MXPA99009840A - Enzymatic stone-wash of denim using xyloglucan/xyloglucanase - Google Patents

Abstract

A new method of manufacturing a fabric or a garment with a stone-washed or worn look, the method comprising coating the yarn or fabric or garment with a polymer, e.g. a xyloglucan, prior to dyeing and afterwards creating the abraded or worn look by enzymatic degradation of said polymer, e.g. by using a xyloglucanase.

Description

STYLE, ENZYMATIC, MIXTURE WASH TYPE USING XILOGLUCAN / XYLOGLUCANASE FIELD OF THE INVENTION The present invention relates to a new method for manufacturing a fabric or a garment with a worn or stone washed appearance, which results in no or very limited loss of strength of the fabric or the garment.

BACKGROUND OF THE INVENTION The popularity of denim fabrics among consumers of all ages has been well documented by sales in a large number of countries around the world. Denim is more often cotton clothing. A conventional dye for denim is the indigo dye that has a characteristic blue color, denim clothes dyed with indigo that has the desirable characteristic of alteration of the dyed threads, with white threads. REF .: 31782 that after normal wear and tear gives the denim a white-on-blue appearance. A popular look for denim is the appearance washed with stone or worn. Traditionally the washing with stones has been carried out by submitting to laundry of the material or garment of denim in the presence of pumice stones, which results in the fabric having a faded or worn appearance, with the appearance of contrast white on blue desired, described above. This appearance washed with stones consists mainly of removing the dye in a way to produce a material with areas that are lighter in color, while maintaining the desirable contrast of white or blue, and a material that is softer in color. its texture Enzymes, particularly cellulases, are currently used in the processing of dyed twill cloth, especially denim. In particular, cellulolytic enzymes or cellulases have been used as a replacement for or in combination with the pumice stones for the traditional "stone wash" process applied to give the denim a discolored appearance. The use of cellulases for stone washing has been become increasingly popular because the use of single stones has several disadvantages. For example, the stones used in the process cause wear and tear on the machinery, these cause problems of environmental waste due to the grain produced, and result in high labor costs associated with the manual removal of stones from garment bags To wear. Consequently, the reduction or elimination of the stones in the washing may be desirable. Contrary to the use of pumice stones, enzymes, particularly cellulases, are safe for machinery, result in few or no waste problems and drastically reduce labor costs. However, many cellulases. they have an activity towards insoluble cellulose, which can result in a reduced strength of the cellulosic fabric in question. An object of the present invention is to create an enzymatic process for the manufacture of a fabric or apparel with a "washed with stones" appearance, a "worn" appearance or any other shape appearance, known in the art based on the provision of cloth or garments with localized variation in color density, where the enzyme used does not have or only has very low activity towards insoluble cellulose. In particular, an object of the present invention is to create an enzymatic process for the manufacture of a fabric or garment with a "stone washed" appearance, a "worn" appearance or any other fashionable appearance known in the art. , by coating the yarn or the fabric or the garment with a polymer before dyeing and thereafter creating the worn or abraded appearance, by degradation of the polymeric coating.

BRIEF DESCRIPTION OF THE INVENTION It has now become possible in a surprising manner to manufacture a fabric or garment with a washed or washed appearance, wherein the manufacturing methods result in a very limited loss of strength of the fabric or garment involved. .

Accordingly, the present invention relates to a method for manufacturing, with a very limited loss of strength, a fabric with a washed or worn appearance, comprising: a) coating the yarn with a biodegradable polymer, by placing contact the thread with a solution of the polymer; b) the yarn dyeing; c) optionally coating the yarn with a sizing agent; d) the fabric of the yarn to form a fabric; e) the optional desizing of the fabric; and f) treating the fabric with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only very low activity towards insoluble cellulose. Yet another embodiment of the present invention relates to a manufacturing method, with a very limited loss of strength, of a fabric with a washed or worn-out appearance, comprising: a) coating the fabric with a biodegradable polymer by contacting the fabric with a solution of the polymer; b) the dyeing of the fabric; c) treating the fabric with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose; and d) optional cutting and sewing of the fabric to form a garment. Yet another embodiment of the present invention relates to a method for manufacturing, with a very limited loss of strength, of a garment with a washed or worn appearance, comprising: a) coating the yarn with a biodegradable polymer , by contacting the yarn with a solution of said polymer; b) the yarn dyeing; c) the optional coating of the yarn with a preserving agent; d) the weaving of the yarns to form a fabric; e) cutting and sewing the fabric to form a garment; f) the optional detachment of the garment; and g) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose. - Still another embodiment of the present invention relates to a method for the manufacture of a garment, with a very limited loss of strength, with a washed-out or worn-out appearance, comprising: a) coating the fabric with a biodegradable polymer, by contacting the fabric with a solution of said polymer; b) the dyeing of the fabric; c) cutting and sewing the fabric to form a garment; and d) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and does not have or only has a low activity towards insoluble cellulose. Yet another embodiment of the present invention relates to a method of manufacturing, with a very limited loss of strength, of a garment with a washed or worn appearance, comprising: a) coating the garment with a biodegradable polymer, by contacting the fabric with a solution of said polymer; b) the dyeing of the garment; c) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the first step in this new method of manufacturing a fabric or garment with a washed or worn appearance is to coat the yarn or fabric or garment with a biodegradable polymer.

A characteristic feature of the polymer for use in this invention is that it must be capable of strongly bonding to the surface of the fibers, yarns, fabrics or garments in question. The biodegradable polymer can typically be a xyloglucan polymer, because xyloglucan binds very strongly to cellulose.

Xyloglucans Xyloglucans appear widely in the primary cell walls of higher plants, where they are bound in close association with cellulose microfibrils. Xyloglucans are linear chains of (1-> G) -D-glucan, but, contrary to cellulose, have numerous xylosyl chain units aggregated at regular sites of the 0-6 position of the chain's glucosyl units (Carpita, NC &Gibeaut, DM (1993): The plant Journal, 3, pp 1-30). Species-specific differences occur as for the distribution of additional fucosyl-galactosyl residues in branching (Hayashi, T. &Maclachlan, G. (1984): Plant Physiol., 75, pp. 596-604). For example tamarind xyloglucan is not fucosylated (Vincken, J.-P. (1996): Enzymatic Modification of Cellulose Networks-Xyloglucan, Thesis of the Agricultural University of Wageningen). The commercially available xyloglucan can be purchased in a purified form of Megazyme (Australia) or as raw polygal tamarind bone powder (POLYGUM 55). According to the present invention, xyloglucan obtained from monocotyledons and / or dicots is preferred, in particular tamarind seeds. The xyloglucan used according to the invention can also be a chemically or enzymatically modified xyloglucan.

Coating with a biodegradable polymer According to the invention, the yarn or cloth or article of clothing is brought into contact with a solution of a biodegradable polymer. This can be done as follows: Initially a biodegradable polymer solution is prepared (eg, a xyloglucan solution), the concentration of which depends on the purity of the biodegradable polymer. Typically the biodegradable polymer solution has a concentration of about 0.05% (w / v) to about 50% (w / v). Purified xyloglucan solutions can be prepared in concentrations in the range of about 0.05% (w / v) to about 10% (w / v). Raw xyloglucan solutions, for example, in the form of tamarind seed powder, can be prepared in concentrations in the range of 0.25% to 50% (w / v). The xyloglucan can be added to the warp yarn by methods usually applied for warp preparation such as a conventional glue, as a foam in a horizontal pad system, as a foam in a roller blade system, or alternatively using wetting boxes or similar rinsing, normally applied before coloring or dyeing.

The coating can be carried out before wetting, simultaneously with wetting or after the wetting process. Depending on the purity of the source of xyloglucan a rinsing procedure before dyeing may be included. A source of xyloglucan such as raw tamarind seed powder will contain impurities other than xyloglucan such as pectin, starch, protein, fat and waxes that may have a negative impact on the adsorption of the dye. The rinse can be a hot rinse or a cold rinse in water, optionally containing a surfactant (for example 0.05-5 g / 1).

Had The next step in the method according to the invention is the dyeing of the yarn or cloth or garment. Preferably, the dyeing of the yarn is a ring dyeing. A preferred embodiment of the invention is the ring dyeing of the yarn with a vat dye such as indigo, or a dye related to indigo such as thioindigo, or a sulfur dye, or a direct dye, or a dye. reactive dye, or a naphthol. The yarn can also be dyed with more than one colorant, for example, first with a sulfur dye and then with a dye to the tub, or vice versa. Indigo can be derived from the indigo, or synthetic, plant material, or the biosynthetic indigo available from Genencor International. The warp yarn can be dyed according to methods known in the art, typically by using a continuous process in which the yarn is repeatedly immersed in dye baths containing the dye in question (for example indigo in reduced form (leuco)).

After each immersion, the indigo is oxidized by exposing the yarn to oxygen (a process known as the oxidation to the air of indigo). Alternatively, the indic can be oxidized with other oxidizing agents as is known in the art. The dyeing can be carried out in the following way: Initially the dry warp yarn is pre-wetted, typically the wetting mixture contains a wetting agent, a chelating agent and sodium hydroxide.

The dyebath typically has the following composition: 4 kg indigo resin BASF Pulver K 0.2 kg Primasol FP (from BASF) 30 liters water preheated to 70-80 ° C 6.5 liters sodium hydroxide 38 ° Bé 3 kg of sodium hydrosulfite The volume is adjusted to 50 liters, and the solution is maintained at 50 ° C for 30 minutes. From this stock solution can be prepared a dyeing bath of 1000 liters: 940 liters of water 2-3 liters of sodium hydroxide 38 ° Bé 1.5-2 kg of sodium hydrosulfite 0.5-1 kg of Setamol WS (from BASF) 50 liters of reserve solution The warp yarn can then be immersed in the dyeing bath for 5 to 60 seconds, squeezed, and oxidized in the air for 1-3 minutes. The treatment can be performed as 4 dives, 8 dives, or other degrees of treatment as is known in the art. After the dyeing operation the dyed yarns are optionally prepared before being woven.

Dressing agents The preparation can be any preparation agent known in the art, for example, derived from natural polymers, such as starches, modified starches, starch derivatives or cellulose derivatives, or synthetic polymers, such as polyvinyl alcohol, polyvinyl acetate, etc. . The threads are then made into fabrics as is known in the art.

Fabrics The invention is more benignly applied to cellulosic or cellulose-containing fabrics, such as cotton, viscose, rayon, ramie, linen, lyocell (for example Tencel, produced by Courtaulds Fibers), or mixtures thereof, or mixtures of any of these fibers together with synthetic fibers (for example polyester, polyamide, nylon) or other natural fibers such as wool and silk. In particular, the fabric is a twill, preferably denim.

After weaving, the fabric is optionally cut and sewn to form a garment. If the garment or cloth was sizing, it can now undergo a desizing process as is known in the art.

The desaturation process In a preferred process of the invention, conventional desizing enzymes, in particular amylolytic enzymes, are used in order to eliminate the starch-containing preparation. Therefore, an amylolytic enzyme, preferably an α-amylase, can be added during the process of the invention. Conventionally, bacterial α-amylases are used for desizing, for example, an α-amylase derived from a strain of Bacillus, particularly a strain of Bacillus li cheniformi s, a strain of Ba cillus amyl oli quefaci ens , or a strain of Bacill us s tearo thermophi l us; or mutants thereof. Examples of commercially available α-amylase products are Termamyl ™, Aquazym ™ Ultra and Aquazym ™ MR [available from Novo Nordisk A / S, Denmark). However, fungal a-amylases can also be used. Examples of fungal α-amylases are those derived from a strain of Aspergillus. Other useful α-amylases are the oxidation-stable α-amylase mutants described in International Patent WO 95/21247. The amylolytic enzyme can be added in conventional amounts used in the desaturation processes, for example, corresponding to an α-amylase activity of about 100 to about 10,000 KNU / liter. Also, in the process according to the present invention, 1 to 10 mM Ca ++ can be added as a stabilizing agent. The fabric or garment can be desized as follows: If starch is used as the dressing agent, an amylase can be applied as a desizing agent: The processing conditions can be 60 to 70 ° C and the pH of 6 to 8 for 10 to 15 minutes, using 2 to 3 grams of Aquazyme 120L (from Novo Nordisk A / S) / liter at a liquor ratio of 5: 1-10: 1. A wetting agent compatible with the amylase can be added to the wash liquor.

Various other desizing methods known in the art may alternatively be applied. Before the finishing process is applied (for example, the "stone washing" process), a hot or cold rinse may optionally be included. The step of finishing process according to the invention is carried out by the use of an enzyme that is capable of degrading the biodegradable polymer. An example of such an enzyme is a xyloglucanase.

Xyloglucanases According to the present invention, a xyloglucanase is defined as an enzyme having an activity towards the substrate xyloglucan. Preferably, the xyloglucanase according to the invention is produced by microorganisms such as fungi or bacteria. Examples of useful xyloglucanases are the endoglucanases that hydrolyze the xyloglucan of the family 12, in particular the endoglucanases that hydrolyze the xyloglucan of the family 12, such as obtained, for example, from Aspergill us as described in International Patent WO 94/14953. Another useful example is a xyloglucanase produced by Tri ch oderma, especially EGIII. Xyloglucanase can also be an endoglucanase with xyloglucanase activity and low activity towards insoluble cellulose, and high activity towards soluble cellulose, for example, endoglucanases of family 7 obtained for example from Humi cola insol ens. The xyloglucanase used can also be an enzyme whose activity has been improved during the addition of a binding domain to cellulose to said enzyme. According to the present invention, the enzyme that is capable of degrading the biodegradable polymer can be added at a concentration of 0.1-25000 μg of protein enzyme / gram of cloth or article of clothing, preferably 0.1-10000 μg of protein enzyme / gram. of cloth or article of clothing, more preferably 0.5-1000 μg of protein enzyme / gram of cloth or article of clothing, in particular 0.5-500 μg of protein enzyme / gram of cloth or article of clothing.

Finishing process The chosen procedure will depend on the enzyme in question. If an endoglucanase which hydrolyzes the xyloglucan, from Aspergillus usulinus, described in WO 94/14953, the processing conditions could be from 30 to 60 ° C, pH 3-6 for 10 to 120 minutes, using 0.5 mg of enzyme / gram of cloth at a liquor ratio of 4: 1 to 20: 1. A surfactant compatible with the enzyme can be added to the wash liquor (for example Novasol P from Novo Nordisk A / S). Alternatively, the process can be performed using a combination of an endoglucanase that hydrolyzes xyloglucan and 0.25-1 kg of pumice stones / kg of pants. The conditions are similar to those described above. If pumice stones are used, there may be a reduced strength of the fabric or article of clothing in question. The denim processing can be carried out in any machinery known in the art, such as scrubbers (front or side loaded) or barrel washers.

Optionally, a hot or cold rinse can be included. Inactivation must be carried out in order to obtain sufficient denaturation of the enzyme used. The inactivation conditions can be from 70 to 100 ° C for 10 to 20 minutes, at pH above 90.5, but the inactivation conditions will of course depend on the specific enzyme in use. Additional finishing processes may be carried out as is known in the art, in order to clean the fabric or obtain a lighter blue shade. You can bleach with mild hydrogen peroxide to clean the fabric, using 1.5 grams of hydrogen peroxide at 35% / liter and 1 gram of soda ash / liter at a pH above 10, for 10 to 20 minutes, at a temperature in the range between 60 and 80 ° C. In addition, a sequestering agent (stabilizer) can be added, for example sodium silicate. A hot rinse is recommended subsequent to bleaching and surfactants can be added. To obtain a lighter blue shade you can bleach with hypochlorite, using 1 gram of sodium hypochlorite / liter and 1 gram of soda ash / liter at pH 9-11 for 10 minutes at 50 ° C. After a rinse, neutralization is carried out using 1.5 grams of sodium metabisulfite / liter for 10 minutes at 50 ° C. A short rinse is recommended, which may contain surfactants. Optionally, other finishing agents such as brighteners or softening agents can be used.

Xyloglucanase activity The activity of xyloglucanase can be measured as indicated below: A) Determination of residual sugar: (according to Vincken, J.-P. (1996): enzymatic modification of cellulose-xyloglucan networks, Thesis of the Agricultural University of Wageningen, pp. 13). A purified source of xyloglucan (for example from Megazyme, Australia) is dissolved in a suitable buffer (250 μg of xyloglucan in 100 μl of buffer) and incubated with 30-400 nanograms of enzyme for 1 or 20 hours. The increase in sugar Reducer is determined according to the Somogyi procedure using glucose for calibration. Other methods for determining the reducing sugar can be performed as set forth in Methods in Enzymology, vol. 160 (Ed Wood, WA &Kellogg, ST (1988), Academic Press Inc., pp 87-112), in which the enzyme concentrations and the incubation time must be adjusted to be within the sensitivity range of the analysis . B) Release of stained soluble fragments: A substrate of xyloglucan stained with azurine and crosslinked xyloglucan substrate (AZCL-xyloglucan) can be obtained from Megazyme Australia. A 0.2% w / v solution of xyloglucan is prepared in a suitable buffer. Incubation between 15-60 minutes with 0.005-1% w / v of enzyme. Enzyme activity is measured as the release of the soluble blue fragments after centrifugation, determined as the absorbance at 620 nm in the supernatant.

Amylolytic activity The amylolytic activity can be determined using potato starch as a substrate. This method is based on the breakdown of potato starch modified by the enzyme, and the reaction is followed by mixing the samples of the starch / enzyme solution with an iodine solution. Initially, a blackish / blue color is formed, but during starch break the blue color becomes weaker and gradually becomes reddish-brown, which is compared to a standard. of colored glass. A Kilo Novo unit of alpha amylase (KNU) is defined as the amount of enzyme which, under standard conditions (for example at 37 ° C + 0.05, Ca2 + 0.0003 M, and pH 5.6) dextrins 5.26 grams of the anhydrous substance of starch Merck soluble Amylum. The present invention is further illustrated in the following example which is not intended to limit the scope of the invention, as claimed.

EXAMPLE 1 Reflection measurements Reflection measurements that define the appearance of the fabric according to the invention were made at a wavelength of 420 nm using a reflectometer having a measuring diaphragm with a diametral dimension of 27 mm (Texflash 2000 from Datacolor International, source of light D65). All reflection measurements are expressed in% related to a white standard (100% reflection). The white standard used was a Datacolor International series No. 2118, white calibration standard. For calibration purposes, a black standard was also used (No. TL-4-405). Evaluation: The higher the value, the lighter the color.

Resistance to the breaking of the warp The standard test method for tear strength or breakage for fabrics woven by pendulum in fall (Elmendorf ADT D 1424 apparatus, using an Elmendorf Tear Tester, Twing-Albert Instrument Company, Philadelphia, USA 19154). However, due to the very high strength of the twill fabric, the dimensions of the cutting die have been reduced to 102 mm x 55 mm. The conditioning of the fabric has been achieved at 20 ° C and at 60% relative humidity for 24 hours before the test.

Loss / gain in weight The conditioning of the fabric has been achieved at 20 ° C and 60% relative humidity for 24 hours before weighing.

EXPERIMENTAL Thorough washing Fabric: 1 kg Greige cotton canvas, style No. 426 (Test Fabrics Inc.) Apparatus: Washing machine, Wascator FL 120 (Electrolux) 3% NaOH wash, 0.5 g Inkmaster 750 / liter bottom: (Rhone Poulenc), 90 ° C, 60 minutes, 12 liters of deionized water. Neutral: 2% acetic acid 100%, 50 ° C, 10 minutes, 12 liters of deionized water. Rinse: Twice in 12 liters of deionized water.

Coating of washed samples thoroughly with Polygum 55 (POLYGAL ag Switzerland): Fabric: 13x24 cm gender samples prepared from the washed cloth thoroughly. Polygum: 500 ml of three different solutions of Polygum 55 (POLYGAL) (0% w / v, 1.0% w / v and 5.0% w / v). Polygum 55 is dissolved in deionized water by heating to approximately 90 ° C and stirred cold overnight (magnetic stirrer). Coating 6 samples of gender are incubated in each : Polygum concentration for 30 minutes at room temperature. They are pressed using a squeegee (DSW Jupiter). The gender samples are dried by runoff. Rinsing: The elimination of impurities is carried out by rinsing the device Wascator FL 120 (Electrolux): A hot rinse in 32 liters of deionized water at 55 ° C for 5 minutes, and two cold rinses in 32 liters of deionized water at 15 ° C for 5 minutes. The gender samples are dried by runoff. Evaluation: The uptake of the polymer and the uptake of the polymer after rinsing is determined as the gain in weight as described above before and subsequent to the rinsing procedure, respectively.

Indigo dyeing of coated fabric samples Reserve solution: 8 g of indigo (BASF) 0.4 g of Primasol FP (BASF) 60 ml of deionized water at 50 ° C (stirring for two hours at 50 ° C) 0.6 g of NaOH 6.0 g of sodium hydrosulfite Final dyeing bath: 100 ml of reserve solution 1.5 g of Setamol WS (BASF) 3. 5 g of sodium hydrosulfite 5 ml of 50% NaOH 1880 ml of deionized water Process: Four polymer-coated samples are applied per concentration of Polygum 55 in the dyeing process. The coated specimens are pre-moistened in 1 liter / 5 g of Setamol WS / liter (BASF) for 5 to 10 minutes, and drained using a squeegee (DSW Jupiter). The gender samples are immersed in the bleaching bath for 20 seconds, squeezed and oxidized in the air for 120 seconds. This sequence is repeated 6 additional times (7 dives). The gender samples are pressed and dried by runoff overnight. Excess indigo is removed by rinsing in the Wascator FL 120 (Electrolux): A warm rinse in 32 liters of deionized water at 55 ° C for 5 minutes and two cold rinses in 32 liters of deionized water at 15 ° C per 5 minutes.

Evaluation : Dye uptake (determined as reflection, as described above) with six determinations / gender sample.

Enzyme treatment of the genre samples coated with the indigo dye: Apparatus: Launder-O-meter LP2 (Atlas Electric Devices Company) Fabric: Gender samples coated with indigo dye are stitched together to form a tube which is placed in the Launder-O-meter container, 1 sample of gender per container. Approximately 18 g / gender sample. Shock absorber: 50 ml of 50 mM citric acid, pH 5.0 is added to each container. Enzyme: A xyloglucanase (endoglucanase that hydrolyzes xyloglucan of family 12) obtained from Aspergillus aculeatus as described in International Patent WO 94/14953. The enzyme is dosed according to the experimental profile.

Time: 60 minutes. Temperature: 50 ° C Auxiliary 30 steel nuts (diameter 16 mm), 10 abrasive: steel nuts (diameter 10 mm), 10 star-shaped magnets (5 grams), 3 star-shaped magnets (3 grams) are added to each container and placed 'inside the cloth tube. Rinse: 2 times in 5 liters of deionized water for 5 minutes; drying by rotating drum. Evaluation: Abrasion is measured on the side of the fabric facing the inside of the launderometer vessel (determined as the reflection as described above) with six determinations / samples of gender; refl. Delta is calculated as (abrasion-uptake of dye). The tear strength is as described above, three determinations / gender sample.

RESULTS The results of the coating experiment with Polygum 55, described above, are described in Table 1.

Table 1 The uptake of the polymer increases with the increase of the concentration of Polygum 55 in the coating bath. The excess polymer is removed during the rinsing process. The results of the dyeing and finishing process are shown in Table 2. When the excess polymer is sufficiently removed in a rinsing process, the uptake of the dye is only slightly affected by the concentration of the polymer, and the dye is uniformly distributed over the fabric For each concentration of Polygum 55, a higher level of abrasion is obtained when a xyloglucanase has been added during the incubation, compared to a treatment without enzyme, thus resulting in a higher delta reflection (Delta refl). Therefore, it is possible to obtain the desired worn appearance on the serge dyed with indigo, by using the new method for dyeing twill. Surprisingly, the increase in delta reflection is not accompanied by a concomitant loss of resistance.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property:

Claims (31)

1. A method for manufacturing, with a very limited loss of strength, a fabric with a washed stone appearance or worn, characterized in that it comprises: a) coating the yarn with a biodegradable polymer, by contacting the yarn with a solution of said polymer; b) the yarn dyeing; c) the optional coating of the yarn with a dressing agent; d) the fabric of the yarn to form a fabric; e) the optional desizing of the fabric; and f) treating the fabric with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose.

2. A method according to claim 1, characterized in that the biodegradable polymer is xyloglucan polymer.

3. A xyloglucan polymer according to claim 2, characterized in that the polymer is obtained from monocotyledons and / or dicotyledons.

4. A xyloglucan polymer according to claim 3, characterized in that the polymer is obtained from tamarind seeds.

5. A method according to claim 1, characterized in that the dyeing is a ring dyeing.

6. A method according to claim 1, characterized in that the biodegradable polymer solution has a concentration of about 0.05% (w / v) up to about 50% (p / v).

7. A method according to claim 1, characterized in that the dyeing is carried out using a dye to the tub, a sulfur dye, a direct dye, a reactive dye or a naphthol.

8. A method according to claim 7, characterized in that the dye to the vat is indigo.

9. A method according to claim 7 or 8, characterized in that the dye to the tub is combined with a sulfur dye.

10. A method according to claim 1, characterized in that the fabric is a cellulosic material.

11. A method according to claim 10, characterized in that the cellulose fabric is twill.

12. A method according to claim 10, characterized in that the cellulose fabric is denim.

13. A method according to claim 1, characterized in that the enzyme is a xyloglucanase.

14. A method according to claim 1, characterized in that the enzyme is an endoglucanase that hydrolyzes xyloglucan of the family 12, obtained from Aspergillus acul ea t us.

15. A method according to claim 1, characterized in that the enzyme is an endoglucanase with xyloglucanase activity.

16. An enzyme according to claim 15, characterized in that the enzyme is an endoglucanase of the family 7 obtained from Humi col a insol ens.

17. An enzyme according to claim 1, characterized in that the enzymatic activity has been improved by the addition of a cellulose binding domain to said enzyme.

18. A method according to claim 1, characterized in that the sizing agent is a natural polymer.

19. A method according to claim 18, characterized in that the dressing agent is starch.

20. A method according to claim 1, characterized in that the desaturation is carried out with an amylase.

21. A method according to claim 1, characterized in that the biodegradable polymer solution is applied at a temperature of about 15 ° C to 90 ° C and at a pH of about 1 to about 12.

22. A method according to claim 1, characterized in that the biodegradable polymer solution contains a divalent cation.

23. A method according to claim 22, characterized in that the divalent cation is calcium.

24. A method according to claim 1, characterized in that the enzyme is added at a concentration of 0.1-10000 μg of protein enzyme / gram of cloth or article of clothing.

25. A method according to claim 24, characterized in that the enzyme is applied at a pH of about 2 to about 7 and at a temperature of about 30 ° C to about 70 ° C.

26. A method according to claim 1, characterized in that the aqueous medium contains a surfactant.

27. A method of manufacturing, with a very limited loss of strength, of a fabric with a washed stone appearance or worn, characterized the method because it comprises: a) the coating of the fabric with a biodegradable polymer, by contacting the fabric with a solution of said polymer; b) the dyeing of the fabric; c) treating the fabric with an effective amount of an enzyme in an aqueous medium, where the enzyme is able to degrade the polymer biodegradable, and does not have or only has a low activity towards insoluble cellulose; and d) optionally cutting and sewing the fabric to form a garment.

28. A method of manufacturing, with a very limited loss of strength, of a garment having the appearance of washing with stones or worn, characterized in that the method comprises: a) coating the yarn with a biodegradable polymer, by contacting the yarn with a solution of said polymer; b) the yarn dyeing; c) the optional coating of the yarn with a dressing agent; d) the weaving of the yarns to form a fabric; e) cutting and sewing the fabric to form a garment; f) the optional detachment of the garment; and g) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and does not have or only has a low activity towards insoluble cellulose.

29. A method for manufacturing a garment, with a very limited loss of strength, with a washed stone appearance or worn, characterized the method because it comprises: a) coating the fabric with a biodegradable polymer, by contacting the fabric with a polymer solution; b) the dyeing of the fabric; c) cutting and sewing the fabric to form a garment; and d) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose.

30. A method of manufacturing, with a very limited loss of strength, of a garment having the appearance of washed with stones or worn, characterized the method because it comprises: a) coating the garment with a biodegradable polymer, by contacting the fabric with a solution of said polymer; b) the dyeing of the garment; c) treating the garment with an effective amount of an enzyme in an aqueous medium, wherein the enzyme is capable of degrading the biodegradable polymer, and has no or only low activity towards insoluble cellulose.

31. A method according to claims 28, 29 or 30, characterized in that the garment is further finished by one or more of the following treatments: bleaching, over-dyeing, polishing, softening, or anti-wrinkle treatment.