MXPA97002777A - Treatment of assisted protein recycling quimicame - Google Patents

Abstract

The present invention relates to a method for treating proteinaceous materials containing disulfide or polysulfide bonds to improve their performance at high relative humidity and when made wet. The method comprises annealing the fabric at a temperature in the range of about 70øC to 160øC at a recovery of between 10 and 25 percent over a period of more than 10 minutes where the fabric is annealed in the presence of a gas that improves the reaction of disulfide exchange. A further embodiment of the invention comprises recoating latex at a temperature on the scale from about 70 ° C to 160 ° C at a recovery of between 10 and 25 percent for a period greater than 10 minutes where the cloth has been treated at least in part with a liquid that improves the disulfide exchange reaction. The present method is particularly applicable for keratinous materials such as for example wool, wool with reduced crystallinity, angora cloth, regenerated protein or mixtures thereof.

Description

CHEMICALLY ASSISTED PROTEIN RECYCLING TREATMENT The present invention relates to a method for treating proteinaceous materials containing disulfide or polysulfide bonds to improve their performance at a high humidity level and when wet. The present invention is particularly applicable to keratinous materials such as for example wool, wool with reduced crystallinity, angora cloth, regenerated protein or mixtures thereof although not limited thereto. Wool is a composite polymer, consisting of water-impenetrable crystalline filaments embedded in an amorphous matrix containing a high concentration of the amino acid cystine. The matrix is therefore highly interlaced and occupies approximately 70% fiber volume. The hygroscopic nature of the wool has also been attributed to the matrix regions. The amount of moisture present in a fiber mass or a yarn or fabric was calculated as moisture recovery. Moisture recovery is the loss in weight of water over complete drying at 105 ° C as a percentage of dry fiber weight. The normal method for determining these values involves weighing, complete drying, weighing and calculation. The recovery of humidity varies with the relative humidity (r.h.) of the atmosphere to which the fibers are exposed. (Figure 1). The mechanical properties of the fibers depend critically on moisture recovery. It has been found that a glass transition temperature (Tg) which is also sensitive to the water content occurs in the matrix region of the wool fiber. The glass transition temperature is the temperature at which the material changes from being in a state where it behaves like a glass, to temperatures below Tg, to be in a state in which it behaves like a rubber, at temperatures above Tg. At relative humidity greater than about 90%, the proteinaceous materials are able to absorb large amounts of water. It is considered that the absorption of water, especially the large amount at relatively high humidity that can cause the proteinaceous materials to change from the "vitreous" state to the "elastic" state. It is considered that this transition is accompanied by a deterioration in the yield of proteinaceous materials. For example, fabrics made from these materials will suffer from high aqueous expansion and a deterioration in mechanical properties, for example the module (see for example the Table 1), the rigidity of bending, draping, wrinkle recovery, etc., as the water content increases. Many chemical treatments are known to reduce the water content at higher relative humidity (Ex. 4) although they are not practical since they require treatment with large amounts of chemical element or cause excessive damage to the material or result in an unacceptable color change .

Table 1: Relative Hookean Module as a Function of Relative Humidity for Wool The methods for the stabilization or fixation of wool fibers, in a desired geometric configuration, have been and still are the subject of considerable study. The methods that have been used to improve the resistance of wool and cotton articles to wrinkling and folding are described in the Patent Specification of RU 1299377 and 1326628. 1299377 describes a method for increasing the strength and recovery from deformation of the yarn. a textile material, the process comprising subjecting the material to an annealing treatment keeping the material at a temperature within the range of 30 ° C to 120 ° C for a period of more than 20 minutes while maintaining the recovery of the fibers at a value corresponding to a relative humidity from 60% to 95%. The increase in resistance to and recovery from deformation was attributed to the rearrangement of the labile hydrogen bonds within the wool fibers to more stable configurations (ie low energy) under conditions of increased temperature and / or recovery. The conditions of increased temperature and / or recovery cause the rupture of deformed hydrogen bonds and as the temperature and / or region are slowly reduced the hydrogen bonds progressively re-form and in doing so assume configurations possessing the lowest possible energy . 1326628 describes a method for increasing the resistance to and recovery of the deformation of a textile material, the process comprising submitting the material to an annealing treatment by keeping the material at a temperature within the range of 30 ° C to 150 ° C for a period of more than 5 minutes, while maintaining the recovery of the fibers to a value corresponding to a relative humidity from 50% to 95%. The process comprises administering the material either before, during or after annealing with a multifunctional compound having at least two reactive sites capable of entangling the textile fiber. A typical chemical system in accordance with 1326628 that imparts a high degree of stabilization of the annealed state is a resorcinol-formaldehyde system. "Traditional annealing" describes the process of annealing the wool to impart a wrinkle recovery degree significantly greater than that of wool that has not been treated. It is also known that this traditional annealing process causes a small reduction in the recovery of wool saturation. Despite repeated attempts over many decades to improve wrinkle recovery by chemical treatments, traditional annealing has remained the most practical and provides the greatest improvement in wrinkle recovery. Unfortunately when the wool is annealed in the traditional way the improvement in wrinkle recovery is not permanent since immersion in cold water or steam ironing will substantially eliminate the benefit of annealing. Therefore much effort has been directed to improve the stability of the annealed state in a traditional way to immersion in cold water and steam ironing although with little success. The importance of the treatment to improve the recovery to the wrinkle of the wool is well known and in spite of the continuous failures this area has maintained a high priority. It has been found that the disulfide exchange reaction occurring to a limited extent during the traditional annealing can be improved. "Disulfide exchange" is used to describe the rearrangement of disulfide or cystine entanglements in wool. The presence of thiol groups facilitates this rearrangement and occurs at approximately 70 ° C in water and at higher temperatures as recovery is reduced. The stresses exerted through the disulfide bonds can be released by the process of the present invention as the disulfide bonds are rearranged. The increase in the disulfide exchange reaction and the subsequent entanglement during annealing reduces the total amount of water that can be absorbed by the proteinaceous material (saturation recovery). It is considered that the reduction in saturation recovery avoids, or at least reduces the probability that, the glass transition temperature is exceeded at relatively high humidity or in cold water. Accordingly, undesirable changes in the properties of the material on the transformation to the "elastic" state are avoided. This provides an improvement in the moisture or high relative humidity properties of the proteinaceous materials. Therefore, properties such as moisture modulus, wrinkle recovery, etc. are improved in this way. In certain embodiments of the present invention, the permanent fixation properties of fabrics made from these proteinaceous materials (permanent press) are also improved. In accordance with the present invention there is provided a process for treating fabric made from proteinaceous materials containing disulfide or polysulfide bonds comprising annealing the fabric at a temperature in the range of 70 ° to 160 ° C at a recovery of between 10% and 25% over a period of more than 10 minutes where the fabric is annealed in the presence of a gas that increases the disulfide exchange reaction. According to a further embodiment of the present invention a process is provided for treating a fabric made of proteinaceous materials containing disulfide or polysulfide bonds comprising annealing the fabric at a temperature on the scale from 70 ° C to 160 ° C for a recovery of between 10% and 25% over a period greater than 10 minutes wherein the fabric has been treated at least in part with a liquid that improves the disulfide exchange reaction. The term "fabric" is used herein to describe woven or non-woven fabric. Non-woven fabrics include those made by knitting or felting. The preferred fabric for the treatment according to the present invention is a type of high quality combed wool. The term "fabric" includes articles made from fabrics that include garments and the like. The term "proteinaceous materials containing disulfide or polysulfide bonds" includes materials containing keratin, wool, wool with reduced crystallinity, angora fabric, regenerated protein or mixtures thereof etc. Combinations are also included, especially combinations of wool with other natural fibers such as cotton, silk and the like and also synthetic materials such as polyester, nylon and the like. Throughout the specification the method of the invention will be explained with reference to wool and wool with reduced crystallinity although it is understood that the method is applicable to other forms of keratin and other proteinaceous material or mixtures thereof. "Annealing" is used to describe the process of raising the temperature of the wool under conditions to which the moisture content of the wool is controlled. Although in the annealing processes described in the literature slow down the cooling that is usually required, in the present specification it is understood that controlled or slow cooling is not always necessary to impart the benefits claimed herein. As a result of the present invention the properties of the fabrics that are improved at a higher relative humidity and when the humidity includes the improvement of their resistance to and recovery from the deformations; the prevention of wrinkling of garments during use; the improvement in its resistance to shrinkage and felting during washing or dry cleaning; a reduction in its water expansion behavior during exposure to conditions of high relative humidity or when it is wet; an increase in the elastic modulus of the material when done wet or at a high relative humidity; an improvement in the draping of a fabric made from a proteinaceous material at high relative humidity or when made wet; a prevention of deterioration of the dimensions and shape of such articles during use or washing and during processing and manufacturing operations etc. The method of the present invention can also be part of a process for permanently fixing the fabric and for improving its dimensional stability preferably with the addition of shrinkage resistance treatment to improve machine washing and drying. The permanent fixing process can be used to improve the dimensional stability of a garment made from fabric, to impart permanent folds or three dimensional structure to the fabric, such as, for example, embellishment. The combination of the process of the present invention with a shrink-resistant process results in a cloth or garment with easy care characteristics. The process of the present invention allows a permanent fixation to be imparted to the fabric, such as a garment, without significant loss of the original dimensions or the cohesively fixed shape. The process of the present invention eliminates the need to restrain or hold the fabric in order to impart permanent fixation. The process of annealing to reduced recovery and under conditions in which the disulfide exchange reaction will increase which allows the occurrence of the disulfide entanglement rearrangement and therefore the entanglement of the matrix will occur in a state of swelling controlled by the fiber recovery at the time of treatment. This process results in reduced swelling at high relative humidity. The occurrence of the disulfide entanglement rearrangement is considered to result in a reduction in saturation recovery. The formation of a permanent fixation that imparts the aforementioned benefits is given by way of example only. The invention achieves an improved performance of fabrics, such as those comprising wool, by increasing the disulfide exchange reaction during annealing, thereby reducing the amount of water absorbed when the proteinaceous material is moist or at high humidity . This process also imparts permanent fixing to the fabric which also results in significantly improved performance. In the process of the present invention, suitable agents can be used to improve the disulfide exchange reaction. Agents that are in the gas phase at the annealing temperature are particularly convenient in the process of the present invention as they can be introduced into the annealing atmosphere in order to increase the disulfide exchange reaction. Gases that increase the disulfide exchange reaction during annealing include, for example, thiol reducing agents eg hydrogen sulfide, polysulfides of the form H2S2, H2S3, H2S4 etc., thioglycolic acid, 1, dithiothreitol, mercaptoethanol, benzylmercaptan , Ethantiol, Bencentiol, 2-Aminoethantiol etc .; reducing agents such as phosphines for example phosphine, tris (hydroxymethyl) phosphine, tri-n-butylphosphine, tri-ethyl phosphine and tertiary phosphines derived from phosphine by reaction with amines and formaldehyde; other reducing agents for example triethylphosphite, sulfur dioxide and the like. It has been found that hydrogen sulfide (H2S) is a preferred gas for increasing the disulfide exchange reaction during annealing. Other agents may be used in liquid form to increase the disulfide exchange reaction, typically pure or in the form of a solution or dispersion. Such liquids that improve the disulfide exchange reaction include thiol reducing agents for example hydrogen sulfide, polysulfides of the form H2S2, H2S3, H2S4 etc., thioglycolic acid, 1,4'-dithiothreitol, mercaptoethanol, benzyl mercaptan, ethantiol, benzothiol, 2-aminoethiol, cysteine, etc.; reducing agents such as phosphines for example phosphine, tetrakis (hydroxymethyl) phosphonium chloride, tris (hydroxymethyl) phosphine, tri-n-butylphosphine, tri-ethyl phosphine and tertiary phosphines derived from phosphine by reaction with amines and formaldehyde; other reducing agents for example triethylphosphite, borohydride, bisulphite, sulfite, dithionite, monoethanolamine sesquisulfide, sulfur, hydroxysulfide, sulfur dioxide etc .; thiolate agents for example acetyl mercaptosuccinic anhydride, thiolactone of N-acetyl-homocysteine, homocysteine thiolactone, thioglycolides etc. Preferably the liquid allowing the disulfide exchange reaction is selected from the group consisting of hydrogen sulfide, thioglycolic acid, 1,4-dithiothreitol, mercaptoethanol, benzyl mercaptan, ethantiol, benzothiol, cysteine. bisulfite, sulfite, dithionite, monoethanolamine sesquisulfate, sulfur, hydrosulphide, sulfur dioxide and thioglycolides. Such agents in the liquid form are conveniently applied to the fabric by brushing or soaking the fabric in the region where the improved properties of wrinkle resistance and permanent fixation are desired prior to annealing. Combinations of the use of gases and liquids can also be used to improve the disulfide exchange reaction. It will be understood that some liquids that can be applied to the fabric before annealing can also be vaporized during annealing and also act as a gas phase agent to improve the disulfide exchange reaction at the annealing temperature. In another embodiment of the present invention, a liquid reagent can be used to brush or soak the desired region of the fabric, which agent can be vaporized to form a gas that enhances the disulfide exchange reaction during the annealing process. Many and many compounds are available, although not all are described in Macaren, JA; Militan, B .; in "Wool Science, The Chemical Reactivity of the Wool Fiber", Science Press, Australia, 1981 and the numerous references in the mima. It has been found that H2S is a gas particularly suitable for improving the disulfide exchange reaction. The reaction of H2S with the wool will be described below with reference to H2S as the agent that improves the disulfide exchange reaction and the improvement due to the introduction of additional thiols is applicable however to other agent either in the form of gas or liquid that improves the disulfide exchange reaction and introduces those disulfide exchange enhancement thiols. The scheme described below underlines the important reactions that are postulated to occur during annealing of the wool and in the method of the present invention. However, the inventors do not wish to bind to any particular theory. The reaction of H2S with disulfides in proteins results in the formation of a dihydrosulfide and a thiol (2) as long as the analogous reaction occurring in the wool forms the hydrodisulfide or residue of pertiocysteine, from the cysteine residue as shown in the scheme (1) below. The disproportion of cysteine can also form pertiocysteine, although it is accompanied by the formation of dehydroalanine as shown in the scheme (2). Thiols can be added spontaneously to the β-position of activated carbonyl double bonds (2) A similar reaction between dehydroalanine and cysteine occurs in the wool and results in the formation of lanthionine as shown in the scheme (3). It is expected that the addition of H2S to dehydroalanine as shown in scheme (4) is also possible.

NH NH-NH HN-CH-CH2-S-CH2-CH- + H2S- - »CH-CH2-SH + HSS-CH2-CH (1) I I -CO OC- -CO oc-cystine cysteine pertiocysteme NH HN- • NH HN-CH-CH2-S-S-CH2-CH- > C = CH2 + CH-CH2-SSH (2) -CO OC- -CO-OC-cystine dehydroalanine pertiocysteine NH HN- -NH HN-C = CH2 + HS-CH2-CH-CH-CH2-S-CH2-CH ( 3) -CO oc- • CO oc- dehydroalanine cysteine lanthionine NH HN- I C = CH2 + H2S CH-CH2-SH (4) I I -CO OC dehydroalanine cysteine These are the main reactions that are considered to be responsible for the chemical changes that occur during traditional annealing or annealing in the presence of H2S. Without the presence of H2S during the annealing or when only a small number of thiols is present the disulfide exchange reaction will eventually be inhibited due to the removal of the catalyst thiols through the reaction with dehydroalanine. The presence of additional thiols during annealing increases the disulfide exchange reaction and allows it to proceed to a state where the reformed disulfide entanglement network is capable of inhibiting the absorption of water at a high relative humidity. A total sulfur analysis of the annealed wool in the presence of the H2S shows an increase in the sulfur content of approximately 40 μmol / g dry wool which indicates that it is the total extension of the reaction and the number of additional thiols formed. Oxidation or blocking of excess thiols after annealing may be desirable in some applications. Accordingly in a preferred embodiment the wool is further treated, after annealing in the presence of an agent that increases the disulfide exchange reaction or after annealing in which an excess of thiols was introduced before annealing, with an additional reagent to oxidize or block excess thiol groups. This can be achieved in any suitable manner by the reaction to remove or convert thiols to species that does not catalyze the disulfide exchange reaction. Numerous compounds are available to achieve this, for example, hydrogen peroxide, peracids, acrylonitrile, formaldehyde, benzoquinone, ethylene oxide, ozone, oxygen, epoxypropane, butadiene diepoxide, butadiene monoxide, trimethylene oxide with many but not all represented in Maclaren, J A .; Milligan, B .; "Wool Science, The Chemical Reactivity of the Wool Fiber", Science Press, Australia, 1981 and given only by way of example. This reaction can be carried out in the gas phase, in solvents that include water or if it is used using an aerosol of the required chemical. By way of example, acrylonitrile, hydrogen peroxide, peracetic acid, oxygen and benzoquinone are exemplified hereinafter. Of course other treatments are possible and can include reactive nucleophiles that react to form additional entanglements or to replace existing entanglements with more stable ones, for example, the disulfide entanglement can be replaced by more stable lathionine entanglement by reaction with cyanide . The current treatment conditions that can be used to execute the method of the present invention can vary considerably. The variables of annealing time, temperature, recovery and the amount of agent to improve the disulfide exchange are interrelated and to a complementary degree. The preferred treatment conditions are for annealing with approximately 15% recovery; at a temperature of about 100 ° C; for a time of about 4 hours; for additional thiols between about 5 and 400 μmol / g dry cloth with about 40 μmol / g dry cloth which is more preferable. In general, the upper limit of the temperature will be set lower than that in which the fabric is permanently damaged, for example by decolorization, while the lower limit will be determined by the economy of time. This recovery can be controlled by precise control of the relative humidity surrounding the fabric. Relative humidity control can be achieved in any suitable way and can include, for example, by preconditioning the fabric to the desired recovery at a suitable temperature followed by annealing in a chamber in which the mass ratio of fabric to volume can be used to obtain the desired recovery at the annealing temperature, by combining of gas streams of different moisture contents to the appropriate mixture to obtain the desired relative humidity and therefore the recovery, by electronic control with feedback using sensors, for example capacitor devices or humidity point sensors etc., to measure the relative humidity or to heat water containing dissolved substances in the correct proportions to reduce the vapor pressure of the water on the solution to the desired relative humidity. The relative humidity of the atmosphere surrounding the fabric can be on the scale from 30 to 95%. preferably on the scale from 75 to 85%. The present invention results in a significant reduction in the absorption of water at high relative humidity (Figure 1) and therefore improves those properties that deteriorate as the water content increases due to the inherent approach or exceeding the transition of the water. glass. The reduction of absorbed water to a high relative humidity beyond that achieved by traditional annealing is considered to occur due to the increased extent of rearrangement of the disulphide bond caused by chemical treatments that introduce additional thiols into the wool and change in the interlacing structure that occurs during the chemically assisted annealing process. In the traditional annealing process, only a modest amount of permanent anchoring occurs so that the extent of the entanglement rearrangement is considered not complete in the proper equilibrium configuration for annealing recovery. It has been found that the annealing treatment can be improved chemically. It has been found that the presence of a small amount of a chemical agent can improve the disulfide exchange reaction or a chemical agent can be used to introduce additional thiols and improve the disulfide exchange reaction, either before or during annealing. It is considered that the chemical agent causes the occurrence of massive disulfide rearrangement and therefore forms a new interlaced network capable of restricting the amount of water absorbed. The invention will be explained more fully with reference to the examples and the drawings that are given by way of example only and in which: Figure 1: is a graph of the absorption isotherm of untreated wool and wool treated as for example 1b which shows the significant reduction in the recovery at high relative humidity. Figure 2: is a graph showing the depression of the glass transition temperature of the wool with increasing water content. The state of the wool is also indicated in relation to the glass transition temperature for the untreated wool and the treated wool as in example 1b which shows that the treatment prevents the wool from exceeding the transition temperature of the glass.

Figure 3: is a graph of wrinkle recovery as measured by the thermo tuning test (Leeder, JD; Textile Res. J., 45, 581, 1975) after the treated wool is submerged in water for 30 minutes and then pressed to steam while it is wet. The treatment conditions were similar to treatment 1b although with the wool at 19.5% recovery and several pressures of H2S. This graph shows the significant improvement in wrinkle recovery that is stable to cold water but not to steam pressure. Untreated wool has a wrinkle recovery of 54% as determined by this method. Figure 4: shows the importance of controlling the recovery during the treatment as in example 1b. The wrinkle test method is as was given for Figure 3 above. Figure 5: shows the effect of a subsequent heat treatment on the fabric as discussed in example 1b. After heating in water or air for 30 minutes the recovery to the wrinkle deteriorates (although more quickly for water) up to the value obtained for the untreated fabric. The wrinkle recoveries were determined as given in Figure 3. Figure 6: shows that the improvement in wrinkle recovery from the treatment as given in example 1b is relatively stable for the exposure time. Figure 7: shows the increased level of fixation that is imparted to the fabric as a result of the treatment as for example 1b compared to the treatment for example 1a.

The level of fixation was obtained by basting in the place of a 180 ° fold in the woolen fabric before annealing. After the annealing and the removal of the basting, the wire cuttings were allowed to relax in water for 15 minutes and their angle was measured; at a lower angle, the greater the degree of fixation. Figure 8: shows the permanent fixation that is imparted with the fabric whether it is restricted or not restricted. The fabric was treated as for example 1b. The level of fixation imparted to the fabric is a restricted configuration was obtained by basting in place of a 180 ° fold in the woolen fabric before treatment. The level of fixation imparted to the fabric in an unrestricted configuration was obtained by cohesive fixation by means of steam pressure (10 s steam, 10 s vacuum) of a fold in the fabric that was allowed to hang freely during the treatment. After the wire cuttings were allowed to relax in water at 50 ° C for 30 minutes and their angle was measured; the extension of the fixation expressed as a percentage is given by 100x (angle-180) / 180. The unrestrained oxidized values are for cloth which has been given a subsequent treatment as detailed in example 8a. Example 1 shows the reduction in saturation recovery that can be obtained by increasing the disulfide exchange reaction during annealing by the presence of H2S.

Example 2 shows the reduction in saturation recovery that can be obtained by the introduction of additional thiols before annealing. Example 3 shows the improved wrinkle recovery of the treated wool fabric. Example 4 shows the improved wrinkle strength of the treated wool fabric. Example 5 shows the increased moisture modulus of the treated wool fibers. Example 6 shows the reduction in saturation recovery of the wool in which part of its crystallinity has been destroyed. Example 7 shows the improved moisture modulus of a wool that has been pretreated to reduce its crystalline fraction. Example 8 shows the improved stability of the treated state at the wet vapor pressure when the additional thiols formed during the treatment are removed by subsequent treatment. Example 9 shows the permanent fixation imparted to the fabric that is treated in an unrestricted manner. Example 10 demonstrates the easy care properties imparted by the treatment.

Example 11 shows the uniform drying performance of the treated fabric (recovery from the wrinkles inserted when the fabric is wet). Example 12 shows the improvement in the aqueous expansion of the treated fabric EXAMPLES Example 1 The effect of the treatment on Saturation Recovery A pure woolen fabric of flat texture construction (176 g / m2, 21 μm diameter wool fibers) was used. Saturation recoveries were determined by immersing the samples in water for 30 minutes with a small amount of detergent, centrifuging to remove excess water, weighing and reweighing after the samples were dried in an oven at 150 ° C. for 1 hour under vacuum.

Example 1a 10 g of fabric was annealed in the traditional manner by conditioning the fabric to 75% relative humidity and annealing at 100 ° C for 4 hours in a 275 ml vessel in the absence of air followed by slow cooling.

Example 1 b 10 g of fabric were conditioned at 75% relative humidity and annealed at 100 ° C for 4 hours in a 275 ml vessel in the absence of air although in the presence of 25 kPa (300 μmol / g dry wool) of H2S followed by slow cooling.

Example 1c The treatment as for Example 1b but followed by an additional treatment to block excess thiols by reaction with acrylonitrile vapor for 30 minutes at 100 ° C.

A small reduction in saturation recovery is evident for annealed wool in the traditional manner in which H2S is not present or in which no additional thiols have been introduced into the wool. However, this reduction is small compared to that obtained by the presence of H2S.

Example 2 Chemicals alternative to H2S are possible, which introduce additional thiols before annealing. After annealing the wool in which additional thiols have been generated, a significant reduction in saturation recovery is possible.

Example 2a 10 g of cloth were soaked in 500 ml of water containing 5 g / l of sodium matabisulfite (Na2S205) at 20 ° C for 3 hours. The fabric was then rinsed completely, conditioned at 75% relative humidity and then annealed in the absence of air for 4 hours at 100 ° C followed by slow cooling. Saturation Recovery = 28% i Example 2b As for example 1b although using sodium dithionite (Na2S204). Saturation Recovery = 28% Example 2c 20 g of cloth were soaked in water saturated with H2S for 1 hour at 20 ° C. The cloth was removed and rinsed thoroughly to remove any residual scent. The fabric was conditioned at a relative humidity of 75% and annealed in the absence of air for 4 hours at 100 ° C followed by slow cooling. Saturation Recovery = 27% Examples 3-5 show the significant change that is possible in the properties of the wool having a lower saturation recovery obtained through the chemical annealing process.

Example 3 Improvement of Wrinkle Recovery A substantial improvement in wrinkle recovery was obtained as measured by the Multiple Fold Test (3) for the fabrics that were annealed as in Example 1. The wrinkle recovery was measured after the samples were submerged in water and left for conditioning for 1 day.

These results clearly show a substantial improvement in wrinkle recovery. This improvement is easily observable during use as a 5% improvement that has been shown to be discernible only during use.

Example 4 Improvement of Shrink Strength The cloth and the treatment as in Example 1b and 1c. Area shrinkage was determined after washing in a suitable equipment (wascator) over the 5A cycle using the normal test method (IWS TM31).

A significant reduction in shrinkage of the fabric is obtained by treatment.

Example 5 Wet Module Increment The wet module on an extension scale of 10% / min of 3 fibers within the Hookean region was measured before the treatment and after the treatment given in Example 1b.

Relative Module = treated / initial = 1.25 This represents a substantial improvement in the wet stiffness of the fiber.

To demonstrate the application capacity of the treatment for fibers other than wool and the regenerated protein which is a poorer fiber since it generally contains little crystallinity, the wool was modified to reduce its crystallinity and given the treatment as detailed in Example 1a , 1b and 1c.

Example 6 Recovery of Saturation of Modified Wool for Reduced Cristallinity. The recovery of saturation of the wool that had destruction of partial crystallinity was determined.

Example 7 Modified Wool Wet Modulus Increase for Cristallinity Reduction The wet modulus of the wool that had partial crystallinity destruction was determined at an extension scale of 100% / min. The average of 50 fibers is given. The Fibers were treated in accordance with the treatment given in Example 1a and also in accordance with the treatment given in Example 1b and 1c.

Example 8 Saturation Regions of Treated Wool After Removal of Additional Thiols and Wet Vapor Pressure. The fabric was treated according to Example 1b. This fabric was then treated by Example 8a Oxidation by reaction with a 2% solution of hydrogen peroxide in water at 20 ° C for 30 minutes.

Example 8b Reaction with acrylonitrile vapor by heating the fabric in the absence of air with acrylonitrile at 100 ° C for 1 hour followed by slow cooling.

Example 8c Steam reaction of peracetic acid by heating the fabric in the absence of air with peracetic acid vapor at 100 ° C for 1 hour.

Example 8d Reaction with benzoquinone vapor by heating the fabric in the absence of air with benzoquinone at 100 ° C for 1 hour.

Example 8e Reaction with an aerosol of 10% hydrogen peroxide / water by generating an aerosol with an ultrasonic humidifier and allowing the drops to make contact with the fabric.

Example 8f Reaction with oxygen by heating at 100 ° C in the presence of oxygen for 1 hour.

The fabrics previously treated were then moistened in water at 20 ° C for 30 minutes and while they were wet they were given a vapor pressure consisting of 10 s of steam and 10 s of vacuum. The improved stability of the reduced recovery state of the wool after the additional thiol removal treatment is demonstrated in the following table.

Example 9 Permanent fixation of wool imparted when not restricted. The level of permanent fixation that remains after the treatment in an unrestricted manner as detailed for Figure 8 is given below by the following treatments.

Example 10 Easy-care permanent pressure properties. A gabardine fabric was given a shrinkage resistance treatment (BAP / silicone) and cooked in the shape of a pair of pants and subjected to vapor pressure so that it contained two seams and two central folds. These pants were conditioned at 75% relative humidity and then suspended without restriction in a large annealing vessel and treated under similar conditions as detailed in Example 1b followed by the additional thiol removal treatment as detailed in the example 8a. An additional trousers was made from the shrink-resistant fabric although there was no additional treatment and it acted as the control. Those pants received five 7.5a wash cycles in a suitable Wascator equipment in accordance with the detailed washing procedure in the test method of the International Wool Secretariat TM31 (1986) with a warm drum drying of 30 minutes between washes . The pants for the shrinkage and appearance of the seams were then examined, folds and softness of the fabric. Although the area shrinkage for both legs was less than 1% the overall appearance of the treated was superior since it retained the acute central folds and flat seams compared to the untreated trousers that lost their flat seams and folds completely after the first wash . The softness of the drum-dried treated fabric was also superior to the untreated fabric.

Example 11 Soft Drying Performance. The performance, gentle drying or recovery to wrinkles inserted when the fabric is wet is shown below. The fabric was treated according to example 1b and given an additional treatment after according to example 8a. The gentle drying performance of the wool that has been soaked in the water for 30 minutes, filled to remove excess water, wrinkled for 15 minutes and allowed to recover for 15 minutes using the multiple fold test (3) given below Example 12 Improvement of aqueous expansion. The fabric that has been dyed into pieces was treated in accordance with the treatment detailed in Example 1b and the detailed treatment was given in Example 8b. The aqueous expansion was then measured by marking the fabric in the warp and weft directions and the difference in length between the wet cloth and after drying in an oven for 1 hour at 100 ° C was measured. The aqueous expansion is given by the difference between the wet and dry lengths expressed as a percentage of the dry length. The warp and weft average are given below. the above examples demonstrate that a significant reduction in the recovery at high relative humidity or when done by wet process will provide a substantial improvement in the properties of the wool that deteriorate under those conditions.

This reduction in recovery is obtained by annealing at a reduced recovery under conditions in which disulfide exchange is possible, for example by the addition of thiols to the wool to facilitate rearrangement. This treatment is also applicable to a material other than wool in which the disulfide bonds can be rearranged and the reformed interlacing to restrict the absorption of water. The arrangement described only by way of explanation has been proposed and many modifications can be made thereto without departing from the spirit and scope of the invention including each novel feature and the combination of novel features described herein.

Claims (29)

1. A process for treating fabric made of proteinaceous materials containing disulfide or polysulfide bonds comprising the annealing of the fabric at a temperature on the scale from 70 ° C to 160 ° C at a recovery of between 10% and 25% for a longer period 10 minutes approximately where the fabric is annealed in the presence of a gas that increases the disulfide exchange reaction.

2. A process according to claim 1, wherein the gas allowing the disulfide exchange reaction is selected from the group consisting of thiol reducing agents including hydrogen sulfide, polysulfides of the form H2S2, H2S3, H2S4 etc. ., thioglycolic acid, 1, 'dithiothreitol, mercaptoethanol, benzylmercaptan, etantiol, benzothiol, 2-aminoethantiol etc .; reducing agents such as phosphines for example phosphine, tris (hydroxymethyl) phosphine, tri-n-butylphosphine, tri-ethyl phosphine and tertiary phosphines derived from phosphine by reaction with amines and formaldehyde; other reducing agents including triethylphosphite, sulfur dioxide.

3. A process according to claim 1 or claim 2, wherein the gas allowing the disulfide exchange reaction is hydrogen sulfide (H2S).

4 A process according to any of claims 1 to 3, wherein the annealing of the fabric is carried out at a temperature of about 100 ° C to a recovery of about 15% over a period of about 4 hours.

5. A process for treating a fabric made of proteinaceous materials containing disulfide or polysulfide bonds comprising annealing the fabric at a temperature on the scale from 70 ° C to 160 ° at a recovery of between 10% and 25% during a period greater than 10 minutes wherein the fabric has been treated at least in part with a liquid that improves the disulfide exchange reaction.

6. A process according to claim 5, wherein the liquid allowing the disulfide exchange reaction is selected from the group consisting of thiol reducing agents including hydrogen sulfide, polysulfides of the form H2S2, H2S3, H2S4 etc. ., thioglycolic acid, 1,4'-dithiothreitol, mercaptoethanol, benzylmercaptan, ethantiol, benzothiol, 2-aminoethiol, cysteine; reducing agents including phosphines for example phosphine, tetrakis (hydroxymethyl) phosphonium chloride, tris (hydroxymethyl) phosphine, tri-n-butylphosphine, tri-ethylfosphine and tertiary phosphines derived from phosphine by reaction with amines and formaldehyde; other reducing agents including triethylphosphite, borohydride, bisulfite, sulfite, dithionite, monoethanolamine sesquisulfide, sulfur, hydroxysulfide, sulfur dioxide etc; thiolate agents including acetyl mercaptosuccinic anhydride, N-acetyl homocysteine thiolactone, homocysteine thiolactone and thioglycolides.

7. A process according to claim 5 or claim 6, wherein the liquid that improves the disulfide exchange reaction is selected from the group consisting of hydrogen sulfide, thioglycolic acid, 1,4-dithiothreitol, mercaptoethanol, benzyl mercaptan , etantiol, bencentiol, cysteine, bisulfite, sulfite, dithionite, monoethanolamine sesquisulfate, sulfur, hydrosulphide, sulfur dioxide and thioglycolides.

8. A process according to any of claims 5 to 7, wherein the fabric is annealed at a temperature of about 100 ° C to a recovery of about 15% over a period of about 4 hours.

9. A process according to any of claims 1 to 8, wherein the fabric is selected from the group consisting of woven and non-woven fabrics, knitting fabrics and felted fabrics.

10. A process according to any of claims 1 to 9, wherein the fabric is a high quality combed wool fabric.

11. A process according to any of claims 1 to 10, wherein the fabric is in the form of an article.

12. A process according to any of claims 1 to 11, wherein the fabric is in the form of a garment.

13. A process according to any of claims 1 to 12, wherein the proteinaceous materials containing disulfide or polysulfide bonds are selected from materials containing keratin, wool, wool with reduced crystallinity, angora cloth, regenerated protein or mixtures of the same.

14. A process according to any of claims 1 to 13, wherein the fabric is made of wool or a combination of wool and other materials.

15. A process according to any of claims 1 to 14, wherein the fabric is annealed in an atmosphere having a relative humidity in the range of 30 to 95%.

16. A process according to any of claims 1 to 15, wherein the fabric is annealed in an atmosphere having a relative humidity of 75 to 85%.

17. A process for permanently fixing a fabric incorporating the process of any of claims 1 to 16.

18. A process for permanently fixing a fabric according to claim 17, wherein the process for permanently fixing the fabric incorporates a treatment of resistance to additional shrinkage.

19. A fabric produced by the process of any of claims 1 to 16.

20. An article made from a cloth whose article has been treated by a process according to any of claims 1 to 16.

21. A garment treated by a process according to any of claims 1 to 16.

22. A cloth produced by the process according to any of claims 17 or 18.

23. An article made from a cloth whose article has been treated by a process according to any of claims 17 or 18.

24. A garment of clothing treated by a process according to any of claims 17 or 18.

25. A process for treating fabric substantially as described heretofore with reference to any of the preceding Examples.

26. A process for permanently securing a fabric substantially as described heretofore with reference to any of the preceding Examples.

27. A fabric substantially as described hereinabove with reference to any of the preceding Examples.

28. An article substantially as heretofore described herein with reference to any of the preceding Examples.

29. A garment substantially as described heretofore with reference to any of the preceding Examples.