FI107335B - Process for producing alkali-soluble cellulose and process for producing fibres, films and other products from soluble cellulose - Google Patents

Description

1 107335

This invention relates to the production of fibers, films and other products from soluble cellulose.

In Vysokomol. Sojed. Ser., Vol. 17 (8), p. 600, 1975 discloses a method for preparing a cellulose film from a solution of cellulose in trifluoroacetic acid at 25-35 ° C. However, this process produces a cellulose solution having a high degree of degradation and the solvent used is very toxic and difficult to regenerate.

15 From the Journal of Macromolecular Science - Review of Macromolecular Chemistry, Vol. C 18, p. 1, 1980, methods are known on a laboratory scale for the preparation of cellulose film and fibers from a solution of cellulose in hydrazine dissolved at 150-200 ° C and 200-345 kPa. Water bath spun membranes and fibers are characterized by high crystallinity. Until now, it has been impossible to apply the above method on a practical scale.

Further, it is known from the Journal of Polymer Science - Polymer 0 Chemical Education, Vol. 18, p. 3469, 1980, Journal of Polymer: 25 Science - Polymer Letter, Vol. 17, p. 479, 1979, Applied Polymer Symposium, Vol. 37, p. 261, 1983, Lenzinger Berichte, Fol. 59, p. 96, 1985, ···. Journal of the American Chemical Society, Vol. 64, p. 121, 1942, Tappi,

Butter. 57, p.86,1974, Chemtech, Vol. 7, p. 702, 1977, Chemical Industry, ly. Butter. 10, p. 296,1969, Cellulose Chemistry and Technology, Vol. 8,107, 30 P. 481, 1947, Vol. 9, p. 325, 1975, Vol. 11, p. 115, 1977, as well as U.S. Patent Nos. 3,236,669, 4,367,191, 4,073,660, 4,076,932, 4,096,933, 4,082,617, and 4,086,419, a number of anhydrous slides. · · «V: tricomponent systems for dissolving cellulose based on e.g. ammonia-ammonium rhodan, lithium chloride-dimethylacetam -. '··! 35, nitric oxide-dimethylformamide, nitric oxide-dimethylsulfoxide, N · [paraformaldehyde-dimethylsulfoxide, sulfur dioxide-dimethylformamide. Em. cellulose leaching systems degrade cellulose and the economic, ecological, technical and toxic aspects 2,107,335 at the same time cause difficulties in their practical application. Only a process using N-methylmorpholine oxide has been applied on an advanced scale to produce fibers under the trade name '' Tencel ''. Cellulose solutions of N-methylmorpholine oxides used for spinning contain 15-25% cellulose. The spinning of the cellulosic fibers is carried out in a water bath at 90-120 ° C using an extrusion system. Tencel cellulose fibers are characterized by the same properties as cotton fibers.

10 Also known in Textile Research Journal, No. 8, p. 501, 1989, a process for preparing cellulose fibers under the name Camilon. Cellulose is dissolved in dimethylformamide and a dicomponent mixture of N 2 O 4. The cellulose fibers are spun from the above solution at a spinning speed of 20-80 m / min, with a maximum spin nozzle loading of 250-350% in a spinning bath comprising dimethylformamide, water and an inorganic salt. The fibers obtained are characterized by a tensile strength of 15-25 cN / tex and an elongation of 15-20%. This method employs highly toxic, uneconomical and difficult to recover solvents, which present many difficulties for the environment. In addition, a method for producing cellulosic fibers and films of this polymer is known from "Man-made Fibers", Heywood Books, London, 1970, "Wlokna Chemizne", Warzawa, 1977 and from Textile Dyer Printer, Vol. 18, p. 150,1964. from a solution in Schweizer solvent, cupram-25 monium hydroxide, The concentration of cellulose is usually 8-: 10% by weight Cellulose fibers are spun into a water bath to obtain properties similar to viscose fibers.

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• o · • • • • • • »» ly. Further, is known in Textile Research Journal, No. 8, p. 501, 30 1989, a process for preparing cellulose fibers by spinning cellulose dissolved in an aqueous solution of zinc chloride.

♦ ♦ ·: Cellulose solution containing 5-8% by weight of polymer with an average polymerization degree of 330-400 spun to obtain cellulose fibers having a tensile strength of 16-25 cN / tex, elongation 17-20% and . ···. 35 tensile strength 14-15 cN / tex. However, dissolving cellulose in an aqueous solution of zinc chloride causes degradation of the polymer and also leads to: several difficulties. The solvent in question is toxic to the environment. ' · · To work and difficult to regenerate.

3, 107335

In addition, a method for making cellulose fibers from a solution of blasted cellulose is known from Japanese Patent Nos. 58-244337 and U.S. Patent 4,634,470. The above-mentioned cellulose is prepared by suitable (lapping or early pretreatment to obtain a product of average molecular weight 200-700 and blast treatment at 100-350 ° C and 10-250 atm. The resulting cellulose is dissolved in an alkaline aqueous solution, usually sodium hydroxide, lithium hydroxide or lithium hydroxide at a polymer concentration of 6 to 12% at 7 [deg.] C. After evaporation, the solution is used in 10 spin acid baths to provide cellulosic fibers with a structured molecular structure similar to those of viscose fibers.

Further, Japanese Patent Nos. 63-77951 and 63-35602 disclose a method for producing cellulose fibers and films by spinning a cellulose solution into an acid bath. The solution is prepared by dissolving pre-treated cellulose having an average degree of polymerization of 100-700 in aqueous sodium hydroxide containing 0.5-5.0% by weight of 20 urea, thiourea and their derivatives as compared to cellulose, or dithiocarboxylic acids such as dithiosalicylic acid or dithiopropionic acid below 10 ° C.

A: Also known from Japanese Patent No. 16-3008401, and in "Cellulose: Sources and Application", Elsevier Pub. Co., London, 1990, a method for preparing cellulose fibers from alkaline solution of cellulose. Cellulose is made from .y. enzymatic treatment of the pulp, the pulp having previously been subjected to an acid treatment at pH 3-6. The enzyme treatment uses hemisel-30 lulase, amylase, pectinase or dextranase at 40-60 ° C for 15 min to several hours.

M * v: The alkaline solution of the above cellulose is spun into an acid bath, usually containing sulfuric acid. The resulting cellulosic fibers have * ·. ···. 35 characterized by fibrillar structure. Known methods for producing cellulosic fibers and membranes require the use of complex multi-component solvents, which are very expensive, many of which i 4 10733E! methods have not been useful due to toxicity, explosion sensitivity and solvent recovery difficulties. It is extremely difficult to dissolve cellulose in a single solvent which is inexpensive. Other known methods employing cellulose detonation require complex equipment and extremely difficult conditions for the preparation of cellulose suitable for dissolution in an alkaline aqueous solution. At the same time, the known enzymatic preparation of cellulose requires suitable pretreatment to disintegrate the polymer, but its efficiency is not high because the enzymes used are not active in the statistical degradation and activation of cellulose by reducing the energy of hydrogen bonds between macromolecules. The fibers obtained by these known methods require special spinning conditions, but the properties of the fibers are not suitable for textile applications.

It is an object of the present invention to prepare fibers, films and other products from cellulose obtained by direct treatment of cellulose with enzymes such as cellulase of the Aspergillus niger IBT type. Soluble cellulose is mixed with aqueous solutions of alkali metal hydroxide 20 to obtain! a homogeneous solution of cellulose followed by degassing of the cellulose solution and optionally filtration followed by preparation of the cellulose fibers, film or other products such as microcrystalline cellulose by spinning an alkaline solution of cellulose in an acidic coagulation and neutralization bath to obtain clear cellulose fibers or membranes; the cellulose solution is blended in an acid: bath to form microcrystalline cellulose.

: 'Ύ— The cellulose products are then washed to neutral pH and possibly dried.

According to the present invention, the preparation of fibers, film, or other products from soluble cellulose comprises mixing soluble cellulose with aqueous solutions of alkali metal hydroxide, v: in particular with aqueous solutions of sodium hydroxide, particularly with solutions of sodium hydroxide or potassium hydroxide 5 to 15% by weight of conc. 35 sensitization, especially at a concentration of 7-12 wt%, at -10 ... + 10 ° C.

In a patient, especially at -5 ° C to 0 ° C, for 15 min to 48 hours, particularly for 30 min to 2 hours, to obtain a homogeneous V · solution of cellulose at a concentration of at least 0.1 wt%, in particular 3-8 wt%, after which the alkaline solution of cellulose is degassed and optionally filtered to provide a cellulose spinning solution which is spun into an acid bath to form cellulose fibers, film or other products.

5

According to a suitable embodiment of the process of the invention, the cellulose in the alkali solution is characterized by an average degree of polymerization of at least 100 and preferably 300-600%, in particular 50-100% water retention value and hydrogen bonding energy of 10 especially up to 16 kJ / mol. -15 kJ / mol.

According to a suitable embodiment of the process of the invention, the alkaline cellulose solution is spun into an acidic coagulation and neutralization bath containing an aqueous solution of inorganic or organic acids, in particular sulfuric or acetic acid, at a concentration of at least 10 g / l and preferably 100-200 g / l. optionally, inorganic or organic salts are added, in particular sodium aluminum sulfate at a concentration of at least 1 g / l and preferably 10-100 g / l, and the resulting cellulosic fibers or film are finalized by washing to obtain a neutral pH and dried.

According to a suitable embodiment of the process of the invention, a basic cellulose solution having a cellulose content of preferably 0.1-1.0% by weight is mixed with an acidic coagulation and neutralization bath using a mixture of at least 10 rpm and preferably 100-1000 rpm, wherein said bath contains an aqueous solution of an inorganic or organic: Y acid, preferably sulfuric or hydrochloric acid, at a concentration of at least 0.5 wt.%, preferably between 1 and 10 wt. optionally added inorganic or organic salt, preferably 30% sodium sulphate at a concentration of at least 0.1% by weight and preferably at least 1-20% by weight at a temperature of at least 10 ° C and most preferably *: ** 20-100 ° C, followed by stabilization for 1 min to 24 hours, preferably 30 min to 2 hours at a temperature of at least 10 ° C and preferably 20 to 100 ° C, at least 10 rpm and most preferably 100 to 1000 rpm at 35 with an acid concentration of at least 0.5% by weight, followed by purification of the microcrystalline cellulose by washing: · to effect a neutralization reaction and possibly drying.

6 10733 ^

According to the method of the invention, the cellulose solution is obtained from soluble cellulose, either native or regenerated by enzymatic treatment of the cellulose, using the cellulase type of the enzymes obtained from Aspergillus niger IBT. The soluble cellulose used in the process of the invention is characterized by an average molecular weight of at least 100 and most preferably from 300 to 600, necessary to provide fibers, film or other products with suitable properties, and hydrogen bond energy of up to 16 kJ / mol, preferably 10-15 kJ / mol.

10

The hydrogen bonding energy of the cellulose is generally in the range of 20-22 kJ / mol. Calculating this value by enzymatic treatment causes breakage of the intermolecular hydrogen bonds. This phenomenon contributes to the breakage of hydrogen bonds connecting the solid state macromolecules and results in swelling and eventually dissolution by the action of one simple solution such as an aqueous solution of alkali metal hydroxides. This solution penetrates between the macromolecules of the activated cellulose and breaks the weak hydrogen bonds formed during the enzyme treatment. Hydroxyl-containing macromolecules dissolved in water and alkali metal hydroxides are converted into liquid form.

By the process of the invention, it is possible to prepare, by a simple and rapid process, a solution of cellulose in a typical non-toxinic, non-explosive inorganic solution, which can also be used for containers typically used in viscose technology. The process of preparing a cellulose solution at a temperature of -10 to + 10 ° C usually requires ______ for 30 minutes to 2 hours for the leaching step and for some time • · ·: y; air exhaust and possible filtration.

In the process of the invention, a cellulose solution ... with a polymer concentration of at least 0.1% by weight, preferably 3-8% by weight, suitable for use in fibers, film or other materials, is prepared. products such as microcrystalline cellulose. The manufacture of cellulosic fibers and film by the process of the invention requires essentially a solution which, from a technical and technological point of view, requires a solution having a cellulose concentration of 3-8%, whereas the manufacture of microcrystalline cellulose requires a solution having a cellulose concentration. is between 0.1% and 1.0% by weight.

j i 7 107335

By the process of the invention, it is possible to prepare cellulose fibers and film by spinning a cellulose solution into an acid bath containing an inorganic or organic acid, usually sulfuric or acetic acid. Coagulation and neutralization processes take place in a hap-5 subcool. In the process of the invention, the spinning process results in the desolvation of the hydroxyl groups of the macromolecules and a suitable coagulation process involving the neutralization of the sodium hydroxide contained in the cellulose solution. Stretching of the formed cellulosic fibers or membrane also results in the proper organization of the su-10 permolecular structure of the resulting product. Adding salts to an acid bath slows down the rate of the coagulation process in the process of the invention. As a result of this phenomenon, a suitably ordered structure of cellulosic fibers and films is obtained, which mainly affects their mechanical properties.

15

In an embodiment of the process of the invention which is agitated at a rotation speed of at least 10 rpm and preferably 100 to 1000 rpm, cellulose precipitation facilitates the formation of microcrystalline cellulose having an average diameter of 1 to 50 µm and having a generally large internal surface. By using a cellulose solution having a polymer concentration of preferably 0.1 to 1.0% by weight, it is possible to form microcrystalline cellulose having a high sorption and a developed inner surface. In the process of the invention, the stabilization process facilitates the production of stable, homogeneous microcrystalline cellulose.

The advantages of the process according to the invention are the production of cellulosic fibers, film ··· and other products using simple, ecological and economic techniques without the use of complex, toxic, explosive and expensive solvents. The soluble cellulose used in the process of the invention can be very easily dissolved in aqueous solutions of alkali metal hydroxides, typically typical aqueous sodium hydroxide solutions, without any special process to produce a stable cellulose solution. The spinning process can be carried out on a typical spinning machine: * · *: 35 tolu using only an acid bath.

** For finishing the resulting products, water is required to purify the main: · ”matter. The dissolution, spinning and finishing processes do not cause 8 107335 ecological problems or toxic by-products; regeneration of the acid bath yields only the sodium salt of the acid used. The process of the invention is simpler and safer than the vise composite process.

5

The process of the invention has the advantage of being able to use typical, simple equipment in the chemical industry, such as the viscose industry. The technical process of the process of the invention is very simple and is closely related to the solubility of soluble cellulose, which is stable in its solid state, deaeration and possible filtration, and involves the spinning of fibers and film or the precipitation of microcrystalline cellulose.

The products obtained by the process of the invention have characteristic properties that are similar or much better than those of viscose products; for example, the mechanical properties of the film obtained by the process according to the invention are generally superior to those of the viscose film.

The purpose is to further develop a process for making fibers, film and other products from soluble cellulose that can be used in the chemical fiber industry, the textile industry; ; in medicine and in the cosmetics industry.

The following methods have been used to obtain soluble cellulose to determine the properties of the products: T: a method for determining the average degree of polymerization of cellulose as described in Das Pat 30 Pier, Vol. 12, p. 187, 1958 and Faserforschung Textil Tech .; . ·. ·! Butter. 7, p. 153, 1973; 9 · · 9 • ·: - method for determining the water retention value of cellulose; (44 | described in Journal of Applied Polymeir; ·: · 35 Science, Vol. 22, p. 177, 1987; * 4 «* 4 I 4 4 · 4 t 4 4 9 107335 method for determination of hydrogen bonding energy Cellulose Chemistry and Technology, Vol. 14, pp. 893, 1980. 5 - Method for determining the degree of solubility of cellulose in an assay in which 5 g of cellulose are dissolved in 100 ml of a 9% aqueous sodium hydroxide solution at -5 ° C with stirring. min at 500 rpm, store for 24 h at -5 ° C, and determine solution characteristics by approximately absorbance determination at max = 400 nm, intensity of diffused light is determined on a Viscomat apparatus, clarity of the solution is determined by microscopy, viscosity and spinning characteristics. All of the above assay results are changed to a scale of 1-5, where a value of 5 refers to the optimum values of the cellulose solution; for evaluating the mechanical properties of cellulose membranes according to Polish standard BN-20 85 / 6385-03 / 09; a method for evaluating the mechanical properties of cellulosic fibers obtained by the Polish standard PN-83 / P- ;. '04653 and PN-84 / P-04654.

: 25

To compare the membranes obtained from soluble cellulose, a viscose film was formed under analogous conditions. Viscose Membrane Mech-.v. These properties had a thickness in the range of 0.02-0.07 mm, a strength in the range of 9.2-23.7 MPa and an elongation in the range of 31-53.5%. The average thickness was 0.048 mm, the average strength 15.7 MPa and the average elongation 40.7%.

The cellulose used in the process is obtained by an enzyme treatment according to Finnish Patent Application 910990 and is characterized by a high degree of solubility in an aqueous alkaline solution, in particular 5-10 p-. % sodium or potassium hydroxide in aqueous solution, preferably having a degree of dissolution of 98-100% at a concentration of at least 3% by weight of cellulose, wherein the average degree of polymerization of the cellulose is at least 100, preferably 300- 600, the water retention value is preferably between 50 and 100%, the crystallinity index is preferably not more than 70%, and the energy of the hydrogen bonds is usually not more than 16 kJ / mol, 5 preferably 10-15 kJ / mol.

Cellulose soluble in the above alkaline aqueous solution ready! enzymatic treatment comprises treating the cellulose pulp with enzymes of cellulase type from Aspergillus niger IBT, characterized by a CMC activity of 0.1-15 U / ml, an FPA activity of 0.01-1.0 U / ml. ml and β-glucosidase activity between 0.1-15.0 U / ml and the ratio of CMC to FPA-j activities between 1-100, preferably 1-40, and CMC activity in the enzyme solution between 0.1-5.0 U / ml, and a concentration of cellulose 15, preferably between 0.1 and 20% by weight.

The cellulose enzyme treatment is usually carried out at a temperature of at least 10 ° C, preferably at a temperature of 20-50 ° C for at least 1 min, preferably 1 to 4 Si, at a pH of not more than 7.0 and most preferably between 4 and 6.

20

The invention will be explained in more detail in the following examples, which do not limit the scope of the claims.

Example 1 3.3 parts by weight of a solution of J: Y-sized cellulose pulp from Fibrenier-type cellulose treated with Aspergillus niger IBT-type cellulase enzyme and characterized by average! degree of polymerization DP = 493, water retention value WRV = 71.0% and hydrogen bonding energy EH = 12.9-15.1 kJ / mol were added at 100 rpm with a mixer and! * *! .... to a homogenizer with a cooling system that included! *: ** 96.7 parts by weight of a 9% aqueous sodium hydroxide solution at an initial temperature of -6 ° C. The added cellulose dissolved within 1 h at a constant temperature of -5 ° C to give a clear, colorless viscous. <; ·. 35 of the solution, which was characterized by a dissolution rate of 5.0.

11 107335

After 24 h, the cellulose solution was transferred to a glass plate to form a thin layer, and after drying at 60 ° C for 15 min, it was transferred to 10 wt% aqueous acetic acid to effect coagulation and neutralization. The resulting cellulose film was washed with cold water to obtain a neutral pH and dried under stretching conditions at room temperature.

The resulting transparent cellulose film was characterized by an average thickness of 0.045 mm, a strength of 25.1 MPa and an elongation of 2.80%.

10

Example 2 3.3 parts by weight of soluble cellulose obtained from Fibrenier-type cellulosic pulp treated with Aspergillus niger IBT-type cellulase enzyme, characterized by an average degree of polymerization DP = 466 and EH = 12.2-15.9 kJ / mol, was mixed with 96.7 parts by weight of a 7% by weight aqueous solution of sodium hydroxide at 500 rpm at -5 ° C for 2 hours to give a clear, colorless, viscous solution characterized by a dissolution rate of 5.0.

After 24 hours, the cellulose solution was used to form a film;] · 'as in Example 1 using a bath containing 100 g / l sulfuric acid and 100 g / l aluminum sulfate at 20 ° C.

The resulting transparent cellulose film was characterized by a thickness of 0.04 mm, a strength of 19.9 MPa and an elongation of 3.4%.

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Example 3 .... r 30 • · ... 4.8 parts by weight of soluble *: ** cellulose obtained from Fibrenier-type cellulose pulp treated with cellulose obtained from Aspergillus niger IBT type. characterized by DP = 547 and EH = 13.2-14.9 kJ / mol was mixed with 95.2 parts by weight of 10 · · ·. 35% by weight aqueous solution of sodium hydroxide at 0 ° C 1. '! - for one hour at 700 rpm to obtain a clear, colorless; * 'viscous solution characterized by a dissolution rate of 4.5.

ia 107335

After 24 h, the cellulose solution was used to form a film according to Example 1 using a bath containing 100 g / l sulfuric acid and 160 g / l sodium sulfate and 160 g / l aluminum sulfate at 23 ° C.

The resulting transparent cellulose film was characterized by a thickness of 0.025 mm, a strength of 23.3 MPa and an elongation of 2.7%.

Example 4 10 6.9 parts by weight of Liu-junk cellulose obtained from Fibrenier-type cellulose pulp treated with a cellulase enzyme of the Aspergillus n / ger1BT type, characterized by DP = 565, WRV =; 62%, Eh = 15.5-16.5 kJ / mol, was dissolved in 93.1 parts by weight of a 9% aqueous sodium hydroxide solution stirred at 100 rpm for 2 hours at -5 ° C. After diluting the resulting solution to 0.5 wt% cellulose, it was added dropwise to a coagulation bath containing 5 wt% aqueous sulfuric acid, stirring at 500 rpm, resulting in a final acid concentration of at least 0.5 wt%. The stabilization was carried out for 1 to 20 hours at 20 ° C. The product was then washed with water: to obtain a neutral pH, and excess water was removed.

This resulted in 65.3 parts by weight of a white microcrystalline cellulose dispersion containing 10.4% by weight of a dry polymer having: 25 DP = 475, WRV = 378 and EH = 13.63 and 16.50 kJ / mol.

Example 5 3.3 parts by weight of soluble cellulose according to Example 4 were dissolved; • · * * 30 as in Example 4 to 96.7 parts by weight of a 9% by weight aqueous solution of sodium hydroxide. After dilution of the resulting solution to 0.1 wt% cellulose, it was added to a coagulation bath containing 2.5 wt% aqueous sulfuric acid and stirred; 400 rpm, whereby an acid concentration-35 of at least 0.4% by weight was finally obtained. The product was stabilized and purified .. · 'as in Example 4.

13 107335

As a result, 38.3 parts by weight of a white microcrystalline cellulose dispersion containing 5.0% by weight of dry polymer having DP = 448, WRV = 435.5% and EH = 12.20 and 13.63 kJ / mol were obtained.

Example 6 5.0 parts by weight of soluble cellulose obtained from Fibrenier-type cellulose pulp treated with Aspergillus π / ger IBT-type cellulase enzyme, characterized by DP = 455, WRV 10 = 86.83%, were dissolved in 95.0% by weight. to 9% by weight aqueous sodium hydroxide solution at -5 ° C for 0.5 hour, followed by degassing for 24 hours under reduced pressure.

The cellulose solution was spun without stretching into a coagulation and neutralization bath containing 100 g / l sulfuric acid, 160 g / l sodium sulfate and 160 g / l aluminum sulfate, and the resulting cellulose fibers were washed with water to obtain a neutral pH and dried.

As a result, 4.95 parts by weight of white monofilament sel-20 cellulose fibers of size 169dtex, strength 0.04cN / tex and elongation 2.80% were obtained.

Further examples of the preparation of soluble cellulose used in the process of the invention are given below. The manufacture has been carried out in accordance with Finnish Patent Application: 910990.

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Example 7 • · «> #> t. 30,100 parts by weight of Fibrenier-type cellulose sheets characterized by an average polymerization rate of DP = 756, a crystallinity index of *: · * Crl = 76.65%, WRV = 62.26% and hydrogen bonding energy

Eh = 20-22 kJ / mol, was shaken for 1 hour, after which the cellulose pulp was transferred to a stirred tank, to which 1900 parts by weight of a 4.8% sodium acetate buffer solution containing Aspergillus niger IBT was added; · * Cellulase, characterized by CMC activity of 1.41 U / ml, FPA activity of 0.07 U / ml and β-glucosidase activity of 1.48 U / ml, and CMC-14 107335 β-glucosidase activity of 1.48 U / ml and a CMC to FPA activity ratio of 20.14. The solution has a cellulose content of 5% by weight.

Enzyme treatment was performed for 24 hours at 20 ° C with a pH of 4.8. The treated cellulose was then filtered and squeezed at 2.5, washed with warm water at 80 ° C and then washed with water to purify the cellulose, followed by air drying at 40 ° C.

104.5 parts by weight of white cellulose were obtained. The product was characterized by an average degree of polymerization DP = 493, WRV = 71%, Crl = 73.3% and hydrogen bonding energy EH = 12.9-15.1 kJ / mol. The solubility of the cellulose in the 9% sodium hydroxide solution was estimated to be 5.0.

15

Example 8 100 parts by weight of cellulose sheets made by Swiecie Mill, Poland, DP 737, WRV 69.5% and EH 20 kJ / mol were torn for 1 hour, after which the pulp was treated as described in Example 7 in 1900. part by weight of a sodium acetate buffer solution, pH 4.8, containing the cellulase described in Example 7.

As a result, 75 parts by weight of white colored cellulose were obtained, which; : 25 DP was 384, WRV 73%, CrI 76% and EH 13.6-16.5 kJ / mol. cellulose; the degree of solubility in 9% sodium hydroxide solution was evaluated. To 4.5.

Example 9 V * '30 100 parts by weight of Fibrenier-type cellulose sheets having the properties of Example 7 were torn for 1 hour, followed by a mass of hand ··; v: 1900 parts by weight of sodium aze. : a buffer of 4.8 pH containing cellulase from Aspergillus niger IBT 35 with a CMC activity of 1.41 U / ml, an FPA activity of 0.05 U / ml, a β-glucose activity of 7.5 U / ml and a ratio of CMC to FPA: V activity of 28.2. The concentration of cellulose was 5% by weight. Enzyme treatment and purification were performed as in Example 7.

is 107335

As a result, 92.5 parts by weight of white cellulose having a DP of 466, Eh of 12.2-16.5 kJ / mol and a degree of dissolution of 4.0 were obtained.

Example 10 100 parts by weight of Fibrenier-type cellulose sheets having the properties of Example 7 were torn for 1 hour, and the resulting pulp was treated, as in Example 7, with 1900 parts by weight of a 4.8% sodium acetate buffer solution containing 10 cellulases from Aspergillus niger IBT with a CMC activity of 2.20 U / ml, a FPA activity of 0.06 U / ml, a β-glucose activity of 2.4 U / ml and a ratio of CMC to FPA activity 36 , 67. The cellulose concentration was 5% by weight. Enzyme treatment was carried out for 5 hours at 50 ° C, with the pH adjusted to 4.8, and purification was carried out as in Example 8.

15

As a result, 78 parts by weight of white cellulose having a DP of 485, Eh of 12.2 to 15.9 kJ / mol and a solubility of 4.0 were obtained.

Example 11 20 100 parts by weight of Fibrenier-type cellulose sheets having the properties of Example 7 were treated, as in Example 7, with cellulase from Aspergillus niger IBT, characterized by CMC activity: Y: 2.20 U / ml, FPA activity 0.06 U / ml, β-glucose activity 2.4 U / ml and: 25 ratio of CMC to FPA activity 36.67. Enzyme treatment was performed for 24 hours at 20 ° C and pH 4.8.

75 parts by weight of white cellulose having a DP of 521, a WRV of 76.6%, a Cr1 of 66.3% and an EH of 12.9-14.0 kJ / mol were obtained. The degree of solubility '· * * 30 was 5.0.

Y: Example 12 100 parts by weight of Fibrenier-type cellulose sheets having Example 7. · *. 35 properties, were shaken for 1 hour, then treated with 2225 parts by weight of a sodium acetate buffer solution having a pH of 4.8 and: Y containing Aspergillus niger IBT-derived cellulase with 16,107,335 CMC activity of 1.40 U / ml, FPA activity 0.095 U / ml, β-glucose activity 2.02 U / ml, and ratio of CMC to FPA activity 14.74. Ent enzyme treatment was performed for 870 min at 33 ° C and pH 4.8. The product was purified as in Example 7.

5

As a result, 89 parts by weight of white cellulose having a DP of 485 and an Eh of 11.0-15.0 kJ / mol were obtained. The solubility was 4.5.

Example 13 10 100 parts by weight of Fibrenier-type cellulose sheets having the properties of Example 7 were torn for 1 hour and treated with 2028 parts by weight of a 4.8% sodium acetate buffer solution containing Aspergillus niger IBT. cellulase with a CMC activity of 1.60 U / ml, an FPA activity of 0.070.06 U / ml, a β-glucose activity of 2.7 U / ml, and a ratio of CMC to FPA activity of 22.9. Enzyme treatment was performed for 1060 min at 37 ° C and pH 4.8. The product was purified as in Example 7.

As a result, 72.8 parts by weight of white cellulose having a DP of 584 and an Eh of 12.3 to 15.9 kJ / mol were obtained. The solubility was 4.5.

Example 14: 25,100 parts by weight of Fibrenier-type cellulose sheets having the properties of Example 7 were prepared as in Example 7. When the resulting solution of ···· was excess pressed according to Example 7, it had CMC activity of 1. , 1 U / ml ha FPA activity 0.056 U / ml and a new enzyme was added to give CMC activity 1.4, FPA activity 30 0.07 U / ml and CMC and FPA activity ratio 20.14. Enzyme treatment was performed for 1440 min at 20 ° C and pH 4.8. The product · · «* · '* was purified as in Example 7.

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The result was 79.2 parts by weight of white cellulose with DP. ···. 35,525 and WRV 76.57. The solubility was 3-4.

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Claims (12)

17 107335 A process for the production of cellulose soluble in aqueous alkali metal hydroxide, wherein the cellulose pulp is treated with a cellulase enzyme mixture so that it is directly soluble in the aqueous alkali metal hydroxide at a concentration of 5 to 10% by weight of the aqueous solution. Process according to Claim 1, characterized in that the cellulose pulp is directly soluble in an aqueous solution of an alkali metal hydroxide when the concentration of the cellulose to be dissolved in the aqueous solution is at least 3% by weight. The process according to claim 1 or 2, characterized in that the alkali-soluble cellulose is characterized by an average degree of polymerization of at least 100, preferably from 300 to 600, preferably from 50 to 100%, and hydrogen bonding energy of up to 16 kJ / mol, preferably 10 -15 kJ / mol, and most preferably a crystallinity index of -20 to 70%. 4. A method according to any one of the preceding claims, characterized in that the cellulase enzyme mixture has a CMC activity between 0.1 and 15 U / ml, an FPA activity between 0.01 and 1.0 U / ml and a β-glucosidase activity between 0, 1 to 15 U / ml, and the ratio of CMC to FPA activities is 1 to 100, preferably 1 to 40, with the concentration of cellulose in the treatment solution being preferably 0.1 to 20% by weight. • · · • · * «« • · · Process according to Claim 1, characterized in that the enzyme treatment is carried out at a temperature of at least 10 ° C, preferably at a temperature of 20 to 50 ° C, with a pH of not more than 7.0 and most preferably between 4 and 6, Preferably with a treatment time of 1-48 hours, followed by possible washing and drying of the pulp. »· • t · • ·: ** ·; 35 A process for preparing cellulose fibers, film or other cellulose products from alkali-soluble cellulose, wherein the cellulose is pretreated to form an alkali solution, followed by mixing the obtained cellulose with alkali metal hydroxide, in particular 18 107335 of sodium hydroxide or potassium hydroxide, film or other cellulose products, characterized in that the cellulose pulp is pretreated with cellulase concentrate and directly dissolved in an aqueous solution of an alkali metal hydroxide having a concentration of 5 to 10% by weight of an alkali metal hydroxide and a concentration of cellulose product in acid bath. Process according to Claim 6, characterized in that the concentration of the cellulose in the aqueous solution is at least 3% by weight, Process according to Claim 6 or 7, characterized in that the cellulose is mixed with an aqueous solution of an alkali metal hydroxide, in particular a solution of sodium hydroxide or potassium hydroxide in a concentration of between 5 and 15% by weight, preferably between 7 and 12% by weight. -10 to + 10 ° C, preferably -5 to 0 ° C, for 15 minutes to 48 hours, preferably 30 minutes to 2 hours, to obtain a homogeneous solution of cellulose at a concentration of at least 0.1 p- %, preferably 3-8% by weight, after which the resulting cellulose solution is degassed and, if necessary, filtered to obtain a solution which is made into cellulose fibers, film or other cellulose products in an acid bath. '· [[[· 25 Process according to any one of claims 6 to 8, characterized in that the cellulose solution is passed into an acidic coagulation and neutralization bath containing an inorganic or organic acid; -...... * ·· preferably an aqueous solution of sulfuric or acetic acid at a concentration; is at least 10 g / l, preferably 100-200 g / l, and optionally added with an inorganic or organic salt, preferably sodium or aluminum sulphate, at a concentration of at least 1 g / l, preferably 10- • 300 g / l, then the resulting cellulose fibers or the resulting cellulose film or other product are washed by washing to obtain a neutral pH and dried. O 35 Process according to any one of claims 6 to 8, characterized in that, for the preparation of microcrystalline cellulose, a cellulose solution having a cellulose content of preferably 0.1 to 1.0% by weight is mixed with acid. to the coagulation and neutralization bath using at least 10 rpm, preferably 100 to 1000 rpm, of the bath containing an aqueous solution of inorganic or organic acid, preferably sulfuric or hydrochloric acid, at a concentration of at least 0.5% by weight, preferably between 1 and 10% by weight optionally, an inorganic or organic salt is added, in particular sodium sulfate at a concentration of at least 0.1% by weight, preferably 1-20% by weight, at least 10 ° C, preferably at 20-100 ° C, followed by stabilization 1 for min-24 hours, preferably 30 min-2 hours, at least 10 ° C, 10 preferably at 20-100 ° C, with stirring at least 10 rpm, preferably 100-1000 rpm, when concentration is at least 0.5% by weight, after which the microcrystalline cellulose is optionally purified with water to obtain a neutral pH and optionally dried. 15 Process according to any one of claims 6 to 10, characterized in that the average degree of polymerization of the cellulose dissolved in the alkali solution is at least 100, preferably 300-600, preferably 50-100% water retention, hydrogen bonding energy not more than 20 16 kJ / mol, preferably 10-15 kJ / mol, and preferably a crystallinity index of up to 70%. The process according to claim 11, characterized in that the pre-treatment of the cellulose is carried out with a cellulase enzyme mixture having a CMC activity of between 0.1 and 15 U / ml, an FPA activity between 0.01 and 1.0; m: U / ml and β-glucosidase activity between 0.1 and 15 U / ml, and the ratio of CMC to FPA activity is 1-100, preferably 1-40, whereby the concentration of cellulose in the treatment solution is preferably 0.1-20 wt%. »30 ♦ I • ♦ •» • ♦ · • · · «·· ♦ 20 107335