MXPA97004549A - Method for the enzymatic treatment of the l - Google Patents

Abstract

The present invention relates to a method for the production of wool or animal hair material with improved properties, such as anti-shrinkage (antifreeze tendency), increased whiteness, improved dyeing capacity, improved softness and / or lower tendency to ball formation, where the method comprises the steps of treating the wool material, wool fibers or animal hair in a process selected from the group consisting of plasma treatment processes and the Delhey processes and subjecting the wool material or from animal hair to a treatment with a proteolytic enzyme (a protease), preferably a serine protease, more preferably a subtilisin, in an amount effective to improve the properties

Description

METHOD FOR THE ENZYMATIC TREATMENT OF WOOL The present invention relates to a method for providing animal wool or hair with improved properties, e.g., reduced felting, increased whiteness, lower tendency to pelletization, improved softness and better staining characteristics, by means of an enzymatic treatment. More specifically, the method comprises subjecting the wool or animal hair material to a plasma treatment and a treatment with a proteolytic enzyme, i.e., a protease.

BACKGROUND OF THE INVENTION For many years the wool industry has tried to develop methods to reduce wool felting, which does not result in the release of substances harmful to the environment. Recent developments have pointed towards the treatment with low temperature plasma or the Delhey process as possible solutions for this problem. Accordingly, it is known to treat wool fiber material with electric gas discharges (so-called plasma), i.e., in a dry process. The plasma treatment provides a change in the surface finish of the wool fiber which reduces the tendency to felting, improves the stamping capacity and accelerates the staining capacity of the wool. The use of plasma treatment in the REF: 24865 textile finish, especially in the wool finish, is highly advantageous because the process is potentially an environmentally acceptable alternative to conventional chlorination finishing processes, cf. Byrne, K.M. et al .: "Corona discharge treatment of wool - commercial implications", in the report D I (1992), Vol. 109, p. 589-599, (Aachener Textiltagung, 1991). In the finishing of textiles, the treatment applied with plasma is a plasma treatment at low temperature or unbalanced (treatment "cold plasma"), in particular, treatment with corona discharge and treatment of luminescent discharge, cf. Thomas, H. et al .: "Environmentally friendly finishing processes for wool by pretreatment with electrical discharge in gas (plasma)" in ITB, vol. 2, 1993. The corona discharge treatment is carried out under atmospheric conditions and is a weak current discharge which provides an oxidation and, therefore, a polarization of the fiber surface. The luminescent discharge treatment is carried out under reduced pressure, i.e., by producing electrons of higher energy than is possible in the corona discharge treatment and can modify the surface of the fiber more intensely. Accordingly, the plasma treatment provides the fabric or animal hair material with less tendency to felting and better staining characteristics, without the use of harmful chemical compounds and without waste water (dry process). Also, the treatment provides improved anti-shrinkage properties to the treated material which, however, currently can not meet the demands of the end users. In addition, the treatment can reduce the soft touch of wool material or animal hair. Japanese Published Patent Application, Tok ai Hei 4-327274, describes a method for anti-shrinkage treatment of, eg, wool fibers, by subjecting the fibers to a low temperature plasma treatment followed by a treatment with an anti-shrinkable resin, eg, urethane block resin? the polyamide epochlohydrin resin; glyoxalic resin; ethylene-urea resin or acrylate resin; and then a weight reduction treatment with a proteolytic enzyme to obtain a smoothing effect. The Delhey process is described in DE-A-43 32 692 and in J. Delhey: PhD Thesis, RWTH Aachen (1994). In this process, the wool is treated in an aqueous solution of hydrogen peroxide in the presence of soluble tungstate, optionally followed by a treatment in a solution or dispersion of synthetic polymers to improve the anti-felting properties of the wool. Nevertheless, this treatment also does not satisfy the final demands of the users. It is the object of the present invention to provide a method for the treatment of wool or animal hair material to obtain wool or animal hair material with a reduced tendency to felting, improved softness, increased whiteness, less tendency to formation of balls and / or better characteristics of staining in an easy and purely biological way without the use of chemical agents or resins harmful to the environment.

BRIEF DESCRIPTION OF THE INVENTION Surprisingly, it has been found that certain properties of wool, or animal hair, treated with plasma or treated with the Delhey method, can be improved by subjecting wool or animal hair, treated with plasma or treated with the Delhey method, to a treatment with a proteolytic enzyme, in an amount effective to provide the desired effect. Depending . of the special characteristics of the real wool subjected to the treatment according to the present invention, the improved properties can be the reduction in the tendency to felting, greater whiteness, reduction in the tendency to the formation of balls, improvement of the softness or improvement of the staining characteristics. Accordingly, according to the present invention, it is possible to obtain good and satisfactory anti-shrinkage properties, without the use of an anti-shrinkable polymeric resin, by treating the wool or animal hair material with a proteolytic enzyme, either before or after the plasma treatment, preferably a plasma treatment at low temperature, or before or after a Delhey treatment. In addition to the improved anti-shrinkage or antifreeze properties, enzyme treatment can also improve the dyeing characteristics of wool or animal hair material; provide convenient bleaching (better whiteness); and a lower tendency to form balls; and provide recovery of the soft touch of the treated material. Accordingly, the present invention relates to a method for producing wool or animal hair material with improved properties comprising the steps of: a) pretreating the wool or animal hair fiber material with a process selected from the group which consists of the processes of plasma treatment and the Delhey process; and b) subjecting the pretreated animal wool or hair material to treatment with a proteolytic enzyme (a protease), in an amount effective to improve the properties. It is contemplated that treatment with the proteolytic enzyme may be carried out before plasma treatment or after plasma treatment, either in a derivative of a Nocardiopsis sp. , or Nocardiopsis dassonvillei, preferably from a strain of Nocardiopsis sp., more preferably from Nocardiopsis sp. , NRRL 18133. 26. The method according to any of claims 1 to 25, characterized in that the amount of proteolytic enzyme is preferably between about 0.2% w / w and about 10% w / w, based on the weight of the wool or hair material of animal. 27. The wool or animal hair material, characterized in that it has been treated in accordance with the method of any of claims 1 to 26. animal hair that has improved anti-shrink or antifreeze properties. Preferably, the anti-shrinkage improvement of wool or animal hair material treated by plasma and enzyme corresponds to a shrinkage area that is less than 10%, more preferably less than 8%, more preferably less than 7%, more preferably less at 5%, still more preferably less than 3%, especially less than 2%, after two cycles of ISO 5A, or at a shrinkage area of less than 15%, more preferably less than 10%, more preferably less than 8%, even more preferably less than 6%, especially less than 5%, after 5 cycles of ISO 5A; Measured according to Test Method IS 31. Preferably, the improvement in the anti-shrink property of wool or animal hair material, in the Delhey process followed by an enzymatic treatment, corresponds to an area of contact that is less than 25%, more preferably less than 20%, more preferably less than 15%, more preferably less than 12%, more preferably less than 10%, more preferably less than 8%, even more preferably less than 5%, especially less than 2% %, after 2 cycles of ISO 5A; or to a shrinkage area of less than 20%, more preferably less than 15%, more preferably less than 12%, still more preferably less than 10%, especially less than 9%, after 5 cycles of ISO 5A, measured in accordance with the IWS Test Method 31.

Test Method IS 31, which is available from the International Wool Secretariat, is applicable to all woolen fabrics that can be washed and to intermediate products, including combed materials, hand-knitted yarn, spinning knitting machine knitting, spinning for weaving and fabrics for use in cutting and sewing. The test can be used to determine the relaxation and felting behavior of an intermediate product. Relaxation shrinkage is determined from the dimensions of the sample before and after subjecting the sample to moist relaxation with gentle agitation. This relaxation is achieved through the program ISO 6330 7A, International Standard, of the International Standards Organization, but differs in that the load is reduced to one kg. After the relaxation, the shrinkage by felting is determined from the dimensions of the shows before and after subjecting it to severe agitation. This agitation is achieved by the program ISO 6330 5A, but differs in that the load is reduced to 1 kg. The number of cycles of the program 5A, to which the sample is subjected, is determined by the final use of the product. In the case of intermediate products, the combed materials are transformed into spinning of a given account, the yarns (including those manufactured from the aforementioned combed materials) are transformed into a single smooth knit fabric with a standard coverage factor. The single knitted, smooth knit fabric is then evaluated according to the principles indicated above. Alternatively, the antifreeze improvement corresponds to a density of a felt ball at or below 0.04, measured in accordance with the IWTO-20-69 test of the felt ball, Aachen. This test was developed at the Deutsche Wollforschungsinstitut, Aachen, in 1960 and is applicable to wool and blends of wool and synthetic fibers that can be carried to a loose condition. The principle of the test is as follows: 1 g of wool and 50 ml of a buffer (pH 7) are placed in a 150 ml standard steel beaker, which is then shaken three-dimensionally for a period of time . Loose wool will form a ball and the diameter of the felt ball is measured. The greater the tendency to felting, the lower the measured diameter of the resulting felt ball and the higher the density. In the present context, the term "whiteness" is intended to indicate how white or wool is appreciated by a visual determination. The degree of whiteness can be conveniently measured in a Datacolor 3890 Spectral Photometer (CIELAB system). More specifically, the present invention provides a method for producing a wool or animal hair material having improved whiteness. It is thought that the improved whiteness is due to the stage of enzymatic treatment leading to an improvement in the degree of whiteness of the enzyme treated wool. Preferably, the whiteness provided in this way to the woolen or animal hair material treated in the Delhey process, followed by an enzymatic treatment, corresponds to an improvement in the degree of whiteness of at least 10 CIÉ units, more preferably at least 12 CIÉ units, measured in the Datacolor 3890 Spectral Photometer (CIELAB system). Also, the improved whiteness of the wool or animal hair material treated with plasma and with the enzyme corresponds to an improvement in the degree of whiteness of at least 8 CIÉ units, more preferably of at least 10 CIÉ units, measured in the Datacolor 3890 Spectral Photometer (CIELAB system). In the present context, the terms "dye uptake" or "dye uptake" are intended to indicate the ability of the wool immersed in a dye bath to absorb the available soluble dye. More specifically, the present invention provides a method for producing wool or animal hair material having improved dye uptake or better dye uptake. It is believed that the improvement in dye uptake or dye uptake is partially due to the stage of the enzymatic treatment leading to an improvement in the ability of the enzyme treated wool to absorb the dye. Preferably, the best dyeing capacity of the woolen or animal hair material produced corresponds to an increase in color intensity of at least 2 DL (units), more preferably, at least 3 DL units, measured with respect to a reference after of a competitive stain in Lanasol Blue 8G at 2%. In the present context, the term "volumetric strength tenacity loss" is intended to indicate the reduction in the toughness of the volumetric resistance of a fiber volumetric material, ie, the wool or animal hair material which is a result, eg, of any modifications or damages suffered during processes such as staining, bleaching, and conventional treatments, so that it is anti-shrinkable. More specifically, the present invention provides a method for producing wool or animal hair material with the improvement of one or more of the aforementioned properties and with a limited loss of toughness of the volumetric strength. Preferably, the loss of the volumetric strength of the woolen or animal hair material subjected to the method of the present invention corresponds to a difference in the toughness of volumetric strength of the woolen or animal hair material produced and the toughness of the strength volumetric of the untreated material less than 20%, more preferably less than 10%, specifically less than 6%, measured in accordance with IWTO-32-82 (E). This standard, which was prepared by the Working Group "Volumetric Resistance of Fibers", of the IWTO Technical Committee and which was adapted in 1979, is designed to determine the tenacity of wool in the form of bundles of parallel fibers in the direction of extension, with a jaw spacing of 3.20 mm, 5 mm or 10.00 mm. In addition, the present invention provides a method for producing wool or animal hair material of improved softness, preferably a softness corresponding at least to the softness of untreated wool. In the present context, the term "reduced tendency to form pellets" is intended to indicate a permanent (and excellent) resistance to the formation of pellets on the surface of wool, wool material, or animal hair treated, in comparison with the corresponding material that has not been subjected to the method of the present invention. The tendency to form balls can be tested in accordance with the Swiss Standard SN 198525, published in 1990 by Schweizerische Normen-Vereinigung, Kirchenweg 4, Postfach, CH-8032, Zürich, Switzerland, which describes a test of resistance to formation of pellets for fabrics, which in turn is based on the Swiss SNV 95 150 standard (Textiles-standard climatic conditions and test conditions for physical tests, under standard climate conditions) and SN 198 529 (Evaluation of Textiles - "Scheuerfestigkeit" - Martindale method). The results of the test are expressed in terms of ball-forming notes "which is a score" on a scale from the ball-forming note 1 (a heavy formation of balls) to a ball-forming note 5 (none or very little ball formation) allowing H-ball formation notes. In another aspect, the present invention provides a method for producing wool or animal hair material that has a reduced tendency to pelletization.

The substrate material The method of the invention can be applied to any desirable animal hair product. The most commercially interesting animal hair is wool, e.g. of sheep, camel, rabbit, goat, llama, i.e., such as merino sheep wool, shetland wool, cashmere wool, alpaca wool, camel hair. The wool or animal hair material subjected to the method of the invention may be of combed materials, fiber, yarn or woven or knitted fabric. The treatment with proteolytic enzymes can also be carried out on loose wool or on a garment made of wool material or animal hair that has been previously treated with plasma. It should be emphasized that wool and other animal hair are products of biological origin. The material can vary greatly, e.g., in chemical composition and structure, depending on the living and health conditions of the animal. Accordingly, the effect (s) obtained by subjecting the wool, or the other animal hair products, to the method of the present invention, may also vary according to the properties of the initial material.

The process Basically, the present invention is carried out in two stages. The plasma treatment step is a low temperature treatment, preferably a corona discharge treatment or a luminescent discharge treatment, see above. This plasma treatment at low temperature is carried out using a gas, preferably a gas selected from the group consisting of air, oxygen, nitrogen, ammonia, helium or argon. Conventionally, air is used but it may be advantageous to use any of the other indicated gases. Preferably, the plasma treatment at low temperature is carried out at a pressure between about 0.1 torr and 5 torr, from about 2 seconds to about 300 seconds, preferably about 5 seconds, up to about 100 seconds, more preferably from about 5 seconds, up to about 30 seconds. The Delhey process is described in J. Delhey: PhD Thesis RWTH Aachen 1994; and in DE-A-43 32 692 and is carried out as follows: The wool is treated in an aqueous peroxide solution - Hydrogen (0.1% to 35% (w / w), preferably 2% to 10% (w / w), in the presence of 2% to 60% (w / w), preferably from 8% to 20% (w / w) of a catalyst (preferably Na 2 W 0 4) and in the presence of a nonionic wetting agent. Preferably, the treatment is carried out at pH from 8 to 11 and room temperature. The treatment time depends on the concentrations of hydrogen peroxide and the catalyst, but preferably it is 2 minutes or less. After the oxidative treatment the wool is rinsed with water. For the removal of the residual hydrogen peroxide and optionally for an additional whiteness, the wool can be further treated in acid solutions of reducing agents (sulphites, phosphites, etc.). The enzymatic treatment step is preferably carried out for between about 1 minute and - about 120 minutes; preferably at a temperature of between about 20 C and about 60 C, more preferably between about 30 C and about 50 C. Alternatively, the wool can be soaked in, or impregnated with, an aqueous solution of the enzyme and then subjected to a vaporized at a conventional temperature and pressure, typically for about 30 seconds to about 3 minutes. The treatment with the proteolytic enzyme is carried out in an acidic or neutral or alkaline medium, which may include a buffer. It may be advantageous to carry out the enzymatic treatment in the presence of one or more conventional anionic, nonionic, or cationic surfactants. An example of a useful nonionic surfactant is Dobanol (from Henkel AG). In addition, wool material or animal hair can be subjected to an ultrasound treatment, either before, or simultaneously with, the treatment with a proteolytic enzyme. The ultrasound treatment can advantageously be carried out at a temperature of about 50 C for about 5 minutes. It is contemplated that the reaction rate of the enzymatic treatment step may be increased by increasing the temperature of the enzyme bath during the treatment, i.é., the total time of the treatment may be reduced. The amount of proteolytic enzyme used in the enzymatic treatment step is preferably between about 0.2% w / w and about 10% w / w, based on the weight of the wool or animal hair material. It should be understood that, in order to reduce the number of stages of the treatment, the enzymatic treatment can be carried out during the staining or degreasing of wool or animal hair material simply by the addition of the protease to the dyeing, rinsing or scouring bath. Preferably, the enzymatic treatment is carried out after the plasma treatment, but the two stages of the treatment can also be carried out in reverse. It should be noted that the handling of wool or animal hair treated with plasma is generally rougher than that of untreated wool. Enzymatic treatment provides a softer feel due to weight loss and a reduction in fiber stiffness. Also, the enzymatic treatment can improve the uptake of softeners, thereby improving the softening effect of additional treatments with softeners. The softness obtained by the enzymatic treatment and the softening agents is more durable than that obtained with softening agents alone.

- - It is also well known that plasma treatment or Delhey treatment can provide certain antencogimiento properties. The degree of them increases after an enzymatic treatment. It is thought that plasma treatment or Delhey treatment provides the oxidation and lipid removal necessary for access of the protease to the surface of the wool fiber. It has been established that the plasma treatment and the Delhey treatment have various advantages for the staining properties of the wool. One of these advantages is the faster absorption of the colorant at low temperatures and an improvement in the exhaustion of the dye bath. The absorption of the dye is further improved by the enzymatic treatment.

The Enzyme A proteolytic enzyme useful for the method of the present invention is any enzyme that has proteolytic activity under the actual conditions of the process. Accordingly, the enzyme may be a proteolytic enzyme of plant origin, e.g., papain, bromelain, phycine; or one of animal origin, e.g., trypsin and chymotrypsin; or of microbial origin, i.e., bacterial; or of fungal or yeast origin. It should be understood that any mixture of various proteolytic enzymes may be applicable to the process of the invention. In a preferred embodiment of the invention, the proteolytic enzyme is a serine protease, a metalloprotease or an aspartate protease. A serine protease is an enzyme that catalyzes the hydrolysis of peptide bonds and in which there is an essential residue of serine in the active site. They are inhibited by diisopropylfluorophosphate, but, in contrast to metalloproteases, are resistant to ethylene diamine tetraacetic acid (EDTA) (although they are stabilized at high temperature by calcium ions). They hydrolyse the simple terminal esters and are similar in activity to the eukaryotic cytotropin, also a serine protease. A more precise term, alkaline protease, which covers a subgroup, reflects the high, optimal pH of some of the serine proteases, from pH 9 to pH 1L.0. Serine proteases usually exhibit maximum proteolytic activity in the alkaline pH range, while metalloproteases and aspartate proteases usually exhibit maximum proteolytic activity in the range of neutral and acid pH, respectively. A subgroup of serine proteases are commonly designated as subtilisins. A subtilisin is a serine protease produced by a Gram-positive bacterium or a fungus. The amino acid sequence of several subtilisins has been determined, including at least six subtilisins of the Bacillus strains, ie subtilisin 168, subtilisin BPN, subtilisin Carlsberg, subtilisin DY, subtilisin amilosacariticus and mesentericopeptidase, a subtilisin of actinomycetales, termitase of Thermoactinomyces vulgaris and a subtilisin of fungus, proteinase K from Tritirachium album. An additional subgroup of subtilisins, subtilases, have been recognized more recently. Subtilases are described as highly alkaline subtilisins and comprise enzymes, such as subtilisin PB92 (MAXACAL, Gist-Brocades, NV), subtilisin 309 (SAVINASER, NOVO NORDISK 'A / S), and subtilisin 147 (ESPERASER, NOVO NORDISK A / S). In the context of this invention, a variant of subtilisin or mutated subtilisin protease indicates a subtilisin that has been produced by an organism that is expressing a mutant gene, derived from a parent microorganism that possessed an original or related gene and that produced an enzyme corresponding relative, the relative gene has been mutated in order to produce the mutant gene from which the mutated subtilisin protease is produced when expressed in a suitable host. These mentioned subtilisins and variants thereof constitute a preferred class of proteases which are * useful in the method of the invention. An example of a useful subtilisin variant is a variant of subtilisin 309 (SAVINASER) where, at position 195, glycine is substituted by phenylalanine (G195F or 195Gly a - - Conveniently, commercial proteases fermented in a conventional manner are useful. Examples of these commercial proteases are Alcalase (produced by submerged fection of a strain of Bacillus licheniformis), Esperase R (produced by submerged fermentation of a Bacillus alkalophilic species), Rennilase (produced by submerged fermentation of a non-pathogenic strain of Mucor p. miehei, Savinase (produced by submerged fermentation of a genetically modified Bacillus strain), eg, the variants described in International Patent Application p published as WO 92/19729, and Durazym (a variant, of a protein engineered by genetics, Savinase) All the commercial proteases mentioned are produced and sold by Novo Nordisk A / S, DK-2880 Bagsvaerd, Denmark Other preferred serine proteases are the proteases of Nocardiopsis, Aspergillus, Rhizopus, Bacillus alkalophilus, B. cereus, N. natto, B. vulgatus, B. mycoide and the subtilisins of Bacillus, especially the proteases of the species Nocardiopsis sp., and Nocardiopsis dessonvillei, such as those described in published International Patent Application, WO 88/03947, especially the proteases of the species Nocardiopsis sp., NRRL 18262 and Nocardiopsis dessonvillei, NRRL 18133. Still, other preferred proteases are serine proteases. of the Bacillus subtilis mutants, described in International Patent Application No. PCT / DK89 / 00002 and in the published International Patent Application WO 91/00345, and the proteases described in EP 415 296 A2. Another preferred class of proteases are metalloproteases of microbial origin. Conveniently, commercial proteases fermented in a conventional manner are useful. Examples of a commercial protease is Neutrase (Zn) (produced by submerged fermentation of a Bacillus subtilis strain) that is produced and sold by Novo Nordisk A / S, DK-2880 Bagsvaerd, Denmark. Other useful, protease enzyme preparations are Bactosol ™ WO and Bactosol ™ SI, available from Sandoz AG, Basle, Switzerland; Toyozyme TM, available from Toys Boseki, Co. Ltd., Japan; and Protemase K ™ (, produced by submerged fermentation of a strain of Bacillus sp. KSM-K16), available from Kao Corporation, Ltd., Japan.

The softeners It may be desirable to treat the wool or animal hair material with a softening agent, either simultaneously with the treatment, with the proteolytic enzyme or after the plasma treatment and the treatment with a proteolytic enzyme. Treatment with softener may be necessary in cases where most of the natural fatty matter on the surface of the fiber has been removed, e.g., as a result of degreasing or plasma treatment. Accordingly, in order to eliminate a possible dry, rough feel of the fiber, it may be necessary to reapply a low concentration of fatty material to the surface of the fiber in the form of a softening or softening agent. The softeners conventionally used in wool are generally cationic softeners, either cationic organic softeners or silicone-based products, but anionic or non-ionic softeners are also useful. Examples of useful softeners are polyethylene softeners and silicone softeners, ie, dimethyl polysiloxanes (silicone oil), H-polysiloxanes, silicone elastomers, aminofunctional dimethyl polysiloxanes, silicone elastomers with amino function and dimethyl polysiloxanes with an epoxide function and organic cationic softeners, eg, alkyl quaternary ammonium derivatives. The invention is further illustrated in the following non-limiting examples.

EXAMPLE 1 In this working example, the effects on the property of the materials were described by the following methods: Shrinkage: IWTO-20-69: Method for determining the properties of felting of loose wool and combed materials. A reduced density of the felt ball corresponds to a lower felting. Degree of Whiteness: W-CIE (from 1986) .. The more positive the resulting CIÉ number, whiter is wool (-0.3 is more positive than -5). Staining capacity: Staining of the samples: The samples were immersed in a tincture solution of Lanasol Blau 8G 2% (w / v) (from Ciba Geigy), with a liquor ratio of 1:13. The dye bath was brought to the boiling point and kept at boiling temperature for 10 minutes. Then, the samples were washed once with tap water and once with distilled water and dried. The sample and the reference were stained in the same dye bath (staining, competitive). Colorimetric evaluation of the color differences: The color of the samples is evaluated in terms of the CIE-LAB / D65 coordinates, by means of a Datacolor Tex flash 200 device. The coordinates of the samples were recorded as a difference of values with respect to to the corresponding reference. A more negative DL value refers to a darker hue; a more positive DH value refers to a blue hue. The wool material, applied, defatted, was merino of 20 microns with a pH value of 9.7 and a degree of whiteness (W-CIE) of -10.7.

Four different plasma-enzyme processes were evaluated. In all processes, the treatment with plasma and with the enzyme of the invention is carried out as follows: Treatment with Plasma: The wool was initially subjected to a plasma treatment at low temperature with the following parameters: Excitation frequency: 4 to 5 kHz. Pressure: 1 mbar. - Time: 20 seconds, gas: air.

Enzymatic treatment: The pretreated wool was immersed in a phosphate solution (0.1 M, pH 8), liquor ratio 1:20. After immersion, a protease Nocardiopsis sp., NRRL 18262, was added to the liquor in a dose of 0.12 g / kg of wool. The enzyme was allowed to act for 45 minutes and 120 minutes, respectively, at 50 ° C; then, the wool was washed in water and dried. In all cases a reference sample treated with plasma was prepared by a corresponding treatment using only buffer.

Process No. 1 Enzyme treatment directly after plasma treatment. Results: Time of the degree of evaluation colori- Density treatment: metric whiteness after the ball 45 minutes (CIÉ) the felt staining test (CIELAB / D65) # (g_ / c_m3,) Reference - 6.4 0.126 Treatment - 0.3 DL = -3.2 0.098 enzymatic DH = 0.7 Degree time of color evaluation- Treatment density: metric whiteness after the ball 120 minutes (CIÉ) the felt staining test (CIELAB / D65) (g / cm3) Reference - 11.2 0.113 Treatment - 2.8 DL = -6.8 < 0.041 enzymatic DH = 6.0 Process No. 2 In order to remove adjacent material from the plasma treated wool before the enzymatic treatment, an ultrasonic treatment was carried out between the plasma treatment and the enzyme: Treatment medium: Pure water Ratio of the liquor: 1:20 Temperature 40 ° C Frequency 35 kHz Treatment time 5 minutes Then it was washed, dried and treated with the enzyme. Results: Time of the degree of evaluation colori- Density treatment: metric whiteness after the ball 45 minutes (CIÉ) the felt staining test (CIELAB / D65) # (g_ / c_m3,) Reference - 5.7 0.115 Treatment - 4.5 DH = 2.4 0.104 enzymatic Degree time of color evaluation- Treatment density: metric whiteness after the ball 120 minutes (CIÉ) the felt staining test (CIELAB / D65) (# g_ / c_m3,) Reference - 9.9 0.112 Treatment - 2.8 DL = -8.1 < 0.041 enzymatic DH = 4.4 Process No. 3 In order to remove material adhered to the surface of the wool treated with plasma before treatment with the enzyme, a treatment with surfactant is carried out between the treatment with plasma and with the enzyme: Means of treatment! Dobanol 0.1% (non-ionic surfactant from Henkel AG) in water. Liquor ratio: 1:20 Temperature: 40 ° C - - Treatment time: 5 minutes.

It was then washed, dried and treated with the enzyme. Results: Degree time of color evaluation- Treatment density: metric whiteness after the ball 45 minutes (CIÉ) the felt staining test (CIELAB / D65) (g / cm3) Reference - 4.8 0.102 Treatment - 3.3 DH = 0.9 0.087 enzymatic Degree time of color evaluation- Treatment density: metric whiteness after the ball 120 minutes (CIÉ) the felt staining test (CIELAB / D65) / (g _ // c_m3-) Reference - 9.0 0.102 Treatment 0.6 DL = - 3.1 0.050 enzymatic DH = 4.6 Process No 4 For the elimination of the adjacent material of the wool treated with plasma before the enzymatic treatment, an ultrasonic treatment with surfactant was carried out between the treatment with plasma and with the enzyme: - - Treatment medium: Dobanol 0.1% in water Liquor ratio: 1:20 Temperature: 40 ° C Frequency: 35 kHz Treatment time: 5 minutes It was then washed, dried and treated enzymatically. Results: Degree time of color evaluation- Treatment density: metric whiteness after the ball 45 minutes (CIÉ) the felt staining test (CIELAB / D65) (g / cm3) Reference - 5.1 0.101 Treatment - 3.2 DL = - 4.2 0.088 enzymatic DH = 2.5 Degree time of color evaluation- Treatment density: metric whiteness after the ball 120 minutes (CIÉ) the felt staining test (CIELAB / D65) (g / cm3) Reference - 6.5 0.098 Treatment 2.1 DL == - 6.5 < 0.041 enzymatic DH = 5.7 The results shown in the tables of processes 1 to 4 show that the enzymatic treatment, in all cases, resulted in an increase in the whiteness, an increase in the intensity of the color and a reduction in the felting.

EXAMPLE 2 1.1 Wool material a) Wool fabric, knitted fabric, treated with plasma and reference. The parameters of the fabric were as follows: - fineness: 24 microns - count of the yarn: tex 25x1 - coverture factor: 0.71 knitted fabric on a circular knitting machine, Maxi Jack (Trabal, Spain) 2 - weight of the fabric 250 g / m - standard finishing procedure (degreasing, staining with stripping, decanting) - dry cleaning (to remove all softeners and surfactants) - plasma treatment with air: treatment time, 60 seconds; voltage, approximately 800 V; current, 2.2 A. b) woven fabric, untreated, flat weave, for the light resistance test. Weight per area 127 g / m 2. 1. 2 Enzyme material The enzyme used was NOVOZYM 654 protease, from Novo Nordisk A / S, DK-2880 Bagsvaerd, lot 94-12. 1. 3 Enzyme treatment Enzymatic treatment was carried out on staining machines. The samples were prepared either according to the IWS 31 test method and then treated enzymatically; or the samples were first treated enzymatically and then prepared according to the IWS 31. In the first case, the samples were twice as thick and 300 mm x 400 mm in size, sewn together at the edges. The samples were treated enzymatically in the Ahiba Turbomat 1000 equipment. 500 ml of the tris- (hydroxymethyl) -aminomethane acetate buffer, pH 8, were added to 65 g of the stitched and knitted sample (ratio of liquor 1: 7.7) 0.166% (owf) NVOZYM 654 were incubated with the wool at a temperature of 50 ° C, for 120 minutes (resp 60 minutes). Inactivation of the enzyme was carried out at 85 C for 10 minutes. The samples were rinsed with tap water for 20 minutes. The references were treated under the same conditions with buffer, without the addition of the enzyme. In the second case, the knitted fabric was treated enzymatically as a single piece in the Ahiba Turbocolor dyeing machine. The liquor ratio was 1: 7.9 and the rinse was carried out in the dyeing machine for 30 minutes, in addition to these conditions, the treatment parameters were the same as those mentioned above. After the enzymatic treatment, the pieces of fabric, with a size of 225 x 300 mm, were sewn together and prepared for the IWS TM 31. In the case of the woven fabric, the 300 x 300 mm samples were prepared in a single layer. A fist was formed before the TM 31 test by folding two sides along 20 mm lines, from the edge. 1. 4 The Delhey process / l Immediately before use, the treatment solution was prepared as follows: 50 ml of H "0- (35%, v / v) and 53 g of Na2W04 x 2 H20 were mixed in 550 ml of H20, with 3 g of Laventin LNB (BASF) (corresponding to 20 g of fabric). 15 seconds later, a sample of woven fabric was wetted in the solution and squeezed in a pad to a 75% weight increase. After a reaction time of 2 minutes, the sample was rinsed with water, from the tap and dried in the air. 1. 5 IWS 31 Test Method The measurements of the dimension were made after the relaxation (lx7A), after the shrinkage of felting (2x5A), and after the shrinkage of felting - - (5x5A). The sizes of the samples were in accordance with subsection 1.3. 1. 6 Determination of weight loss The weight loss of the samples was determined by measuring the dry weight of the samples before and after treatment with the enzyme or with the buffer. Part of the samples were dried at 110 C for 4 hours, cooled in a desiccator and weighed. 1. 7 Degree of whiteness The degree of whiteness was measured in a colorimeter Datacolor 3890 (Datacolor, Mari, Germany). The degree of whiteness is given as W-CIE. 1. 8 Dye uptake The fabrics were stained with 2% Lanasol Blue 8G in small batches (4 ml, 2 x 200 mg of woven cloth, 2 x 500 mg of knitted cloth, 10 minutes at 100 ° C). The samples treated respectively with buffer and the enzyme-treated samples were stained in competition. The color measurements were made in the Datacolor 3890 colorimeter. The given values are difference values, DL (color intensity). 1. 9 Wettability test (drop test) / 2 / Distilled water (0.25 g) was dripped from a height of 40 mm onto the stretched fabric and the time is taken when the drop is completely impregnated (no more reflectance on the surface) . An average value of 3 measurements was taken.

II. Results II.l Determination of loosening and shrinkage of felting in the washing of wool samples II.1.1 Wool cloth samples, knitted, treated with plasma The results of loosening and shrinkage of felting, of samples of wool Wool treated with plasma, with a size of 225x300 mm, treated with the enzyme and buffer, respectively, are listed in Table 1 (lx7A, 2x5A) and in Table 2 (lx7A, 5x5A).

Table 1: Relaxation (lx7A) and shrinkage of felting (2x5A) of the wool samples treated with plasma, treated with NOVOZYM 654, 0.166% (owf), respectively damped, for 120 minutes (sample size 225x300 mm).

Samples Relaxation /% shrinkage of shrinkage of felting /% area /% EncogiX /% Relaxing Shrinkage Width Length Width Length of the total Total /% Reference fabric 4.78 -11.32 1.11 -17.54 -6.00 -16.24 -22.24 5.95 -11.92 0.01 -17.05 -5.26 -17.04 -22.30 -22.27 Fabric treated with plasma 5.90 -12.27 5.90 -12.62 -5.65 -5.98 - 11.63 5.72 -12.27 6.23 -12.69 -5.85 -5.67 -11.52 -11.6 Plasma + shock absorber 5.08 -8.09 5.32 -12.13 -2.60 -6.16 -8.76 4.09 -7.99 4.69 -10.77 -3.57 -5.57 -9.14 -8.95 Plasma + enzyme 5.29 -8.36 3.95 -8.45 -2.63 -4.17 -6.80 3.77 -6.63 4.35 -9.23 -2.61 -4.48 -7.09 -6.95 Table 2: Relaxation (lx7A) and shrinkage of felting (5x5A) of the wool samples treated with plasma, treated with NOVOZYM 654 0.166% (owf), respectively damped, for 120 minutes (sample size 225x300 mm).

Shrinkage shrinkage samples of 'felted /% area /% EncogiX /% Relax Shrinkage Width Total length /% Reference -10.80 -30.39 -6.00 -44.47 -50.47 50.20 -10.73 -30.63 -5.26 -44.65 -49.91 Plasma 1.89 -18.06 - 5.65 -15.98 -21.48 2.33 -17.00 -5.85 -14.30 -20.15 -20.82 Plasma + shock absorber 7.87 -18.22 -2.60 -8.92 -11.52 7.37 -18.20 -3.57 -9.49 -13.06 -12.30 Plasma + ezima 6.32 -12.72 -2.63 5.60 -8.23 6.88 -14.02 -2.61 -6.18 -8.79 -8.51 The relaxation and shrinkage of felting of the larger samples of wool are listed in Table 3 and 4. Table 3: Relaxation (lx7A) and shrinkage of felting (2x5A) of reference samples / wool treated with plasma, - - treated with NOVOZYM 654, 0.166% (owf), respectively damped, for 120 minutes (sample size 300x400 mm).

Samples Relaxation /% shrinkage of enfolétrate /% area /% EncogiX /% Relax- Shrinkage Width Length Width Total length Total /% Reference + 3.74 -6.21 0.90 -16.76 -2.24 -15.71 -17.95 Plasma damper + shock absorber 2.28 -4.86 6.01 -13.50 -2.47 -6.68 -9.15 Reference + enzyme 2.84 -3.95 1.95 -14.21 -1.0 -11.98 -12.98 1.20 -3.69 4.56 -15 72 -2.45 -10.44 -12.89 -12.94 Plasma + enzyme 2.11 -4.26 4.34 -7.45 -2.06 -2.79 -4.85 1.93 -3.29 5.79 -9.25 -1.29 -2.92 -4.21 -4.53 Table 4: Relaxation (lx7A) and shrinkage of felting (5x5A) of reference samples / plasma treated wool, treated with NOVOZYM 654, 0.166% (owf), respectively damped, for 120 minutes (sample size 300x400 mm).

From these results it can be deduced that the enzymatic treatment leads to a further reduction of the shrinkage of felting of the wool treated with plasma. In the case of the samples of 225x300 mm, the additional reduction reaches 40% (22.8% for the treatment with shock absorber) and, in the case of the samples of 300x400 mm, it increases to 61% (21% for the treatment with shock absorber), for the 2x5A test. But also, in the case of knitted wool fabric, the shrinkage of felting is reduced by the enzymatic treatment. Samples of knitted fabric, reference and those treated with plasma (300x400 mm, double seam), were also treated with NOVOZYM 654 0.83% (owf) for 120 and 60 minutes. The results of loosening and shrinkage of felting are listed in Tables 5A through d. Table 5a: Relaxation (lx7A) and shrinkage of felting (2x5A) of reference samples / wool treated with plasma, treated with NOVOZYM 654 0.83% (owf), respectively damped, for 120 minutes (sample size 300x400 mm). Samples Relaxation /% Shrinkage of enfilade /% area /% EncogiX /% Relax Shrinkage Width Length Width Total length /% Reference + 2.23 -6.15 1.02 -18.05 -3.78 -16.85 -20.63 Plasma damper + shock absorber 1.64 -6.77 7.32 - 10.17 -5.02 -2.11 -7.13 Reference + enzyme 2.08 -6.77 3.41 -15.24 -4.96 -11.31 -16.27 1.72 -5.65 3.04 -14.48 -3.45 -11.00 -14.45 -15.36 Plasma + enzyme 1.72 -5.55 4.85 10.31 -3.73 -4.96 -8.69 3.38 -6.68 4.00 -8.24 -3.07 -4.13 -7.20 -7.95 Table 5b: Relaxation (lx7A) and shrinkage of felting (2x5A) of reference samples / wool treated with plasma, treated with NVOZYM 654 0.83% (owf), respectively damped, for 60 minutes (sample size 300x400 mm).

Samples Relaxation /% shrinkage of enfolétrate /% area /% EncogiX /% relax- shrinkage width length width total length of the total /% reference + 1.99 -5.57 0.87 -17.33 -3.47 -16.31 -19.78 shock absorber Plasma + shock absorber 1.18 -7.60 6.00 -11.38 -6.33 -5.12 -11.45 Reference + Enzyme 0.85 -4.18 4.30 -14.92 -3.29 -9.98 -13.27 1.10 -1.19 2.89 -16.87 -0.08 -13.49 • 13.57 -13.42 Plasma + enzyme 4.00 -6.30 3.70 -7.56 -2.05 -3.58 -5.63 1.27 -4.77 5.46 -7.79 -3.44 -1.90 -5.34 -5.49 Table 5c: Relaxation (lx7A) and felting shrinkage (5x5A) of the reference samples / plasma treated wool, treated with NOVOZYM 654 0.83% (owf), respectively damped, for 120 minutes (sample size 300x400 mm).

Samples Shrinkage shrinkage of filler /% area /% EncogiX /% Relax- Shrinkage Anchorage Length Total /% Reference + -9.91 -29.41 -3.78 -42.23 -46.01 Damper Plasma + damper 7.69 -16.22 -5.02 -7.28 -12.30 Reference + enzyme -5.01 -24.13 -4.96 -30.35 -35.31 -5.50 -24.73 -3.45 -31.59 -35.04 -35.2 Plasma + enzyme 8.78 -14.68 -3.73 -4.61 -8.34 5.96 -11.56 -3.07 -4.91 -7.98 -8.2 Table 5d: Relaxation (lx7A) and shrinkage of felting (5x5A) of the reference / wool samples treated with plasma, treated with NOVOZYM 654, 0.83% (owf), respectively damped, for 60 minutes (sample size 300x400 mm) Samples shrinkage shrinkage /% area /% EncogiX /% relax- shrinkage width total length /% Reference + -12.09 -29.63 -3.47 -45.30 -48.77 cushion Plasma + shock absorber 5.70 -18.35 -6.33 -11.60 -17.93 Reference + enzyme -3.60 -24.91 -3.29 -29.41 -32.70 -3.24 -25.77 -0.08 -32.36 -32.44 -32.6 Plasma + enzyme 8.16 -13.42 -3.44 -4.16 -7.60 5.72 -12.39 -2.05 -5.96 -8.01 -7.8 In the case of the test (2x5A), the shrinkage reduction caused by the enzymatic treatment of the untreated wool fabric reaches 25%. In the case of incubation, of the treated wool are plasma, with NOVOZYM 0.83% owf for 120 minutes, the shrinkage was not reduced, but it was slightly reinforced. On the contrary, if the treatment time is reduced to 60 minutes with NOVOZYM 654 0.83%, the total shrinkage is reduced by 50%. Using higher concentrations of enzyme, the treatment time is decisive for the antifreeze effect. .1.2 woven cloth treated according to the Delhey process These tests were carried out on woven cloth. The results on the relaxation and the shrinkage of felting of Delhey samples with a size of 300x300 mm (280x280 mm), treated with enzymes / buffer, are shown in Table 6. Table 6a: Relaxation (lx7A) and shrinkage of felting ( 2x5A) of the Delhey or untreated samples, treated with NOVOZYM 654 0.166% (owf) or buffer, respectively, (sample size 280x280 mm). Samples Relaxation /% shrinkage of shrinkage of felting /% area /% EncogiX /% Relaxing Shrinkage Width Length Width Total length of total /% Reference untreated -2.53 -2.63 -12.00 -8.80 -5.23 -21.95 -27.18 -2.69 -2.72 -12.49 -7.70 -5.48 -21.15 -26.63 -26.91 Reference treated with 0.24 -1.60 -2.30 -5.16 -1.36 -7.58 -8.94 Delhey method -0.24 -1.09 -2.23 -4.90 -1.33 -7.24 -8.55 -8.75 Delhey treated method 0.05 -0.89 -1.34 -3.62 -0.84 -5.01 -5.85 with shock absorber 0.35 -0.85 -1.52 -4.21 -0.50 -5.79 -6.29 -6.07 (120 ') Delhey method treated 0.24 -0.24 0 -1.96 -0 -1.96 -1.96 with enzyme (120 '), 0.90 -0.05 0 -1.89 0.95 -1.89 -0.94 -1.45 0.166% Table 6b: Relaxation (lx7A) and shrinkage of felting (5x5A) of Delhey or untreated samples, treated with NOVOZYM 654 0.166% (owf) or buffer, respectively, (sample size 280x280 mm).

Samples Shrink Shrinkage of felting /% area /% EncogiX /% Relax Shrinkage Width Total length /% Reference not treated -31.10 -28.02 -5.23 -67.83 -73.06 -31.19 -25.98 -5.48 -65.27 -70.75 -71.9 Reference treated with -12.02 -16.31 -1.36 -30.29 -31.65 Delhey method -10.83 -16.92 -1.33 -29.58 -30.91 -31.3 Delhey method treated -8.41 - 11.81 -0.84 -21.21 -22.05 with shock absorber -10.61 - 14.50 -0.50 -26.65 -27.15 -24.6 (120 ') Delhey method treated -1.80 -7.00 -0 -8.93 -8.93 with enzyme (120), - 1.50 -6.52 0.95 8.11 -7.16 -8.0 0.166% 2x5A: The treatment according to Delhey reduces the total shrinkage of the woven fabric already used in approximately 70%. By the enzymatic treatment (120 minutes, 0.166% owf of the enzyme) the shrinkage is further reduced by more than 80%. The total shrinkage reduction achieved with the combined process adds up to 95%.

II.2 Degree of whiteness The two different dimensions of the sample of the knitted fabric result in the conclusion that, in the case of samples of 300x400 mm (double thickness), the rinsing with water of the key after the enzymatic treatment it was less effective, which is recorded in the lower degree of whiteness of the samples treated with enzyme (Table 7a) and in an increase in weight after treatment (not registered). It appears that the residual fragments of enzyme and protein were inactivated, but not completely removed from the fabric. Therefore, the wool samples were treated and rinsed in a single thickness cloth. In addition, the rinse was carried out on the Ahiba Turbocolor machine, where the tap water is compressed through the fabric (Table 7b). Table 7c lists the results of the whiteness measurements for woven fabric samples, treated according to Delhey / 1 / and post-treated with enzyme / buffer.

- - Table 7: Degree of whiteness of the material treated with plasma, the reference material and the material post-treated with enzyme. a) 300x400 mm, knitted fabric treated and washed, double-stitched: time • t, concentration -CIE ^ -CIE X of the enzyme references not treated 2.3 plasma 1.4 120 minutes 0.166% untreated owf 1.9 -0.4 1.9 - 0.4 -0.4 plasma 0.3 -1.1 0.5 -0.9 -1.0 60 minutes 0.83% untreated owf -2.2 -4.5 -2.1 -4.4 -4.5 plasma -2.9 -4.3 -2.0 -3.4 -3.9 120 minutes 0.83% untreated owf -2.8 - 5.1 -2.2 -4.5 -4.8 plasma -2.2 -3.6 -3.3 -4.7 -4.2 - - time, concentration W-CIE ¿^ W-CIE X of the enzyme references, treated with shock absorber 120 minutes untreated -0.1 -2.4 plasma, 60 minutes 0.5 -0.9 untreated -0.1 -2.4 plasma 0.6 -0.8 b) 225x300 mm knitted fabric treated in a single layer and washed in double layer samples W-CIE W-CIE reference treated with plasma 1.4 plasma fabric treated with shock absorber (120 minutes) 1.7 0.3 plasma fabric treated with enzyme ( 120 minutes, 0.166% Novozym 654 owf) 4.0 2.6 c) Delhey process, woven cloth 280x280 mm samples W-CIE A -CIE reference untreated 15.5 Delhey treated reference 9.6 -5.9 Delhey treated with shock absorber (120 minutes) 15.8 0.3 Delhey treated with enzyme (120 minutes, 0.166% Novozym 654 owf ) 27.8 12.3 In contrast to the enzymatically treated double layer samples, the plasma wool samples treated with plasma, treated in a single layer with enzymes, show a reinforced degree of whiteness, compared to the reference. After the Delhey process (performed as given in 1.4), the degree of whiteness of the samples is less than that of the corresponding reference. The values were increased again by the following treatment with buffer; and after the enzymatic treatment, the degree of whiteness was increased by a W-CIE value of 12.3.

II.3 Staining capacity of the samples The treated fabrics were stained with Lanasol Blue 8G, comparatively with the corresponding reference, and the color differences (DL values) of the respective pairs of - the samples were measured (Table 8).

Table 8: Color differences of the samples and references dyed in competition.

Samples DL corresponding reference / sample Woven Fabric not treated / treated by the Delhey method -10.2 Delhey treated with buffer / Delhey -7.1 treated with enzyme treated by the Delhey / Delhey method -4.0 treated with enzyme Non-treated / enzyme-treated cloth of the genus -6.1 plasma / plasma treated with -3.6 buffer, 120 minutes plasma treated with buffer / plasma -0.5 treated with enzyme (0.166%, 120 minutes) The greatest difference in the uptake of the dye is observed in the case of the fabric treated with the Delhey method, compared with the untreated fabric. The samples treated by the Delhey method enzymatically show a higher uptake than the reference treated with the Delhey method. In the case of the samples treated with plasma, the uptake of the dye is further reinforced by the enzymatic treatment.

II.4 Evaluation of the touch In general, the tact of the samples treated with enzyme is better than that of the reference. Therefore, a tendency is observed and perceived that the samples become smoother, with an increase in the concentration of the enzyme. In these cases, the treatment time plays a minor role.

II.5 Wettability The samples that were used in the staining test (II.3) were also evaluated for wettability (Table 9). In this test it became obvious that either the plasma treatment or the capillary forces along the fabric were not equal. It could also be possible that dry cleaning, before plasma treatment, was not effective enough. In the case of the knitted fabric treated only with plasma, e.g., three different values for rinsing were measured (11.3 minutes, 10 seconds, 5.45 minutes). Both sides of the fabric were evaluated. The fabric is heterogeneous with respect to wettability only in the case of the fabric treated with plasma post-treated with the enzyme soaking was rapid and equal (50, 45 and 42 seconds). But, only for one side of the fabric. During enzymatic binding, the fabric became entangled around the support in the staining machine. Consequently, part of the fabric is more exposed to liquor even though the liquor is pumped (from the outside in) through the roller. This may be the reason for the different wettability behavior of the samples post-treated with the enzyme. The samples treated by the Delhey process medium do not show rapid soaking but the wettability is reinforced, compared to the untreated reference Table 9: Results of the wettability test for wool samples that were treated differently.

Knitted fabric: I-V I: treated with enzyme (0.166%, 120 minutes) II: untreated III: plasma fabric treated with the enzyme (0.166%, 120 minutes) - - IV: plasma fabric treated with shock absorber (120 minutes) V: treated with plasma Woven fabric: VI-IX VI: fabric of the Delhey method treated with enzyme (0.166%, 120 minutes) VII: Delhey method treated with shock absorber (120 minutes) VIII: treated with Delhey - IX method: untreated.

It is noted that, in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or substances to which it refers. Having described the invention as above, the content of the following is claimed as property.

Claims (27)

1. A method for producing animal hair or fabric material with improved properties, characterized in that it comprises the steps of: a. treating the wool material, wool fibers or animal hair in a process selected from the group consisting of plasma treatment processes and the Delhey processes; and b. subject the material of wool or animal hair to a treatment with a proteolytic enzyme (a protease), in an effective amount to improve the properties.

2. The method, according to claim 1, characterized in that the plasma treatment is a low temperature treatment, preferably a corona discharge treatment or a luminescent discharge treatment.

3. The method, according to claim 1, characterized in that the process is the Delhey process.

4. The method according to claim 2, characterized in that the improved property of the woolen or animal hair material produced is an improved anti-shrink or antifreeze property, preferably corresponding to a shrinkage area of less than 10%, more preferably less than 8%, more preferably less than 7%, more preferably less than 5%, even more preferably less than 3%, especially less than 2%, after 2 ISO 5A cycles, or to a shrinkage area of less than 15%, more preferably less than 10%, more preferably less than 8%, even more preferably less than 6%, especially less than 5%, after 5 cycles of ISO 5A measured in accordance with Test Method IWS 31, or with a density of felt ball at, or below, 0.04 measured according to the Aachen felt ball test IWTO-20-69.

5. The method according to claim 3, characterized in that the improved property of the woolen or animal hair material produced is an improved anti-shrink or antifreeze property, preferably corresponding to a shrinkage area of less than 25%, more preferably less than 20%, more preferably less than. 15%, more preferably less than 12%, more preferably less than 10%, more preferably less than 8%, even more preferably less than 5%, especially less than 2%, after 2 ISO 5A cycles or less shrinkage area at 20%, more preferably less than 15%, more preferably less than 12%, even more preferably less than 10%, especially less than 9%, after 5 ISO 5A cycles measured in accordance with Test Method IWS 31.

6. The method, according to claim 2 or 4, characterized in that the improved property of the wool or animal hair material produced is an improved degree of whiteness, preferably corresponding to an improvement of at least 8 CIÉ units, more preferably of minus 10 CIÉ units, measured in a Datacolor 3890 spectral photometer (CIELAB system).

7. The method according to claim 3 or 5, characterized in that the improved property of the wool or animal hair material produced is an improved degree of whiteness, preferably corresponding to an improvement of * at least 10 CIÉ units, more preferably from at least 12 CIÉ units, measured in a Datacolor 3890 spectral photometer (CIELAB system).

8. The method according to any of claims 1 to 7, characterized in that the improved property of the animal wool or animal hair material produced is an improvement in the staining capacity, preferably corresponding to an increase in the color hue in the minus 2 DL (units), more preferably at least 3 DL units measured with respect to an untreated reference after competitive staining in 2% Lanasol Blue 8G.

9. The method according to any of claims 1 to 8, characterized in that the loss of toughness of the volumetric strength of the woolen or animal hair material produced, compared to the toughness of the volumetric strength of the untreated material, preferably it is less than 20%, more preferably less than 10%, more preferably less than 8%, especially less than 6%, measured in accordance with IWTO-32-82.

10. The method according to any one of claims 1 to 9, characterized in that the improved property of the wool or animal hair material produced is an improved softness, preferably a softness corresponding at least to the softness of the untreated wool.

11. The method according to any one of claims 1 to 10, characterized in that the improved property of the wool or animal hair material produced is a lower tendency to ball.

12. The method according to any of claims 2, 4, or 6 to 11, characterized in that the plasma treatment at low temperature is carried out using a gas selected from the group consisting of air, oxygen, nitrogen, ammonia, helium or argon .

13. The method according to any of claims 2, 4, or 6 to 12, characterized in that the plasma treatment at low temperature is carried out from about 2 seconds to about 300 seconds, preferably for about 5 seconds to about 100 seconds, more preferably from about 5 seconds to about 30 seconds and / or at a pressure between about 0.1 torr and 5 torr.

14. The method according to any of claims 1 to 13, characterized in that treatment with a proteolytic enzyme is preferably carried out for a time between about 1 minute and about 120 minutes; and / or preferably at a temperature between about 20 ° C and about 70 ° C, more preferably between about 30 C and about 60 C, especially between about 40 ° C and about 60 ° C.

15. The method according to any of claims 1 to 14, characterized in that the treatment with a proteolytic enzyme is carried out in an acidic or neutral, or alkaline medium, optionally in the presence of one or more anionic, nonionic or cationic surfactants.

16. The method according to any of claims 1 to 15, characterized in that the wool or animal hair material is further subjected to an ultrasonic treatment, either before or at the same time as the treatment with a proteolytic enzyme.

17. The method according to any of claims 1 to 16, characterized in that the wool or animal hair material is subjected to a treatment with a softener or softening agent, either simultaneously with the treatment with a proteolytic enzyme or after plasma treatment and treatment with a proteolytic enzyme.

18. The method, according to any of claims 1 to 17, characterized in that the proteolytic enzyme is of plant origin, such as papain, bromelain and ficin or of animal origin, such as trypsin.

19. The method according to any of claims 1 to 17, characterized in that the proteolytic enzyme is of microbial origin, such as a microbial protease, a fungal protease and a protease that can be produced or that can be derived from the yeast.

20. The method according to claim 19, characterized in that the proteolytic enzyme is a serine protease, preferably a subtilisin, more preferably a subtilisin derived from Bacillus or Tritirachium album.

21. The method, according to claim 20, characterized in that the serine protease is selected from subtilisin PB92, subtilisin 309 and subtilisin 147.

22. The method according to claim 21, characterized in that the serine protease is a variant of subtilisin of subtilisin 309, which has the glycine in position 195 substituted with phenylalanine (G195F).

23. The method according to claim 20, characterized in that the serine protease can be produced or can be derived from a strain of B. licheniformis, B. alkalophilus, B. cereus, B. natto, B. vulgatus or B. mycoide .

24. The method according to claim 20, characterized in that the serine protease is a protease that can be produced or that can be derived from a strain belonging to a genus selected from Nocardiopsis, Aspergillus, Rhizopus and Mucor.

25. The method according to claim 24, characterized in that the protease can be produced by or can be derived from a strain of Nocardiopsis sp. , or Nocardiopsis dassonvillei, preferably from a strain of Nocardiopsis sp., more preferably from Nocardiopsis sp. , NRRL 18133.

26. The method according to any of claims 1 to 25, characterized in that the amount of proteolytic enzyme is preferably between about 0.2% w / w and about 10% w / w, based on the weight of the wool or hair material of animal.

27. The wool or animal hair material, characterized in that it has been treated in accordance with the method of any of claims 1 to 26.