in the spin pack passing through a

filter, a distributor plate preferably configured as a heat exchanger and the spinning capillary or capillaries or the slot of the spinneret die or dies,
e) leading the solution jets which have been formed into filaments or a film through a conditioned gap with drawing,
f) the oriented jets of solution being coagulated by treatment with a temperature-controlled solution which is miscible with the ionic liquid but constitutes a coagulant for the cellulose and, at the end of the coagulation bath sector, being separated from the coagulation bath by diversion or deflection, and
g) the formed article in the form of filament yarn, fiber tow or film/membrane being withdrawn, subjected to a single or multiple stage coagulant wash, optionally spin finished and dried or cut into staple fibers, spin finished and dried.
Preferably, the spinning solution does not attain the spinning temperature until passing through the distributor plate configured as a heat exchanger.
In a preferred embodiment of the process of the present invention, the spinning solution is formed in spinning capillaries 0.4 to 5 mm in overall length (1), having a cylindrical portion (L = 0.5 - 3 D) , a conical portion (1-L) and an outlet diameter (D) of 0.05 to 0.25 mm having a circularly round arrangement of the spinning capillaries for filament yarns and a rectangular arrangement of the spinning capillaries for fibers.
The spinning solution is advantageously formed into a flat film using a broad slot die having a gap width of 0.1 to 2.0 mm in thickness. Blown films are suitably

produced using annular slot dies having a gap width of about 0.1 to 1.5 mm.
The dispersing and dissolving of dry cellulose, without prior inclusion of costly and inconvenient grinding processes, in anhydrous ionic liquids, for example in l-butyl-3-methylimidazolium chloride, does not lead to a nodule-free suspension nor, even after very long dissolving times, to a homogeneous solution that meets the requirements of a spinning operation. Finely ground cellulose is very bulky, does not flow freely, and is prone to deflagrations in the presence of air. It has further emerged that this way of dissolving the cellulose is associated with a significant degradation in molar mass. A spruce sulfite pulp having a cuoxam DP of 550 prior to dissolving by microwave heating was found to give a cellulose having a cuoxam DP of 172 after regeneration from the solution. Spinning such solutions into fibers is not possible.
The process of the present invention is capable of utilizing chemical pulps from wood or cellulosic fibers from annual plants, in particular cotton 1inters, produced by the sulfite, sulfate/prehydrolysis sulfate or organosolve process using elemental chlorine free (ECF) and/or total chlorine free (TCF) bleaching. Preference is given to using mixtures of celluloses having a medium molar mass (cuoxam DP 400-800) in admixture with high molecular weight (cuoxam DP 800-3000) or low molecular weight (cuoxam DP 20-400) celluloses.
Preferred ionic liquids are melts of 1,3-dialkyl-imidazolium halides. The ionic liquid has added to it for stabilization, before and/or during the dissolving, basic substances of low vapor pressure in such an

amount that the suspension of cellulose/aqueous ionic liquid has a pH of 8 or more. The basic compound having a low vapor pressure is particularly preferably an alkali metal hydroxide, such as KOH or NaOH.
In the process of the present invention, the pulp is beaten up to the individual fiber by vigorous shearing in water. After pressing off, there is a swollen cellulose containing about 50 % by mass of water. The press-moist cellulose can easily be converted, for example in aqueous 1-butyl-3-methylimidazolium chloride which concurrently contains sufficient alkali metal hydroxide as to produce a pH > 8, into a homogeneous suspension which by shearing, temperature increase and pressure reduction after distillative removal of the water transitions into a homogeneous spinning solution. Under these conditions, the dissolving time is only a fraction of that required to dissolve dry cellulose in anhydrous l-butyl-3-methylimidazolium chloride. Molar mass degradation is below 10 %. Spinning solution quality can be characterized similarly to the Lyocell process by determination of particle content cppm and the class width specific particle distribution [q3x = f (x)] by laser diffraction (see Kosan B. Michels Ch. Chemical Fibers International 48 (1999) 4 pp. 50-54] and also of zero shear viscosity Ή 9 and relaxation
time XBm [see Michels Ch. Das Papier 52 (1998) 1 pp.
3-8]. In practice, these solutions have relaxation time spectra [H = f (A) ] , since the cellulose has a molar mass distribution. λ&m is then the relaxation time at
the frequency maximum in the weighted relaxation time spectrum [H*A = f(A) ] . In contradistinction to cellulose/amine oxide hydrate solutions, cellulose solvation in 1-butyl-3-methylimidazolium chloride or 1-ethyl-3-methylimidazolium chloride proceeds distinctly more slowly and the attainment of minimum

zero shear viscosity (complete solvation) is significantly more dependent on dissolving temperature and dissolving time.
The temperature function of zero shear viscosity and relaxation time is given by the relation (1)
(1)
Its knowledge is of significant importance for forming highly elastic solutions in the spinneret die channel and gap.
Cellulose concentration and cellulose or cellulose mixture molar mass are advantageously so chosen that a zero shear viscosity of 1000 to 100 000 Pass and preferably of 10 000 to 80 000 Pa s becomes established at 85 °C for the spinning solution.
Molar mass stability for a prolonged period at elevated temperature benefits from the addition of antioxidants as well as of bases. Antioxidants are in particular organic compounds having at least one conjugated double bond and two hydroxyl or amino groups, such as hydroquinone, p-phenylenediamine, gallic esters, tannins and the like. As is evident from DTA/DSC and reaction-calorimetrie measurements, thermal stability of spinning solutions according to the present invention is significantly higher than that of stabilized Lyocell spinning solutions. Whereas stabilized cellulose/amine oxide hydrate solutions represent a risk of explosive decomposition at above 130 °C, 1-butyl-3-methylimidazolium chloride is stable up to 250 °C at least and, in the stabilized spinning solution, cellulose starts to decompose at above 213 °C.

The forming of the solution into filaments, fibers and films/membranes is effected in a modified dry-jet wet-spinning process by the solution being fed via a temperature-controllable tubular line and pressure-equalizing apparatus to the spin pack at dissolving temperature 9L , being forced therein to a safety
spinning filter, adjusted in a temperature-controllable
heat exchanger to the requisite spinning temperature 9sp, allowed to relax in accordance with the solution's
relaxation time λ9m at the spinning temperature, formed
through spinneret dies into filaments or films and
being led through a gap to the coagulation bath while
undergoing drawing. Between the heat exchanger outlet
and the spinning capillaries there should remain a
volume V in cm3 which is not less than the product of volume stream vL in cm3/s and relaxation time Km in s
at the spinning temperature.
(2)
In the gap, which consists of a conditioned zone, the filament sheet is subjected - perpendicularly to its direction of transport and in a sheetlike manner - to a flow of conditioned air at preferably 15 to 25 °C and 20 to 80 % relative humidity.
Filament formation can be represented as a two-stage operation. The solution jet undergoes, predominantly under the influence of the shearing stress rD, at constant temperature, a narrowing in the spinning capillary from the spinning capillary's entry cross section AE to the exit cross section AAr i.e., the draw in the die SVD follows from
(3)
DE and DA correspond respectively to the entry and exit

filament consolidation in the gap should be associated with disruptions in the fiber sheath and has an adverse effect on the fibrillation characteristics of the fibers. In addition, the jets of solution are highly hygroscopic, take up water from the conditioned environment, and a partial coagulation of the cellulose takes place in the edge zones.
It has been determined in relation to the process of the present invention that very good fiber properties are achieved when the surface area increase ∆Oa attains
values Surface area increase normalized to the gap a = 1 is a further important parameter.

surface area increase is a measure of the rate of
surface area change and should be as small as possible. Good fiber properties are obtained at values van mm/min, and in particular at van The conditioning of the gap, preferably by means of air of defined temperature and humidity, as well as providing a cooling and stabilizing effect to the moving yarn, results in a partial precipitation of the cellulose, preferentially in the edge zones of the filaments. This enhances spinning consistency, in particular at high capillary densities, promotes the formation of a core-sheath structure, and improves fiber properties. As it passes through the conditioned drawing zone, the filament sheet is preferably additionally subj ected to a likewise conditioned stream of gas.

In the process of the present invention, the oriented jets of solution are routed through an aqueous coagulation bath containing up to 50 % by mass or preferably up to 25 % by mass of the ionic liquid used for dissolving, to regenerate the cellulose.
We have further found that when for example 1,3-dialkylimidazolium halides are used as a solvent, the slightly brown coagulation bath can be decolorized by treatment with alkaline hydrogen peroxide at 60 to 80 °C and the cations entrained by the pulp or other, ancillary products can be removed via cation exchangers. The coagulation bath thus cleaned or purified can be returned into the circuit as a solvent after it has been concentrated by distillation.
The process of the present invention and the apparatus will now be elucidated by reference to drawings and by examples, where
Figure 1 shows a graphical depiction of the particle
size distribution of a typical cellulose/-1-butyl-3-methylimidazolium chloride spinning solution containing 11.5 % by mass of cotton linters pulp;
Figure 2 shows a graphical depiction of the weighted
relaxation time spectrum of a spinning solution containing 12.5 % by mass of eucalyptus prehydrolysis sulfate pulp at 85 °C;
Figure 3 shows a graphical depiction of the
temperature function of zero shear viscosity and relaxation time for the spinning solution according to Figure 2;
Figure 4 shows the DSC-determined enthalpy as a
function of the temperature for 1-butyl-

3-methylimidazolium chloride and for a spinning solution containing 12 % by mass of spruce sulfite pulp and 1-butyl-3-methylimidazolium chloride as solvent;
Figure 5 shows the schematic depiction of an apparatus
for carrying out the process for producing filament yarns and fibers;
Figure 6 shows the schematic depiction of a preferred
apparatus for producing fibers and films;
Figure 7 shows a schematic depiction of the
distributor plate configured as a heat exchanger.
Figure 1 shows the density distribution q3*(x) determined by laser distribution against the particle size in µm for a spinning solution stabilized with 0.22 % by mass of NaOH (based on the solvent), consisting of 11.5 % by mass of cotton linters pulp (cuoxam DP 650) and 88.5 % by mass of 1-butyl-3-imidazolium chloride and having a zero shear viscosity of 31 650 Pa s and a relaxation time of 5.3 s at 85 °C. The particle content of 20 ppm divides into 81 % Figure 2 shows the weighted relaxation time spectrum (H*A) = f (A) for a spinning solution stabilized with 0.22 % by mass of NaOH and 0.04 % by mass of propyl gallate (based on the solvent), composed of 12.5 % by mass of a eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569) and 87.5 % by mass of 1-butyl-3-methylimidazolium chloride and having a zero shear viscosity of 27 010 Pa s and a relaxation time of 9.5 s at 85 °C. Particle content was 22 ppm with a 40 % fraction
Figure 3 contains the temperature function of zero shear viscosity and relaxation time (at the frequency maximum) in the temperature range 70-130 °C for the spinning solution in Figure 2. Comparison of the spinning solutions in figures 1 to 3 illustrates the influence of pulp provenience, molar mass (cuoxam DP), cellulose concentration, stabilization and temperature on zero shear viscosity, relaxation time and solution state.
Figure 4 shows the results relating the thermal analysis of the solvent 1-butyl-3-methylimidazolium chloride and of a stabilized spinning solution composed of 12 % by mass of eucalyptus prehydrolysis sulfate pulp and 88 % by mass of l-butyl-3-methylimidazolium chloride. While the solvent has no changes up to 250 °C besides the endothermic melting peak, the spinning solution curve contains an exothermic peak starting at 213 °C as well as the endothermic melting peak. The exothermic peak starting at 213 °C evidently marks the onset of the thermal degradation of the cellulose.
Figure 5 shows a spinning appliance for carrying out the process of the present invention. The spinning appliance consists of a temperature-controllable tubular line (1) , pressure-equalizing apparatus (2) , spin pack (3), drawing zone (9), coagulation bath (11) and withdrawal godet roll (18) . The spin pack (3) comprises a distributor plate which is configured as a heat exchanger (5) and comprises a solution filter (4), an inflow chamber (6) and at least one spinneret die
(7). Situated between the spin pack (3) and the coagulation bath (11) is the conditioned drawing zone
(9) with gas supply/distribution (10), the length of which is adjustable through vertical movement of the

coagulation bath (11) • The coagulation bath container (11) comprises the inflow chamber (12) for forming a laminar coagulation bath current, the overflow (13), the floor opening (14) confined by a yarn-routing element consisting of ceramic, the receiving trough (15) , coagulation bath pump (16) and thermostat (17) . The yarn-guiding element in the floor opening (14) and the withdrawal godet roll (18) are used to separate the filament bundle (19) from the coagulation bath (11) by withdrawing at an angle (3, which is preferably less than 70 °.
Figure 6 shows a spinning apparatus which is preferably used for spinning fibers and films. The construction up to the spinneret die (7) substantially corresponds to that of figure 5. Here the spinneret die (7) forms a rectangle and contains rowed spinning capillaries or a slot for spinning films. The conditioned drawing zone (9) and the gas supply/distribution (10) are adapted to this rectangular shape. The length of the drawing zone (9) is adjusted by vertical displacement of coagulation bath (11). As indicated by the dotted line, the drawing zone (9) is substantially enclosed. Opposite the gas supply/distribution (10) , openings for conducting away the conditioned quench gas are arranged. The coagulation bath (11) is again formed from inflow or calming chamber (12), overflow (13), deflecting roller or roll (14), receiving trough (15), pump (16) and thermostat (17) . Yarn sheet (19) and coagulation bath (11) are separated by deflecting at an angle > 90 and withdrawal via the pair of godet rolls (18). When films are spun, a driven roll (14) performs the task of deflection and further guiding rollers become responsible for the transportation to the pair of godet rolls (18) .

Figure 7 shows in schematic form the construction of the distributor plate configured as a heat exchanger
(5) and comprising solution filter (4) , seals (8) and
heaters (H) . The spinning solution at temperature Tl
(9) passes through the solution filter (4), flows
through a multiplicity of bores (R) while concurrently heating up to the spinning temperature T2 (9p) and
passes at this temperature through the inflow chamber
(6) and the die (7). The heat exchanger (5) preferably
consists of nickelized or chromed aluminum, copper or
brass. It further advantageously comprises a hollow,
closed off by seals (8), for receiving the filter pack
(4), a separate heating system (H) and flow channels
(R) .
Examples 1 to 7
A spruce sulfite pulp (cuoxam DP 550; ECF bleached) was beaten up in water at a liquor ratio of 20:1 and was dewatered by pressing off to 40 % by mass. Dispersion of 75 g of press-moist cellulose in 275 g of 1-butyl-3-methylimidazolium chloride (BMIMC1) with 20 % by mass of water and stabilizing additives as indicated in Table 1 gave 350 g of homogeneous suspension which after introduction into a vertical kneader was converted into a homogeneous solution under vigorous shearing, gradually rising temperature from 85 to 120 °C and decreasing pressure from 850 to 20 mbar by complete removal of water. The dissolving time was a uniform 60 minutes. The solution with 12 % by mass of cellulose and 88 % by mass of BMIMC1 (refractive index 1.5228 at 50 °C) was investigated immediately after dissolving and after spinning (corresponds to 2 0 hours at 85 °C). The results are given in Table 1.

The addition of alkali led to a significant stabilization of the cellulose. Evidently, the BMIMC1 detaches traces of hydrochloric acid at high temperature and they led to cleavage of the 1,4-acetal bond of the cellulose. The addition of a small amount of radical scavengers as in Examples 5 to 7 provided a further improvement in the thermal long-term stability of the spinning solutions.
Example 8
37 5 g of eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569; TCF bleached) were beaten up in water in a liquor ratio of 15:1 in a jet stream mixer, separated from the liquor via a centrifuge down to 50 % by mass, coarsely comminuted and dispersed press-moist in 3088 g of l-butyl-3-imidazolium chloride (BMIMC1) with 15 % by mass of water also containing 0.22 % by mass of sodium

hydroxide and 0.036 % by mass of propyl gallate. Introducing the suspension into a vertical kneader, evaporating 838 g of water during 60 minutes under vigorous shearing, elevated temperature (85 to 130 °C) and vacuum (800 to 15 mbar) produced a homogeneous solution composed of 12.5 % by mass of cellulose and 87.5% by mass of BIMIMC1 and having a zero shear viscosity of 32 680 Pa s, a relaxation time of 9.8 s at 85 °C and a temperature function as per
In ήo = 16.9874 + 9799* 1/T
Particle content of the solution was 18 ppm with 65 % The solution was spun in an experimental machine according to Figure 5. The requisite spinning solution amount mL was fed at 85 °C bulk temperature via a
temperature-controlled tubular line at the same
temperature to the spin pack by means of a spin pump
(0.10 ml/revolution), filtered, heated in the heat exchanger to the spinning temperature 9 , relaxed in
the inflow chamber with about 8 ml volume and pressed through dies containing 30 or in the case of trial # 7.12, 60 spinning capillaries having an L/DA ratio of 1 or, in the case of trial # 5.3, of 2 and an exit diameter of DA. The jets of solution passed while undergoing SVa drawing through the conditioned air gap of length a and were additionally quenched with 25 (fibers) or 100 1/min (filament yarn) of air at 25 °C and humidity according to table. The oriented sheet of yarn passed through the spin bath at a temperature of 20 °C while the cellulose was simultaneously coagulated, was separated from the coagulation bath at the withdrawal speed va at an angle (3 = 4 0 °, withdrawn via godet rolls and sent to the af tertreatment. The aftertreatment was carried out batchwise and

tensionlessly for the fiber samples, whereas in the case of filament yarn (trial # 7.12) it was carried out continuously under minimal tension ( Spinning conditions and also fiber and filament yarn properties are recited hereinbelow in Tables 2 and 3. Table 2 also shows the computed surface area increase AOa and also the rate van of surface area increase.

exhaustively described by Mieck K.P. et al. in Melliand Textilberichte 7 4 (1993) 945 and Lenzinger Berichte 74 (1994) 61-68.
Cuoxam DP was 531 for the dissolved cellulose and 52 9 for the fiber. Fiber properties comprised high tenacities and moduli in the conditioned and wet states and also an elevated wet abrasion resistance compared with Lyocell fibers.
Example 9
A cotton 1inters pulp (cuoxam DP 650) was converted similarly to Example 8 into a spinning solution having 11.5 % by mass of cellulose, a zero shear viscosity of 31 650 Pa s at 85 °C, a relaxation time of 5.3s at 85 °C, a particle content of 20 ppm, particles
Pump rate Diameter DA Spinning temperature Draw ratio SVa Air gap
Relative humidity Spin bath Withdrawal speed

1.35 g/min
100 Vim (30 capillaries)
100 °C
9.3
12 mm
7.5 g,0
20 °c
50.2 m/min

Fibers were obtained having very high tenacities and moduli in the conditioned and wet states:

Fineness
Tenacity conditioned
wet Elongation at break conditioned
Initial modulus
Wet abrasion resistance Fiber cuoxam DP

wet
conditioned
wet

1.27 dtex
67.7 cN/tex
60.9 cN/tex
9.0 Q.
8.8 Q.
1366 cN/tex
511 cN/tex
43 cycles
624

Example 10
A mixture of 85 % by mass of beech prehydrolysis sulfate pulp (cuoxam DP 390; TCF bleached) and 15 % by mass of spruce sulfite pulp (cuoxam DP 780; ECF bleached) was conjointly beaten up in water to the individual fiber using a jet stream mixer and separated from the liquor via a screen belt press. 1020 g of the press-moist cellulose having a water content of 52 % by mass were intensively mixed in 3478 g of BMIMC1 with 15 % by mass of water which concurrently contained 0.22 % of sodium hydroxide and 0.036 % of propyl gallate, in a vertical kneader, and under shearing, elevated

temperature (85/130 °C) and vacuum (700/20 mbar) 1044 g of water were distilled off during 60 minutes and subsequently dissolved for 60 minutes. The solution formed contained 14.0 % by mass of cellulose having a cuoxam DP of 465 for the dissolved cellulose. Zero shear viscosity at 85 °C was 13 100 Pa s, relaxation time was 5.5 s. Particle analysis revealed a 28 ppm content with a particle size distribution of 82 % 40 pm. A machine according to Figure 6 was 'used to spin the solution. A spin pump carried 19.1 g/min of spinning solution at 90 °C into the spin pack, which is filtered through a screen filter (mesh size 25 µm), heated up to 110 °C in the heat exchanger and pressed through a rectangular die containing 900 spinning capillaries (arranged over an area of 1 x 3 cm) having an exit diameter of 75 pm. The sheet of filament passed while being drawed to a ratio of 5.1 through the conditioned gap 2.8 cm in length, and was quenched over a width of 9 cm with 160 1/min of air at 23 °C and 70 % relative humidity. Surface area increase during drawing was 0.128 cm2/min + filament, its rate was 0.46 mm/min.
After cellulose coagulation in the spin bath at 23 °C and deflection, the filament sheet arrived at a pair of godet rolls at a withdrawal speed of 22 m/min. Cutting of the tow of fiber into staple 40 mm in length, washing and finishing was followed by drying at 90 °C down to a residual moisture content of 10 % by mass. The following values were obtained for the mechanical fiber properties:

1.50 dtex
44.1 cN/tex
40.0 cN/tex
12.1
12.0 o
32.2 cN/tex
920 cN/tex
340 cN/tex
130 cycles
Fineness
Tenacity conditioned Tenacity wet
Elongation at break conditioned Elongation at break wet Loop tenacity conditioned Modulus conditioned Modulus wet WAR Example 11
A mixture of cotton linters pulps (80 % by mass of cuoxam DP 4 65 and 20 % by mass of cuoxam DP 650) were prepared similarly to Example 9. The press-moist cellulose mixture had a water content of 45 % by mass. In a horizontal single screw mixing/kneading reactor of the type Diskotherm B (LIST AG ARISDORF Switzerland), in the first shearing zone, continuously, 819 g/min of preheated 1-ethyl-3-methylimidazolium chloride (EMIMC1), containing 10 % by mass of water, 0.28 % of sodium hydroxide and 0.04 % of tannin, at 90 °C were metered via a precision gear pump and 200 g/min of comminuted cellulose via a belt scale and valveless plunger metering pump, mixed and heated up to 120 °C under a vacuum of 30 mbar and 172 g/min of water were distilled off. The pale yellow homogeneous solution produced in the second shearing zone contained 13 % by mass of cellulose (zero shear viscosity 11 450 Pa s at 85 °C) and was cooled to 110 °C and fed by a vertical double screw conveyor to a wide film laboratory plant. It corresponded in construction to the arrangement in Figure 6. 847 g/min of spinning solution were fed via a pressure-equalizing apparatus and precision gear pump to the spin pack, filtered, homogenized to 110 °C in the heat exchanger and pressed through a film die 100 mm in slot width and 1.2 mm in slot thickness. The

100 mm in slot width and 1.2 mm in slot thickness. The solution formed into flat film was drawed to a ratio of 3.2 while passing through a conditioned air gap (20 °C; 55 % relative humidity) 15 mm in length, arriving in the coagulation bath (an EMIMCl-containing aqueous solution), deflected via a driven roll and attracted by the two rolls at 20 m/min. Washing, drying and finishing gave a conditioned film 40 µm in thickness and 61 g/m in mass per unit area. The longitudinal tensile strength of the film was 27.2 cN/tex, its longitudinal elongation was 16.8 %.
Example 12
234 g of eucalyptus prehydrolysis sulfate pulp (cuoxam DP 569; TCF bleached) were beaten up in water in a liquor ratio of 25:1 using an ultra-mixer, adjusted to pH 10 with sodium hydroxide, separated from the liquor by pressing off to 26.7 % by mass, coarsely comminuted and dispersed press-moist in 1520.5 g of 1-butyl-3-methylimidazolium chloride (BMIMC1) containing 22 % by mass of water, 1.4 g of sodium hydroxide and 1.2 g of propyl gallate.
Introducing the suspension (2400 g) into a horizontal twin-screw kneader of the type CPR 2.5 batch (List-AG Arisdorf), evaporating 980 g of water during 90 minutes under intensive shearing (screw speed 30/24 to 90/72 rpm) , increased bulk temperature (85 to 145 °C) and vacuum (800 to 10 mbar) produced a homogeneous concentrated solution composed of 16.5% by mass of cellulose and 83.5 % by mass of BMIMC1 (cellulose :BMIMC1 molar ratio // 1:4.67) having a zero shear viscosity of 72 560 Pa s, a relaxation time of 4.8 s at 85 °C and a temperature function as per
In ή = -15.35831 + 9505*1/T

Particle content of the solution was 33 ppm with a 61 % fraction The solution was spun in an laboratory equipment according to Figure 5. The requisite spinning solution amount mL was fed at 95 °C bulk temperature via a
temperature-controlled tubular line at the same
temperature to the spin pack by means of a spin pump
(0.10 ml/revolution), filtered, heated in the heat exchanger to the spinning temperature 9S , relaxed in
the inflow chamber with about 8 ml volume and pressed through dies containing 60 spinning capillaries having an L/DA ratio of 1 and an exit diameter of DA. The jets of solution passed while undergoing SVa drawing through the conditioned air gap of length a and were additionally quenched with 85 1/min of air at 25 °C and 2.5 g/m of water. The oriented sheet of yarn passed through the spin bath at a temperature of 20 °C while the cellulose was simultaneously coagulated, was separated from the coagulation bath at the withdrawal speed va at an angle (3 = 40 °, withdrawn via godet rolls and sent to the discontinuous aftertreatment. Spinning conditions and fiber properties are to be found hereinbelow in Tables 4 and 5.

We claim:
1. A process for producing a shaped article of cellulose by dissolving cellulose in an ionic liquid, forming the viscous solution into a shaped article and regenerating the cellulose, which comprises
a) cellulose or a cellulose mixture being dispersed in water by shearing to the individual fiber, pressed off and the press-moist cellulose or cellulose mixture being
b) dispersed in the ionic liquid in the presence of basic substances, the water being removed under shearing, increasing temperature and decreasing pressure and converted into a homogeneous solution,
c) feeding the solution through one or more temperature-controllable tubular lines and a pressure-equalizing apparatus to at least one spin pack,
d) the solution in the spin pack passing through a filter, a distributor plate configured as a heat exchanger and the spinning capillary or capillaries or the slot of the spinneret die or dies,
e) leading the solution jets which have been formed into filaments or a film through a conditioned gap with drawing,
f) the oriented jets of solution being coagulated by treatment with a temperature-controlled solution which is miscible with the ionic liquid but constitutes a coagulant for the cellulose and, at the end of the coagulation bath sector, being separated from the coagulation bath by diversion or deflection,

and g) the formed article in the form of filament yarn, fiber tow or film/membrane being withdrawn, subjected to a single or multiple stage coagulant wash, spin finished and dried or cut into staple fibers, spin finished and dried.
The process according to claim 1 that utilizes chemical pulps from wood or cellulosic fibers from annual plants, such as cotton 1inters, produced by the sulfite, sulfate/prehydrolysis sulfate or organosolve process using elemental chlorine free (ECF) and/or total chlorine free (TCF) bleaching.
The process according to claim 1 that utilizes
celluloses of medium molar masse (cuoxam DP
400-800) in admixture with high molecular weight
(cuoxam DP 800-3000) or low molecular weight
(cuoxam DP 20-400) celluloses.
The process according to claim 1 that utilizes 1,3-dialkylimidazolium halides as ionic liquid.
The process according to claim 1 wherein the ionic liquid has added to it for stabilization, before and/or during the dissolving, basic substances of low vapor pressure in such an amount that the suspension of cellulose/aqueous ionic liquid has a pH > 8.
The process according to claims 1 and 5 wherein the basic substances of low vapor pressure are alkali metal hydroxides.
The process according to claim 1 wherein the

spinning solution contains further stabilizers in the form of organic compounds having at least one conjugated double bond and two hydroxyl or amino groups, preferably hydroquinone, phenylenediamine, gallic esters or tannins.
The process according to claim 1 wherein the ionic liquid consists of a recycled coagulation bath.
The process according to claim 1 wherein the aqueous coagulation bath is subjected to a hot treatment with alkaline hydrogen peroxide solution, metal ions entrained are removed by ion exchangers and the ionic liquid is concentrated by distillation.
The process according to claim 1 wherein the cellulose concentration and the molar mass of the cellulose or cellulose mixture are chosen such that at 85 °C a zero shear viscosity in the range from 1000 to 100 000 Pa s and preferably in the range from 1000 to 80 000 Pa s for the spinning solution and a relaxation time in the range from 0.5 to 90 s becomes established.
The process according to claim 1 wherein the spinning solution does not attain the spinning temperature until passing through the distributor plate configured as a heat exchanger.
The process according to claim 1 wherein the spinning solution is formed in spinning capillaries 0.4 to 5 mm in overall length (1), having a cylindrical portion (L = 0.5 - 3 D), a conical portion (1-L) and an outlet diameter (D) of 0.05 to 0.25 mm having a circularly round

arrangement of the spinning capillaries for filament yarns and a rectangular arrangement of the spinning capillaries for fibers.
The process according to claim 1 wherein the spinning solution is formed in slot dies 0.1 to 2.0 mm in thickness to form flat film or in circular slot dies 0.1 to 1.5 mm in gap width to form blown film.
The process according to claim 1 wherein the sheet
of filaments passing through the conditioned
drawing zone is additionally subjected to a
conditioned stream of gas.
The process according to claim 1 wherein the surface area increase per unit time DO in the
course of forming the cellulose solution in gap a satisfies the relation

where T10 is the fiber fineness in dtex, va is the withdrawal speed in m/min, DA is the outlet diameter of the spinning capillary in cm, pL is the density of the spinning solution in g/cm and cCelli. is the cellulose concentration in % by mass.
The process according to claim 1 wherein the rate of surface area increase van in gap a satisfies
the relation

where DOa is the surface area increase in cm /min and a is the gap length in cm.
The process according to claim 1 wherein the

filament yarn sheet passes through the coagulation bath and through an opening, in the floor of the coagulation bath container, which is formed by a yarn-guiding element, is separated from the coagulation bath stream by being diverted at an angle β The process according to claim 1 wherein the fiber tow filament sheet passes through the coagulation bath, is separated from the coagulation bath by being deflected over a rod or roller at an angle > 90 and is transported over a pair of godet rolls,
The process according to claim 1 wherein the flat film is led through the coagulation bath over a roll, is deflected at an angle of > 90 ° using that roll and is separated from the coagulation bath and transported over a second roll.
Apparatus for producing cellulose fibers or filament yarns from chemical pulps and ionic liquids as a solvent (fig. 5), consisting of a temperature controllable tubular line (1) and pressure-equalizing apparatus (2)
• a spin pack (3), solution filter (4), temperature controllable heat exchanger (5) with seals (8), inflow chamber (6) and spinneret die (7)
• a drawing zone (9) with gas supply/distribution (10)
• a coagulation bath (11) with inflow chamber (12) , overflow (13), yarn-guiding element/floor opening (14), receiving trough (15), pump (16)

and thermostat (17) and
• a withdrawal godet roll (18) .
21. Apparatus for producing cellulose fibers or films
from chemical pulps and ionic liquids as a solvent
(fig. 6), consisting of
• a rectangular spinneret die (7),
• a drawing zone (9) with gas supply/distribution
(10)
• a coagulation bath (11) with inflow chamber
(12), overflow (13), deflecting roller (14), receiving trough (15), pump (16) and thermostat (17) and
• two godet rolls (18) .
22. Apparatus according to claim 18 or 19 (fig. 7)
wherein the heat exchanger (5) consists of
• nickelized or chromed aluminum, copper or brass
• a well, closed off by seals (8), for receiving
the filter pack (4)
• a separate heating system (H)
• and the flow channels (R).

23. Apparatus according to claim 18 wherein the volume
V in cm3 of the inflow chamber (6) between the heat
exchanger (5) and the spinneret die (7) satisfies
the relation
v = vL-K (')
where V^ is the volume stream of the cellulose solution in cm3/s and λm is the relaxation time at
the frequency maximum of the relaxation time spectrum of the spinning solution.
Dated this 26 day of December 2006

Documents:

4750-CHENP-2006 CORRESPONDE OTHERS 04-09-2012.pdf

4750-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 05-04-2013.pdf

4750-CHENP-2006 FORM-18.pdf

4750-CHENP-2006 POWER OF ATTORNEY 05-04-2013.pdf

4750-CHENP-2006 POWER OF ATTORNEY.pdf

4750-CHENP-2006 AMENDED PAGES OF SPECIFICATION 05-04-2013.pdf

4750-CHENP-2006 AMENDED CLAIMS 05-04-2013.pdf

4750-CHENP-2006 FORM-3 05-04-2013.pdf

4750-CHENP-2006 OTHER PATENT DOCUMENT 05-04-2013.pdf

4750-chenp-2006-abstract.pdf

4750-chenp-2006-claims.pdf

4750-chenp-2006-correspondnece-others.pdf

4750-chenp-2006-description(complete).pdf

4750-chenp-2006-drawings.pdf

4750-chenp-2006-form 1.pdf

4750-chenp-2006-form 3.pdf

4750-chenp-2006-form 5.pdf

4750-chenp-2006-pct.pdf

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Patent Number

256560

Indian Patent Application Number

4750/CHENP/2006

PG Journal Number

27/2013

Publication Date

05-Jul-2013

Grant Date

02-Jul-2013

Date of Filing

26-Dec-2006

Name of Patentee

THUERINGISCHES INSTITUT FUR TEXTIL-UND KUNSTSTOFFFORSCHUNG E V

Applicant Address

BRIETSCHEIDSTRASSE 97 D-07407 RUDOLSTADT GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	MICHELS CHRISTOPH	MARKSTRASSE 36 07407 RUDOLSTADT GERMANY
2	KOSAN BIRGIT	GUSTAV -LILIENTHAL-STRASSE 9 D-07407 RUDOLSTADT GERMANY
3	MEISTER FRANK	AUGUST-BEBEL-STRASSE 2A 07407 RUDOLSTADT GERMANY

PCT International Classification Number

D01D 4/06

PCT International Application Number

PCT/DE05/01118

PCT International Filing date

2005-06-23

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	102004031025.4	2004-06-26	Germany