MXPA00002876A - Treatment of cellulose fabrics with cellulases - Google Patents

Abstract

This invention relates to a cellulase treatment of cellulosic fabric to achieve biopolishing effects, reducing dust or lint and reducing pilling during at least one laundry cycle in said fabric comprising treating said fabric with cellulase after the scouring step and before the bleaching step.

Description

TREATMENT OF CELLULOSE FABRICS WITH CELLULASES FIELD OF THE INVENTION This invention relates to an improvement of the cellulase treatment of an undyed cellulose fabric, the improvement comprises the treatment of the fabrics with cellulase after the cleaning step and before the bleaching step. As a result, there will be a reduction in caking for at least one wash cycle in the fabrics compared to the prior art methods for the cellulase treatment.

BACKGROUND OF THE INVENTION The newer manufactured cotton fabrics and fabrics with cotton blends have a fairly hard and stiff texture unless they are treated with the finishing components. Moreover, the surface of the fabric is not always smooth due to the small protruding hair fibers that are formed from the individual cotton fibers. Moreover, after a relatively short period of use, collections of yarns appear on the surface (surface of yarns) that give the appearance of "bouncing" on the surface, which causes the fabric to look unattractive. In fabrics REF .: 32819 polyester, this phenomenon is currently "caked" and gives an unattractive similar appearance to the fabric. The term "caked" will also apply to cellulosic fabrics in the present application. The softness and smoothness of the fabric can be obtained by the use of finer yarns, which implies higher costs, in the manufacture of a given fabric. A second method, which is carried out in a first proposal is to use yarns prepared by the ring chain spinning process as opposed to the less expensive open-end process. However, the resulting cost is higher and the fabric that is produced decreases in accordance with the size of the yarn. A less expensive method of ensuring a smooth and smooth "texture" fabric is to impregnate the finished fabric with a softening agent, typically a cationic active surface compound, sometimes a silicone base. However, this treatment does not eliminate the bumps and lint. Moreover, the fabric acquires a "greasy" texture and is not wash-proof, and its moisture absorbency is considerably reduced. This proposal can have a negative influence on other wet stages of the process, notably in the cause of an undesirable pick up of dyes by the finished fabric.

Another known method for obtaining a soft and smooth fabric is to treat the cellulosic fabrics with cellulases. See Bazin et al., "Enzimatic Bio-Polishing of Cellulosic Fabric", presented at the 58th Congress of the Chemical and Textile Industry Association in Mulhouse, France (October 25, 1991) and Asferg et al., "Softening and polishing of cotton fabrics by cellulase treatment ", ITB Dyeing / Printing / Finishing (February 1990). The cellulase treatment of the surface of the fabric improves the quality of the fabric with respect to texture and appearance without losing the ability to get wet. The most important effects are less lint and matting, increased gloss / luster, better fabric texture, increased duration of softness and improved water absorbency. These effects are referred to as bio-polishing effects. Several methods involving cellulase treatment have been published in the art. For example, WO 9320278 discloses that bio-polishing is achieved during the manufacture of cellulosic fabrics by the succession of (1) treatment of the fabric with cellulase without significant mechanical treatment, and (2) mechanical treatment. The benefit of mechanical action is also disclosed in Cavaco-Paulo et al., 1994, Biocatalysis 10: 353-360. Cavaco-Paulo et al., 1996, Textile Res. J. 66: 287-294 reports that at low levels of agitation, pretreatment with the endoglucanase monocomponent did not cause significant weight loss in a cotton fabric. At high levels of agitation, a significant loss of weight was observed together with the microfibrillar material torn from the surface of the fiber. Although this improvement in the removal of surface and lint fibers is satisfactory in the laboratory, the textile industry follows a trend towards less mechanical action in the batch equipment now in operation. By not using the mechanical action there is a minor disturbance in the surface of the fabric that presents fewer opportunities for caking and an unsatisfactory aesthetic appearance of the fabric when the customer buys it. A consequence of this change is that the more aggressive multicomponent cellulases such as those produced by T. longibrachia tum are used to minimize caking in the treated fabric. For example, WO 9412578 discloses that the treatment of the cellulosic fabric comprises (a) a first treatment with a cellulase to achieve a weight loss of 0.05 to 10%, by weight, of the fabric; (b) a second treatment with a cellulase to obtain a weight loss of 0.05-10%, by weight, of the fabric after step (a). It has also been found that treatment with cellulase reduces the threads. The U.S. Patent No. 5,466,601 shows a process that selectively removes the embedded precursors from the cellulose yarns of the cotton fabric by applying a cellulase solution continuously during the manufacturing process. In the batch process of cotton fabrics, called interlaced points, the cellulase treatment has been applied at the end of the processing process, in the washing, bleaching and drying of the fabrics (see above Cavaco-Paolo et al.). In some cases, the cellulase treatment has been tested after the dyeing step with mixed results (WR Goynes et al., Textile Chemist and Colorist, December 1996, pp. 25-29) on the finished fabric, or after the conversion into clothing. Not much attention is paid to the morphology or chemical content of the cuticle and the primary wall of the cotton fiber. Published reports describing the composition of these parts of the cotton fiber describe the presence of several carbohydrate lipids, proteins and polymers including partially esterified polygalacturonic acid such as methyl ester. (Carpita and Gibeaut, The Plant Journal (1993) 3 (1), 1-30). During the course of washing and bleaching / polishing with alkaline peroxide certain chemical changes will occur both in the cuticle and in the primary wall of the fiber. These changes are important for the final acceptance of the fabric and how it behaves during the subsequent processing and in the final use. During the application of caustic, both in the washing process and in the bleached / polished, the fiber wall would suffer a process of inflammation due to the presence of charged carbohydrate polymers or due to the oxidation caused by the action of peroxide . Once dry, however, the matrix formed by these polymers could prevent rehydration and access to fibrils / microfibrils in which the action of the cellulase is necessary to eliminate the materials that later cause the caking effect. This same effect is known in wood fibers and is referred to as "conching", which implies that the drying of the fiber wall of the pulp changes the subsequent rehydration and significantly impedes water reabsorption. This is of some consequence in the process of the recycled fibers and in their reconversion into paper. This same effect, when applied to cotton fibers after they have been rehydrated and dried, is a way of explaining the need for higher levels of mechanical agitation to achieve a medial effect with certain kinds of cellulases. It is an object of the present invention to provide an improved enzymatic process for the treatment of cellulosic fabrics. It is also an object of the invention to reduce the caking of the fabric during subsequent washes. It is also an object of the present invention to improve the uniformity and speed of the dye uptake during the dyeing step of a dyed fabric.

SUMMARY OF THE INVENTION The invention is directed to an improved process for the treatment of 100% cellulose fabric not stained with cellulase comprising washing the fabric under alkaline conditions, treating the fabric with cellulase bleach and drying the fabric, in which the improvement comprises the treatment of the fabric with cellulase before the bleaching step. As a result, there is a reduction in caking during at least one wash cycle compared to the prior art methods. The reduction of caking also occurs in the cellulosic fabric when the fabric is treated with cellulase according to the method of the present invention if it is compared when the treatment is applied without cellulase. Biopulsing effects will also be achieved. As defined herein, a "wash cycle" is at least about 45 minutes and includes washing and drying. In one embodiment, a wash cycle is from about 45 minutes to almost 120 minutes. In a preferred embodiment, a wash cycle is from about 45 minutes to almost 95 minutes. In a preferred embodiment, the caking is a fabric is reduced during at least five wash cycles. In a more preferred embodiment, the caking is reduced during at least 15 washing cycles. Surprisingly, it has been found that by moving the cellulase treatment (bio-polishing) closer to the final front of the wet process stages, the cellulase can more easily access the fibrils / microfibrils which cause threads and caking in the finished fabric. Moreover, the mechanical agitation during the biopolishing stage becomes much less important in order to reduce the tendency for the fabric to form a shag of surface filaments.

In contrast to the processes mentioned in the prior art, both a multicomponent and a monocomponent cellulase can be used. Additionally, only one treatment with cellulase is necessary. In the process of the present invention, the cellulase treatment is almost the beginning of the wet process sequence. Even all the fibrils / fines produced by the cellulase treatment should have a greater chance to diffuse away from the fabric to produce less cumbersome leftovers at the fabric conversion stage. The method of the present invention also has the advantage that it eliminates the need for a cellulase inactivation step, since the cellulase-treated fabric is subjected to a bleaching step with alkaline peroxide after the bio-polishing step.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows the experimental strategies for biopolishing during the wet process. Figure 2 shows the break data for several samples. Figure 3 shows the Nu-Martindale caking for the Washing sequence: Bio-polishing: Bleached.

Figure 4 shows the Washing Caking: Bio-polishing: Bleached after the Washing / Drying Treatment.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to an improved process for treating a 100% cellulose fabric without dyeing. The 100% cellulosic fabric can be cotton, ramina or synthetic cellulose, especially that made by the use of fibers produced by the Lyocell process. The process of the invention involves four stages: washing the fabric; treatment of the fabric washed with cellulase; bleached cellulase-treated fabric; and drying the bleached cloth. Additionally, the method of the invention may also comprise the step of dyeing the fabric after bleaching and before drying. The steps involved in the process of the present invention are described in detail below.

Washing During the washing step, the fabric is treated with a washing agent, which includes but is not limited to sodium hydroxide, commercial soda, trisodium phosphate and other alkaline materials that produce a high pH. In addition, under these alkaline conditions, surfactant (s) could be included. Such surfactants could include non-ionic, anionic or mixtures or such classes of surfactants. The washing step will usually be carried out at elevated temperatures (80-100 ° C) and for periods as long as about one hour and preferably at least about 30 minutes at that temperature.

Cellulase treatment The process of the invention comprises the cellulase treatment of the fabric. The cellulase to be used according to the present invention can be any cellulase having cellulolytic activity, ie, hydrolyzed cellulose, both in the acid pH range, as in the neutral or alkaline pH and having cellobiohydrolase activity, exo-cellobiohydrolases, endoglucosease, and / or beta-glucosidase (multicomponent or monocomponent). The cellulase can be of fungal or bacterial origin, so it can be obtained or isolated and purified from microorganisms which are known to be capable of producing cellulolytic enzymes, for example, Humicola, Coprinus, Thielavia, Myceliopthora, Fusarium, Myceliophthora, Acremonium, Cephalosporium, Scytalidium um, Penicillium or Aspergillus (see, for example, EP 458162), especially those produced or produced by a selected strain of Humicola insolens species (reclassified as Scytalidium thermophilum, see for example, US Patent No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Mycelioph thora thermophila , Meripilus giganteus, Thielavia terrestris, Acremonium sp. , Acremonium persi cinum, Acremonium acremonium, Acremonium brachypenium, Acremonium dichromosporum, Acremonium obclava tum, Acremonium pinkertoniae, Acremonium roseogriseum, Acremonium colorless tum and Acremonium fura tum; preferably of the species Humicola insolens, DSM 1800, Fusarium oxysporum, DSM 2672, Mycelioph thora thermophila r CBS 117.65, Cephalosporium sp. , RYM-202, CBS 478.94, Acremoni um sp. , CBS 265.95, Acremonium persicinum, CBS 169.65, Acremonium acremonium, AHU 9519, Cephalosporium sp. , CBS 535.71, Acremonium brachypenia um, CBS 866.73, Acremonium um dichromosporum, CBS 683.73, Acremonium um obclava tum, CBS 311.74, Acremoni um pinkertoniae, CBS 157.70, Acremonium roseogriseum, CBS 134.56, Acremonium colorless tum, CBS 146.62 and Acremonium fura tum , CBS 299.70H. Cellulase can also be obtained from Tri choderma (particularly T. viride, T. reesei and T. koningii), alkalophilic Bacillus (see, for example, US Patent No. 3,844,890 and EP 458162) and Streptomyces (see, for example, EP 458162).

The cellulase that is used in the method of the present invention can be produced by the fermentation of the microbial strains mentioned above in a nutrient medium containing available carbon and sources of nitrogen and inorganic salts, using procedures known in the art (see , for example, Bennett, JW and LaSure, L. (editors), More Gene Manipulation in Fungi, Academic Press, CA, 1991). The appropriate medium is available from commercial suppliers or can be prepared according to the published compositions (for example, in catalogs of the American Type Culture Collection). The ranges of temperature and other conditions necessary for the growth and production of the cellulase are known in the art (see, for example, Bailey, JE and Ollis, DF, Biochemical Engineering Fundamentals, McGra-Hill Book Company, NY, 1986) . As defined herein, the term "fermentation" is any method for the cultivation of cells that result in the expression or isolation of the cellulase. The fermentation can, however, be understood as comprising the culture in flasks that are agitated, small or large-scale fermentation (which includes continuous fermentation, batching, batch feeding, or solid state fermentation) in fermentors of laboratory or industrial that work in appropriate means and under conditions that allow the cellulase to be expressed or isolated. The resulting cellulase that is produced by the methods described above can be recovered from the fermentation medium by conventional methods including, but not limited to, centrifugation, filtration, spray drier, evaporation or precipitation. The recovered protein is then purified by a variety of chromatographic procedures, such as, for example, ion exchange chromatography, gel filtration chromatography, affinity chromatography or the desired one. The cellulase may be a multicomponent or monocomponent cellulase. An example of a multicomponent cellulase is Cellusoft L ™, which is produced by a Tri choderma sp. and is supplied by Novo Nordisk A / S, Denmark. A monocomponent cellulase is a component essentially free of other cellulase components that usually occur in a cellulase system that is produced by a given microorganism. The single component can be a recombined component, i.e., produced by the cloning of a DNA sequence encoding the single component and the subsequent cell transformed with the DNA sequence and expressed in a host, cf. for example International Patent Applications WO 91/17243 and WO 91/17244 which are incorporated in this way by reference. Other examples of monocomponent cellulases include but are not limited to those mentioned in JP-07203960-A and WO-9206209. The host is preferably a heterologous host, but the host may under certain conditions also be the homologous host. In a specific embodiment, the monocomponent cellulase is Cellusoft Ultra ™ which is supplied by Novo Nordisk A / S, Denmark. This cellulase is a variant of a monocomponent cellulase that is produced by the Humi cola sp. In another embodiment, the cellulase is an optimized combination of a multicomponent cellulase and a monocomponent, designed to provide better results in the biopolishing of cotton fabrics. The enzyme dose depends greatly on the reaction time of the enzyme, i.e., a relatively short enzymatic reaction time requires a relative increase in the enzyme dose and vice versa. The reactions can be run at a pH of almost 4 to almost 9.5 at a temperature of almost 10 to almost 65 ° C for about 1 minute to about 72 hours. If the pH is between almost 4 and almost 6.5, an enzyme dose of almost 200 to almost 2,000 EGU / kg. of cloth is used. EGU works for the endoglucanase units as a measure of the viscosity change in carboxymethylcellulose (CMC) at a pH of 6.0. It is defined in the Novo Nordisk AF 275/1-GB Analytical Method, available on request from Novo Nordisk Biochem. If the pH is between 6.5 to almost 9.5, an enzyme dose of about 1,000 to about 10,000 ECU / kg. of cloth is used. The endo-cellulase units, determined by a change in viscosity in CMC at a pH of 7.5, are detailed in the Novo Nordisk AF 302.1 / 1-GB Analytical Method, available from Novo Nordisk Biochem.

Bleached During the bleaching stage, the fabric is treated with a bleaching agent which includes, but is not limited to, hydrogen peroxide, sodium hypochlorite and / or sodium chlorite. Peroxide bleaching can be carried out by the use, for example, of an ink tray, a dye dispenser or a tube apparatus J to apply the bleach peroxide liquor to the fabric. The individual chemical constituents in the bleach liquor can be 0.5-2% (by weight of cloth, ept) of hydrogen peroxide, 0.5-2% of sodium hydroxide, 1-4% of sodium silicate (42 'Be) , diethylenetriaminepentacetic acid (DTPA) as its sodium salt. The bleach liquor may also include a surfactant, a lubricant and / or a stabilizer. Both the ink bucket and the dyer's jet are batch processing units, and the bleaching would take as little as 30 minutes and as long as 150 minutes, at temperatures as low as 50 ° C and as high as 85 ° C. At the end of the selected time, the bleaching liquor is drained and the cloth is washed in a weak diluted acid containing a reducing agent (<2% sodium bisulfite (ept) or sodium thiosulfate) to neutralize the caustic and the residual peroxide. After a wash with fresh running water, the fabric can be dyed or dried subsequently for any subsequent process. A general treatment for bleaching cotton fabric is provided by W.S. Hickman, Rev. Prog. Coloration, 26, 29-46 (1996).

Dyeing The dyeing step can optionally be inserted between the bleaching stage and the drying stage. Cellulosic fabrics are dyed by the use of various kinds of dyes, which include both direct dyes and reactive dyes. The direct dyes are dependent on the affinity of the dye for the cellulose matrix in the fiber. The amount of ink that is taken can be increased by the addition of an inorganic salt to the ink bath to help increase the amount of dyeing and the final color yield. An example of this procedure, in ASTM Standard Method D 1464-90, is published in the ASTM Annual Book by the American Testing and Materials Society, 1916 Race St., Philadelphia, PA 19103; (1990). This method uses both a direct red and a direct green dye to characterize the cotton dyeing behavior. In this example, the application of the two dyes can generate an indication about the relative maturity of the fibers that are confined in the fabric and thus serve as an analytical tool. The direct application of the dyes alone or in other combinations can give a fabric of the desired color for final use. The reactive dyes contain a functional group which will react with a hydroxyl residue in the cellulose backbone. In a specific embodiment, the application is usually a two-stage process, the first resulting from the absorption of the dye in the cellulosic fiber. This can be achieved by adding amounts of an inorganic salt (sodium chloride or sodium sulfate) to the dyeing bath to minimize the solubility of the dye in the dyeing bath. After the absorption step is complete, the pH of the dyeing bath is increased (> pH 11) by the addition of a source of hydroxyl anions to the dyeing bath. The subsequent ionization of the hydroxyl cellulosic groups causes them to react with the reactive portion of the dye, and in this way the dye is fixed to the fiber. There are several classes of reactive dyes including, but not limited to, those groups reactive with monochlorotriazine, dichlorotriazine and vinylsulfone. For a dyer's fountain that contains both the fabric and the water-liquor ratio of 10-15: 1, the selected dye will be added to 2-4% ept of dye. The inorganic salt will be added (4-10% ept) and the heating cycle will begin. After a given amount of time to ensure sufficient absorption of the dye by the fabric, and at a desired temperature, a sufficient caustic preparation will be added to increase the pH to 11 or greater, and the dyeing cycle will continue until it is judged complete. The dye liquor can then be drained, and the fabric will be subjected to several washes with fresh water to ensure that the dye which failed to react with the fabric is removed.

Drying A standard drying method that is applied to woven fabrics after the wet process consists of drying them under limited conditions in a piece of equipment similar to a soft structure. In this unit, the fabric is held firmly between two movable locks, which can firmly grasp the fabric on each of the two sides. The fabric moves through some form of ovens which will dry the fabric in a sustained way. At the end of this drying process the fabric can be placed in rolled form, or subjected to another type of treatment such as cutting, scorching, etc. Another drying process that is applied to textile fabrics is to pass the fabric in motion through heated garret cylinders, alternating the sides of the fabric, which will equal the speed of drying on the two surfaces of the fabric roll or of the fabric. weft fabric EXAMPLES Example 1 Experimental Equipment: Werner-Mathis JFO dyer jet, sold by Werner Mathis, E.U., Concord, NC.

Nu-Martindale caking tester, James H. Heal and sold by Crosrol, Inc., Greenville, S.C. Mullen rupture tester, manufactured by B.F. Perkins, Chicopee, MA. Optical viewfinder Macbeth OMS-1, manufactured by Macbeth Division, Kollmorgen Instr. Corp., New Windsor, NY. Balance, pH meter, etc.

Chemicals / Enzymes: Enzymes: Cellusoft Ultra ™, 162 ECU / g (Novo Nordisk, A / S); Cellusoft L ™, 810 EGU / g (Novo Nordisk A / S); Mix A, 302 EGU Cellusoft L ™ + 112 ECU Cellusoft Ultra ™ / g. Shock absorber: 0.05 M sodium acetate, sodium acetate trihydrate, adjusted to pH 5 +/- 0.1. Chemicals: The Discoterge 1467 is a patented washing aid, made and distributed by Callaway Chemicals, Columbus, GA. It contains, among other things, a mixture of surfactant suitable for washing. Levapon HT is a textile stabilizer for bleaching with peroxide manufactured and distributed by Bayer Corp., Rock Hill, SC. Inkmaster 750 is a non-ionic surfactant from Rhone Poulenc (used at 0.5% ept (by weight of cloth) in an alkaline wash, 0.1% ept for bio-polishing and 0.25% ept in the peroxide stage). Inkmaster 750 is described in European Patent 0 717 144 Al as a nonionic surfactant made from linear or branched hip alcohol having a carbon number of 16 to 20, oxyethylene groups of 10 to 20, oxypropylene groups between 4 and 8. 50% hydrogen peroxide, from Aldrich (product of Catalog 42,065). Sodium silicate, 42 'Be, containing 14% NaOH and 27% Si02 (product of the Aldrich Catalog 33.844-3). Fabric: An interwoven fabric of unbleached cotton is used as a test cloth. The weight of this fabric is ~ 200g / m2.

Conditions for Individual Stages: Alkaline Wash A roll of unbleached cotton woven cloth is prepared by cutting a 5.5 m long roll of the fabric as received. Each piece of 5.5 m will then provide, by sewing, two rolls suitable for bio-polishing. The cooked rolls are conditioned in the room of constant temperature and humidity at night before weighing them. After weighing, the roll is washed in a standard Kenmore washer, centrifuged to remove excess water, and placed in the Mathis dry cleaner's spout. The alkaline washing is carried out by the use of sodium hydroxide at 2.5% ept (using 50% aqueous sodium hydroxide) and a detergent according to the instructions. Washing is performed by the use of a liquor ratio of 7.5: 1: genres and 90 ° C for 60 minutes. The desired flow is ~ 75 L / min and is determined by the foam levels in the unit. The velocity of the roofing with the trim is 13, which corresponds to a fabric speed of 16 m / min. At the end of the washing sequence, the liquor is drained, and the residual liquor is separated from the roll by the continuous operation of the blade with blade. A solution of acetic acid (2% glacial acetic acid, ept) in 18 L of hot water is added and the jet is operated for another 10 min to neutralize the residual caustic.

Bio-polishing The bio-polishing stage is carried out with a liquor ratio: 7.5: 1 genres containing Inkmaster 750 at 0.1% ept. The buffer used is 0.05 M sodium acetate at pH 5; The concentrated buffer solution is added to the volume of hot water required in the containment tank of the dyer's outlet. The diluted buffer solution is added to the fabric and allowed to circulate through the dyer's jet for almost 5 min. before removing a 200 mL aliquot used to measure the pH of the liquor. If the pH is high, small amounts (1-2 L) of glacial acetic acid are added to reach the goal of 5 +/- 0.1. Once the pH is reached, the unit is programmed to operate for 60 minutes at 55 ° C. The enzyme is added when this temperature is reached. At the end of 60 min. From the period of bio-polishing, the liquor is drained, although small quantities are removed to examine the presence of released fibers. Again, the fabric is run through the dyeing with nozzle for a short period to remove any free liquor from the fabric.

Bleached with Peroxide 4 g of DTPA and the desired amount of surfactant are suspended in one liter of water and stirred with a magnetic stirrer; enough caustic is added to the suspension of DTPA to take it to the solution as its sodium salt. A separate preparation which comprises 2% (ept) of 50% NaOH is weighed and combined with an additional 3% (ept) of sodium silicate (42 'Be). The hot water is charged to the containment tank; with the liter of DTPA: added surfactant, the volume is sufficient so that the total still provides a liquor: gender ratio of 7.5: 1. The liquor is poured into the dyer's outlet and programmed to obtain a temperature of 70 ° C and to remain there for 60 min.

The hydrogen peroxide, at 50% by weight, is weighed to provide 1% of 100% active material ept. It is added to the dyer's jet when the temperature, 60 ° C, is reached and allowed to circulate. The combined caustic / silicate charge is added when the temperature approaches 70 ° C. The liquor from the dilution and washing of this material is removed from the dyer's outlet. At this stage the formation of extreme foam is observed and the liquor flow may need to be reduced to minimize the potential for foaming. After 60 min. At this temperature, the liquor is removed (drained), but the liquor samples are collected to visually examine the presence of fibers released during the process. Again, any free liquor is separated from the fabric by the operation of the dyeing with nozzle after the liquor has been dredged. The cloth is washed by the use of 18 L of hot water containing 2% (ept) of glacial acetic acid and 2% (ept) of sodium thiosulfate. After 15 minutes, this is removed and another 18 L of hot water are added for a final wash of 10 min.

The cloth roll is removed, centrifuged and dried for 50 min. in a drum dryer. The hilcahos are removed and weighed, and the cloth is dried for about 20 more minutes. The roll of tissue dried in the drum was allowed under condition AATCC (65% ± 2% relative humidity and 70 ° F ± 2) for at least 24 hours.

Results Caked The data that is contained in Table 1 compares the caking results obtained with the method of Washed-Biopolished-Bleached / Polished-Dried (Sample "A") described above and with the same biopolished cloth after it was subjected to the Washing-Bleached-Drying treatment (Sample "B") using a cellulase mixture commercial multicomponent (Cellusoft L ™), a commercial monocomponent cellulase (Cellusoft Ultra ™) and a mixture of Cellusoft L ™ and Cellusoft Ultra ™. It is necessary to inactivate the residual activity of the cellulase in the fabrics of Sample "B" using a treatment with 2% sodium carbonate (ept) at 80 ° C for 20 min. The amount of caking is determined by the placement of the samples of the fabric specimens in the Nu-Martindale caking tester. This unit has a counter that quantifies the number of revolutions that the fabric has experienced. It stops automatically after 125, 500 and 2000 revolutions to allow the operator to make a visual comparison of the amount of caking with the standards provided with the unit. The complete operation is carried out as is Method ASTM D 4970-89. The scale of measurement goes from 1.5 to 5, with the higher values that represent little or no caking at the point where the observations were made.

Table 1 Treated Cloth Caking Values It is clear that superior results are obtained when the biopolishing stage is added as an intermediate stage between washing and bleaching (Series "A").

Changes in Physical Properties Any large change in physical properties in woven fabrics is undesirable for commercial acceptance of this concept. The breaking property in the Mullen Rupture Tester is the pressure that is required to break the web; it is measured in psi (pounds / square inch) and is the physical property that is used here as a guide to monitor the changes that are caused by the cellulase during these treatments. The tests were performed by the use of the Mullen Tester, Model C, manufactured by B.F. Perkins, Chicopee, MA. This test method is described in ASTM Method D-2210-64 which measures the force required to break the fabric to be tested by a hydraulically operated diaphragm. The fabric is tested in a state of subjection; The strength to break this fabric is measured in pounds per square inch (psi). This method is a well-known technique and is used in the textile industry and in other industries where stress or rupture properties are important in the final operation of the product.

Figure 2 and Table 2 contain the data of rupture of the samples with the best performance according to the results of the caking. The base values for washing only and washing / bleaching are only comparable and could indicate that washing and bleaching conditions did not unnecessarily soften the fabric. Only a small reduction in burst values are observed for the samples treated with Cellusoft Ultra ™, Mixture A and Cellusoft L ™. Achieving a minimum loss of physical properties, here measured by the Mullen breakage property, is important for end users of the fabric since greater losses in physical properties could be reflected in the premature failure of the garment made with the fabric They can also be reflected in an unexpected failure in the wet state, since the properties of the fiber are inferior when they are wet to those of the fibers in their dry state.

Table 2 Breakpoints Example 2 Experimental Equipment The equipment used in this example is the same as that used in Example 1.

Tests / Caked Analysis (Nu-Martindale), AATCC 124-1996 washing evaluation test method, with visual examination of the pellet after 5, 15 and 30 cycles, and Mullen rupture test on fabrics after washing treatment: biopolishing : bleached Chemicals / Enzymes The enzymes, buffers, cloth and other materials used are the same as in Example 1 with the exception that the Cellusoft L ™ that is used has an activity of 783 EGU / g.

Conditions for Individual Stages: Alkaline Wash A roll of unbleached woven cotton test cloth is prepared by cutting a roll of 5.5 m length from the fabric as received. Each piece of 5.5 m will then provide, after sewing, two rolls available for bio-polishing. The cooked rolls are conditioned in the room of constant temperature and humidity at night before weighing them. After weighing, the roll is washed in a standard Kenmore washer, centrifuged to remove excess water, and placed in the Mathis dry cleaner's spout. The alkaline wash is carried out by the use of 2.5% sodium hydroxide ept (use 50% aqueous sodium hydroxide) and a detergent according to the instructions. The washing is done by the use of a liquor ratio: genera of 7.5: 1, and 90 ° C for 60 minutes. The desired flow is ~ 75L / minutes and is determined by the foam levels in the unit. The speed of the dyeing with fixed blade is 13, which corresponds to a fabric speed of 16 m / min. At the end of the washing sequence, the liquor is drained and the remaining residual liquor is eliminated from the roll by the continuous operation of the dyeing with nozzle. A solution of acetic acid (2% glacial acetic acid, ept) in 18 L of hot water is added and the spout is operated for another 10 minutes to neutralize the remaining caustic.

Bio-polishing The bio-polishing stage is carried out under a liquor ratio: 7.5: 1 genera containing Inkmaster 750 (surfactant) at 0.1% ept. The buffer used is 0.05M sodium acetate at pH 5; a concentrated buffer solution is added to the volume of hot water required in the containment tank of the dyer's outlet. The diluted buffer solution is added to the fabric and allowed to circulate through the dyer's outlet for around 5 min. before taking an aliquot of 200 mL that is used to measure the pH of the liquor. If the pH is high, small amounts (1-2 mL) of glacial acetic acid are added to achieve the goal of 5 +/- 0.1. Once the pH is reached, the unit is programmed to run 60 minutes at 55 ° C. The enzyme is added when this temperature is reached. At the end of 60 min. From the period of bio-polishing, the liquor is drained, although small quantities are removed to examine the presence of released fibers. Again, the fabric is run through the dyeing with a blade for a short period to eliminate any presence of liquor from the fabric.

Bleached with Peroxide 4 g of DTPA and the desired amount of Ink aster, 750 (0.25% ept) is suspended in one liter of water and stirred with a magnetic stirrer. A separate preparation comprising 2% (ept) of 50% NaOH is weighed and added to the DTPA / Inkmaster preparation and combined with additional 3% sodium silicate (42 'Be) (ept). The hot water is charged to the containment tank; with the liter of DTPA: added surfactant, the volume is sufficient for the total yet to provide a liquor ratio: 7.5: 1 genera. The liquor is emptied at the dyer's outlet and programmed to reach a temperature of 70 ° C and remain there for 60 min. The hydrogen peroxide, 50% by weight, is weighed to provide 1% of the 100% active material ept. It is added to the dyer's jet when the temperature reached 60 ° C and allowed it to circulate. The combined caustic / silicate charge is added when the temperature approaches 70 ° C. The liquor of the dilution and washing of this material is removed from the spout. Foaming is observed at this stage and the liquor flow is lowered to reduce the potential for foam formation. The foam formation decreases while the bleaching stage proceeds.

After 60 min. At this temperature, the liquor is extracted (drained), but the liquor samples are collected for a visual examination by the presence of fibers released during the process. Again, any free liquor is removed from the fabric by carrying out the dyeing with aspadera after the liquor has been extracted. The cloth is washed by the use of 18 L of hot water which contains 2% (ept) of glacial acetic acid and 2% (ept) of sodium thiosulfate. After 15 minutes, this is drained and another 18 L of hot water is added for a final wash of 10 min. The fabric roll is removed, centrifuged and dried for 50 minutes in a drum dryer. The roll of tissue dried in the drum was allowed to condition under AATCC conditions (relative humidity of 65% ± 2% and 70 ° F ± 2) for at least 24 hours (until no later changes in weight are observed) and dry weight It is recorded.

Repetitive Wash Test The bio-polishing rolls are divided into six sections of equal length and re-joined by seams inside the roll. Three of the completed rolls, which contain 5 different sections are then tested with the AATCC Washing Test Method 124-1996, which uses the 1993 AATCC detergent. The rolls are removed from the test at 5, 15 and 30 cycles and a ballast, in the form of intertwined raw cotton rolls are added to achieve the weight of 1.8 kg. who asks for this method.

Results Nu-Martindale Caking The amount of caking is determined by the mounting of the samples of the fabric specimens in the Nu-Martindale caking tester. This unit has a counter, which counts the number of revolutions that the fabric has experienced. It shuts off automatically after 125, 500 and 2000 revolutions which allows the operator to make a visual comparison of the amount of caking with the standards provided by the unit. The entire operation operates according to ASTM Method D 4970-89. The measurement scale goes from 1.5 to 5, with the higher values representing no / little matted at the point where the observations are made. The results are shown in Figure 3. It appears that in each of these three cell preparations, the method using the bio-polishing step between washing and bleaching offers superior caking results. It appears that better caking results are obtained by the use of either the enzyme mixture or the multicomponent enzyme.

Caking during Washing To determine more clearly the degree of caking during normal use of the fabric, caking is observed while the fabric is subjected to Figure 4 which provides the caking response observed by the AATCC Washing Test Method 124-1996 . This method specifies the use of the 1993 AATCC detergent to eliminate source variability. The visual qualification of these fabrics after 5, 15 and 30 cycles is shown in Figure 4. This value assumes an arbitrary scale where a 5 represents the best appearance, and this decreases as it moves to a lower value. There is a discrepancy in the appearance of the original fabrics between the fabrics treated with cellulase and those that were treated without enzymes. The appearance quality of all fabrics decreases with the increase of the washing and drying cycles, still the samples treated with cellulase seem to maintain their properties after 15 washing cycles. The quality of the control fabrics continues to degrade with the increase of the washing cycles. In contrast to the Nu-Martindale matting results obtained in the previous section, there is little or no difference between the fabric treated with Cellusoft Ultra ™ monocomponent and the other fabrics treated with a multicomponent cellulase. This is an important difference between the two caking methods, and could show that the important factor is the process sequence, cellulase treatment, and not necessarily the type of cellulase preparation.

Changes in Physical Properties The loss of resistance to rupture (Mullen) is shown in Table 3. The trends are similar to those previously obtained by the use of washed, bleached and dried interlaced cotton fabric. The greatest damage to fabric resistance occurs with Trichoderma, while the least damage occurs when the amount of Cellusoft Ultra ™ increases. Again, there is only a slight reduction in the break values in the samples treated with enzyme.

Table 3 Rupture Values for Treated Cotton Fabrics Treated (Average of 10 readings / sample) Example 3 Experimental Equipment The Werner-Mathis JFO dyer jet, sold by Werner Mathis, E.U., Concord, NC. The Nu-Martindale caking tester, James H. Heal and sold by Crosrol, Inc., Greenville, S.C. The rupture tester Mullen, manufactured by B.F. Perkins, Chicopee, MA. Optical viewfinder Macbeth OMS-1, manufactured by Macbeth Division, Kollmorgen Instr. Corp., New Windsor, NY. Balance, pH meter, etc.

Tests / Analysis Weight loss of the fabric, visual examination for the fibers released in the spent liquors, brightness / color response, caked (Nu-Martindale), AATCC washing evaluation test method 124-1996, with visual examination of the after 5, 15 and 30 cycles, and proof of Mullen rupture in the fabrics after the washing treatment: bio-polished: bleached.

Chemicals / Enzymes Enzymes: Cellusoft Ultra ™, 162 ECU / g (Novo Nordisk, A / S); Cellusoft L ™, 810 EGU / g (Novo Nordisk A / S); Mix A, 302 EGU Cellusoft L ™ + 112 ECU Cellusoft Ultra ™ / g. Shock absorber: 0.05 M sodium acetate, sodium acetate trihydrate, adjusted to pH 5 ± 0.1. Sodium silicate, 42 'Be, containing 14% NaOH and 27% Si02 (product of the Aldrich Catalog 33,844-3). Fabric: A woven interwoven fabric of unbleached cotton. The weight of this cloth is -200 g / m2. 5.5 m long is cut from the fabric, divided halfway along the longitudinal axis of the fabric and re-stitched to form a roll having a weight > 800g. These rolls can be conditioned under the AATCC conditions as described in the previous examples and weighed just before the treatment at the dyer's outlet. They will be loaded into the dispenser after moistening in a washing machine, followed by removal of excess water in the centrifuge by Batch.

Conditions for Individual Stages: Alkaline Wash Alkaline washing is carried out by the use of 2.5% ept sodium hydroxide (use 50% aqueous sodium hydroxide) and a 0.5% ept surfactant. The washing is done by the use of a ratio of 12: 1 liquor: genres, and 90 ° C for 60 minutes. The desired flow is ~ 75 L / min and is determined by the foam levels in the unit. The speed of the dyeing with fixed blade is 13, which corresponds to a fabric speed of 16 m / min. At the end of the washing sequence, hot water is added to represent an overflow of the washing condition and the spout is operated to remove residual caustic. This liquor is cooled to 77 ° C, then drained and the glacial acetic acid (~ 1% ept) will be added in a liquor 20: 1 ratio: goods to try to bring the pH of the fabric below a pH of about 5.

Bio-polishing The bio-polishing step is done with a liquor ratio: 10: 1 genders containing 0.1% surfactant ept. The buffer used is 0.05 M sodium acetate at pH 5 (± 0.1); a concentrated buffer solution is added to the volume of hot water required in the containment tank of the dyer's outlet. The diluted buffer solution is added to the fabric and allowed to circulate through the dyer's jet for almost 5 min. before removing a 200 mL aliquot used to measure the pH of the liquor. If the pH is high, small amounts of glacial acetic acid are added to reach the goal of 5 +/- 0.1. Once the desired pH is reached, the unit is programmed to operate for 60 minutes at 55 ° C. The enzyme is added when this temperature is reached. At the end the 60 min. From the period of bio-polishing, the liquor is drained, although small quantities are removed to examine the presence of released fibers. Again, the fabric is run through the dyeing with nozzle for a short period to remove any free liquor from the fabric.

Bleached with Peroxide Sufficient water is added from the containment tank to the spout so that the total provides a liquor ratio: 10: 1 genera. The additives include the lubricant, Multiplus ™ that is added at 0.75 g / L, the Kierlon TX 199 ™ surfactant is added at 1 g / L and the Prestogen K ™ stabilizer is added at 0.4 g / L. The Multiplus ™, the Kierlon TX 199 ™ and the Prestogen K ™ are obtained from BASF. After these materials are dissolved in sufficient water and added to the dispenser, 50% NaOH is added to provide a final concentration of 0.4 g / L. After all the liquor is in the dispenser, it is programmed to reach a temperature of 93 ° C and to remain there for 45 min. The hydrogen peroxide, at 50% by weight, is weighed to provide 1% of the 100% active material ept. It is added to the dyer's jet when the temperature of 66 ° C is reached. At this stage the formation of foam is observed and the liquor flow may need to be reduced to minimize the potential for foaming. After 45 min. at this temperature, the liquor is removed (drained), but the liquor samples are collected to visually examine for the presence of fibers released during the process. The fabric will be rinsed for 10 min. with hot water (71 ° C) (liquor / 20: 1 sorts).

After 10 minutes, this is removed and repeated washing with hot water is performed. After a cold rinse (38 ° C), excess caustic and peroxide are considered to be removed from the roll. The fabric roll is removed, centrifuged and dried for 50 min. in a drum dryer. The yarns are removed and weighed, and the cloth was dried for another 20 minutes. The roll of tissue dried in the drum is brought to the condition under the AATCC conditions (65% ± 2% relative humidity and 70 ° F ± 2) for at least 24 hours (until no further weight change was observed) and the dry weight is recorded.

Repetitive Wash Test Approximately 0.5 m of each of the samples are sectioned and reassembled into rolls in such a way that a segment of each treatment condition is included. The two outer samples will comprise a sample subjected only to washing / bleaching at one end and a control without any treatment apart from the wetting at the other end. The desired weight of these rolls will not be greater than 600 g, so that three of the rolls will reach 1.8 kg, the weight of the "cloth that is used for the AATCC washing performance test. indicated by this test and the rolls are removed after 5, 15 and 30 cycles.

Results Nu-Martindale Caking The amount of caking is determined by the mounting of the samples of the fabric specimens in the Nu-Martindale caking tester. This unit has a counter, which counts the number of revolutions, which the fabric has experienced. It shuts off automatically after 125, 500 and 2000 revolutions which allows the operator to make a visual comparison of the amount of caking with the standards provided by the unit. The entire operation is run according to ASTM Method D 4970-89. The measurement scale goes from 1.5 to 5, with the upper values representing no / small caking at the point where the observations are made. The results are shown in Table 4 below.

Table 4 Treated Fabric Caking Values It turns out that in each of these three cellulase preparations, the method that uses the bio-polishing step between washing and bleaching offers superior caking results. Presents that the best caking results are obtained by the use of both the enzyme mixture and the multicomponent enzyme.

Caked during Washing As performed in Example 2, woven fabric rolls formed by segments of the treatment conditions used herein are subjected to AATCC Washing Test Method 124-1996. Again, the 1993 AATCC Detergent is used in the washing tests. The rolls are removed after 5, 15 and 30 wash cycles when using this test. Rather than using a numerical scale to assess the amount of caking which occurred in each of these joints, the segments in the individual rolls are subjectively compared. Even after 30 wash cycles, it is difficult to discern the differences between any of the fabrics treated with cellulase from these series of runs. There is, however, no difficulty in observing large differences between the fabrics treated with cellulase and the samples of control cloth, the deteriorated untreated or the washed and bleached.

Changes in Physical Properties The loss of resistance to rupture (Mullen) is shown in Table 5. Again, there is only a slight reduction in the values of rupture in the samples treated with enzyme.

Table 5 Breakpoints The invention described and claimed herein is not to be limited in scope by the specific embodiment mentioned herein, since these embodiments were intended as illustrations of various aspects of the invention. Any equivalent mode is directed to be within the scope of this invention. In itself, various modifications of the invention in addition to those shown and described herein will become apparent to those tools in the art of the foregoing description. Such modifications are also intended to fall within the scope of the claims set forth in the appendix. Several references are cited here, disclosures of which are incorporated by reference in their entirety.

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.

Claims (24)

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

1. A process for treating a 100% uncolored cellulose fabric characterized in that it comprises a) washing the fabric under alkaline conditions; b) the treatment of the fabric with cellulase; c) bleaching the fabric and d) drying the fabric.

The process according to claim 1, characterized in that the cellulosic fabric is a cotton fabric

3. The process according to claim 1, characterized in that the fabric is washed by treating the fabric with one or more washed agents selected from the group consisting of sodium hydroxide, commercial soda, phosphates and surfactants

4. The process according to claim 1, characterized in that the fabric is treated with at least one of the washing agents for almost 30 min. 60 min.

5. The process according to claim 1, characterized in that the fabric is treated with at least one washing agent at a temperature between almost 80 and almost 100 ° C.

6. The process according to claim 1, characterized in that the cellulase is a multicomponent cellulase.

The process according to claim 6, characterized in that the cellulase is derived from the Trichoderma.

8. The process according to claim 1, characterized in that the cellulase is a monocomponent cellulase.

9. The process according to claim 8, characterized in that the monocomponent cellulase is derived from Humicola.

10. The process according to claim 1, characterized in that the cellulase is a mixture of a multicomponent and monocomponent cellulase.

11. The process according to claim 1, characterized in that the fabric is treated with cellulase at a pH between almost 4 and almost 9.5.

12. The process according to claim 1, characterized in that the fabric is treated with cellulase at a temperature between almost 10 and almost 65 ° C.

The process according to claim 1, characterized in that the fabric is treated with cellulase between about 1 minute and about 72 hours.

The process according to claim 1, characterized in that the fabric is treated with cellulase at a pH between almost 4 and about 6.5.

15. The process according to claim 14, characterized in that the fabric is treated with between about 200 and about 2,000 EGU / kg. of cloth.

16. The process according to claim 1, characterized in that the fabric is treated with cellulase at a pH between almost 6.5 and about 9.5.

17. The process according to claim 16, characterized in that the fabric is treated with between about 1,000 and about 10,000 ECU / kg. of cloth.

18. The process according to claim 1, characterized in that the fabric is bleached with at least one of the bleaching agents selected from the group consisting of hydrogen peroxide, sodium hypochlorite and sodium chlorite. «:

19. The process according to claim 1, characterized in that the fabric during the bleaching step is treated with a bleaching liquor comprising a bleaching agent and a surfactant.

20. The process according to claim 1, characterized in that the fabric during the bleaching step is treated with a bleaching liquor comprising a bleaching agent and a lubricant.

The process according to claim 1, characterized in that the fabric during the bleaching step is treated with a bleaching liquor comprising a bleaching agent and a stabilizer.

22. The process according to claim 1, characterized in that the fabric during the bleaching step is treated with a bleaching liquor comprising a bleaching agent, a lubricant, a surfactant and a stabilizer.

23. The process according to claim 1, characterized in that the fabric is treated with at least one bleaching agent at a temperature between about 50 and about 85 ° C.

24. The process according to claim 1, characterized in that it also comprises a dyeing step after step (c) and before step (d). . A process for reducing caking during at least one wash cycle in the fabric characterized in that it comprises: a) Washing the fabric under alkaline conditions; b) treatment of the washed fabric of step (a) with cellulase; c) blanching the treated fabric of step (b); and d) drying the bleached fabric of step (c).