MXPA05007414A - Compositions and treated substrates having reversibly adaptable surface energy properties and method for making the same. - Google Patents

Abstract

The present invention relates generally to substrates that exhibit useful, auto adaptable surface energy properties that depend on the environment of the substrate. Such surface energy properties provide relatively high advancing and receding contact angles for liquids when in contact with the target substrate surface. The substrates exhibit low surface energy quantities of at most about 20 millijoules per square meter (mJ/m2) at a temperature of about 25 degrees C and a surface energy greater than about 20 mJ/m2 at, or with exposure to, a temperature of about 40 degrees C. More specifically, encompassed within the present invention are textile substrates having this highly desirable unique surface energy modification property and which exhibit wash durable oil and water repellency and stain release features. Novel compositions and formulations that impart such surface energy modifications to substrates are also encompassed within this invention, as well as methods for producing such treated substrates.

Description

COMPOSITIONS AND TREATED SUBSTRATES WHICH HAVE PROPERTIES OF REVERSIBLY ADAPTABLE SURFACE ENERGY AND METHOD FOR DO THE SAME FIELD OF THE INVENTION The present invention relates generally to substrates that exhibit useful, self-adapting surface energy properties that depend on the environment of the substrate. Such surface energy properties provide progressive and regressive contact angles for liquids when they come into contact with the surface of the target substrate. In particular, the substrates exhibit low surface energy amounts of at most 20 millijoules per square meter (mJ / m2), as measured by Goniometry and calculated by the Fowkes equation, at a temperature of approximately 25 degrees C and an energy surface area greater than approximately 20 mJ / m2 a, or with an exposure to, a temperature of approximately 40 degrees C. This unique ability for automatic surface energy modification, in turn, provides surfaces that are repellent to water and oil, which exhibit certain grades of dye resistance, and which impart effective dye release properties to the target substrate. In addition, this unique surface energy profile is repeatable and reversible depending on the exposed environment. The novel compositions and formulations imparting such surface energy modifications to substrates are also comprised within this invention, as well as methods for producing such treated substrates. More specifically, woven substrates are comprised within the present invention that have this highly desirable unique surface energy modification property and which exhibit durable repellency to oil and water wash and soil / stain release characteristics.

BACKGROUND OF THE INVENTION There has long been a need, particularly within the textile industry, to provide substrates, such as clothing fabrics, as an example, which exhibit a number of durable properties to wash simultaneously. Most notably, water repellency, oil repellency, stain resistance, and stain release characteristics are highly desirable to facilitate substrates cleaning, if complete staining thereof is not avoided. Unfortunately, the provision of such simultaneous and durable features to washing has been severely limited due to the general difficulties with meeting certain surface energy requirements over the life of the durable washout of such a substrate. Generally, coatings or other treatments have not been readily available or have been widely known, which can provide co-existing water and oil repellency and release of staining on a durable basis to wash fabrics (or other surfaces) due to that the surface energy profile required for one of these properties is unevenly different from the • surface energy profile required to impart the other property at the same time. Although there have been some cases of initial simultaneous existence of both properties in certain substrates (as noted below), unfortunately, the degree of wash durability thereof has been unacceptable for the long-term use of objective substrates. As a result, any significant reduction in oil or water repellency consequently reduces stain repellency as well. With a reduced propensity to repel stains, the ability to effect the release of the appropriate stain can likewise be diminished, particularly to exposure to higher staining grades and where the surface energy profile necessary for the proper staining release function (which is similar to that need to impart the aforementioned water and oil repellency properties) is compromised (for example, it is not durable to washing).

Therefore, truly effective treatments for stain release and long-term stain repellents, which are durable to washing, have not been forthcoming, since the simultaneous prevention of both polar (aqueous) and non-polar liquid (olefinic) penetrations ) within the surfaces of the fabric have been very difficult to achieve that they can withstand extended common washing procedures. This problem with the above oil and water repellent surface treatments is more prominently observed on normal high-stained substrates such as cotton-containing fabrics. Such fabrics are generally difficult to modify on their surfaces to the degree necessary to impart both oil and water repellent characteristics therein and to retain an acceptable feel. At least three properties (stain release, water repellency and oil repellency) are not simply available to the textile industry on a durable basis to wash due to the aforementioned surface energy problems. A description of such surface energy properties helps to allow a better understanding of such phenomenon. A fundamental physical property of any material is its surface energy. This property is usually expressed in mJ / m2. Depending on the magnitude of this property, the material can be classified as having a high surface energy or a low surface energy. This property generally depends on the composition of the substrate. For example, a substrate having a surface containing a significant portion of polar hydrophilic groups, such as hydroxyl groups, carboxylic acid groups, amine groups and the like, generally exhibit a high surface energy. Conversely, a substrate having a surface containing a significant portion of hydrophobic, non-polar groups, such as silicone, fluorinated groups, and the like, generally exhibit a low surface energy. It is easily known that when a polar liquid, such as water, becomes. placed in contact with the surface of a substrate, the liquid will spontaneously wet the surface only if the surface tension of the liquid is less than the surface energy of the substrate. Conversely, if the surface tension of the liquid is higher than the surface energy of the substrate, spontaneous wetting will not occur easily, and the liquid will remain pooled on the surface of the substrate. As might be expected then, the surface energy modification of the substrate has long been a major field of research for a variety of materials and for a multitude of reasons. For example, it is often desirable to increase the surface energy of a substrate that facilitates its ability to absorb liquid or to increase adhesion between a coating and a substrate. Practical examples include the chemical treatment of paper or plastic to improve its wetting with inks for printing and plastic crown treatment to increase adhesion between the plastic and other material, such as for the aluminum coating of Mylar® films in packaging applications . The woven substrates have also been modified to create substrates with high surface energy resulting in a tissue substrate that is hydrophilic and exhibits improved comfort and stain release properties. As an example, the detergent industry has used this technique to determine effective methods for cleaning various woven substrates. The modification of surface energy has also been used in other coating applications, such as to produce non-stick surfaces that exhibit low surface energy through the application of Teflon ™ for cooking products and kitchen utensils. Woven substrates have also been modified with low surface energy treatments to produce woven substrates that are hydrophobic, and that exhibit repellent properties (such as for water repellent waterproof clothing). It has been commonly observed that substrates treated with fluorinated polymers generally exhibit a contact angle of more than 100 degrees with water. The progressive and regressive contact angles are very similar. The largest component of the surface energy of such treatments is dispersive. Substrates treated with dual functional repellents, such as those described in US Patent No. 3,574,791 to Sherman et al., Generally exhibit lower contact angles with water when compared to traditional fluorochemical repellents, and therefore tend to They exhibit inferior repellency. The measured surface energy contains significant polar and dispersive components. The differences can usually be measured between the progressive and the regressive contact angles. In some cases, a measurable degree of hysteresis exists between the progressive and regressive contact angle, indicating that the surface energy has changed in the presence of a liquid. Except for liquid adsorption, the hysteresis is indicative that the surface energy has changed (kinetically or thermodynamically) in the presence of a liquid or environmental condition. This measurable degree of hysteresis provides additional evidence that the substrate self-adapts to its environment. A method to achieve the ideal performance for woven applications would be obtained from a composition that provides high progressive contact angles (ie, >; 90 degrees), exhibiting non-porous behavior, to impart resistance to staining and to provide regressive contact angles (i.e.,> 90 degrees), exhibiting porous behavior, to impart release of staining to the substrate. Another method to achieve the ideal performance for such applications would be obtained from a composition that imparts high progression contact angles and high regression between a stained substance and the substrate, followed by contact angles of progression and low regression during exposure to a cleaning procedure. It would be desirable for a porous or dyeable surface to exhibit high contact angles against a variety of liquids to avoid adsorption or staining. It would also be desirable for such surfaces to adapt to a change in their environment, such as in the cleaning medium, to improve the removal of stains and dirt. Other environmental conditions that could induce a change in the surface energy of a substrate include changes in temperature, moisture content, and other environmental factors. A surface that reversibly adapts to its environment would be highly desirable, so that the surface is resistant to staining and cleanable and retains its effect through a number of usage cycles. In many end-use applications, such as clothing, carpets, upholstery and the like, the presence of product retention is extremely important.

Although stain resistance treatments have been developed for each of these exemplary applications, many similar stain resistant clothing treatments have been found, such treatments have an adverse effect on subsequent cleaning. In this way, it would be highly desirable to develop woven substrates resistant to dirt and staining, despite the end use application, which possesses improved cleaning ability using appropriate cleaning techniques. With the development of XPS, SIMS, and other surface analytical techniques, it has been possible to detect certain chemical groups on the surface of materials. For example, one can measure the concentration and depth profile of functional groups, such as portions of CF3 commonly found in chemicals resistant to fluoropolymer staining. Through appropriate sample preparation techniques, it is also possible to observe changes that take place on the surface of a substrate and that occur as a result of changes in the environment to which the substrate is exposed. For example, a substrate that is observed to contain predominantly low surface energy groups, such as CF3 groups, under a first set of conditions can be shown to contain high, significant, hydrophilic surface energy groups, such as hydroxyl groups, as their surface under a second different set of conditions. This polarity change usually allows the surface of the substrate to moisten (ie, absorb liquid), thereby improving release to staining. Since the environment of the substrate is returned to the first set of conditions, it can be observed, for example, that the CF3 groups return to the surface of the substrate, thus returning the substrate to its low surface energy, staining resistance state . Some treatment compositions, such as polymers, possess other properties, such as vitreous transition temperature, which may influence the final performance of the treated substrate. For example, a hard polymer characterized by a high vitreous transition temperature can provide increased protection against moisture, especially forced moisture. However, this high, rigid vitreous transition polymer would probably require more work to adapt to changes in its environment, due to less intrapolymer flexibility. In addition, the molecular weight of the polymer and the addition of the co-monomers can improve wetting, adhesion, chemical reactivity and durability for a variety of substrates as well. As would be apparent in this way, the modification to provide an appropriate surface energy profile that imparts durable oil repellency properties to simultaneous washing, water repellency, stain resistance and release of staining to a target substrate has been sought after by many years without success. The invention as described herein, illustrates that certain combinations of chemicals and processing conditions allow and / or facilitate the design of the surface properties of a target substrate to obtain the desired balance of surface energy profiles to impart simultaneous repellency and characteristics. of release of staining to them. In addition, this unique combination of features has surprisingly shown to be quite durable at routine exposure as well as industrial cleaning methods.

DESCRIPTION OF THE PREVIOUS TECHNIQUE All the North American Patents listed below are fully incorporated herein by reference. U.S. Patent No. 2,841,573 to Ahlbrecht, et al., And U.S. Patent No. 3,645,990 to Raynolds describe the use of fluoropolymers that impart resistance to oil and water to woven substrates. Although a certain degree of resistance to substrate staining is indeed provided, such treatments tend to have limited durability against washing.

In addition, such polymers exhibit the release of staining, especially in circumstances when the stains wet the substrate by force or allowed to dry on the substrate. In fact, the removal of the stain was more difficult under these circumstances than if no treatment was applied to the substrate. In addition, fluoropolymers, silicones, waxes and various other compounds have been disclosed to impart repellency to tissues and other substrates. With the exception of fluoropolymers, such compounds usually provide only water repellency and have limited durability against washing. These techniques are described, for example, in U.S. Patent No. 4,421,796 to Burril, et al. U.S. Patent No. 3,574,791 for Sherman, et al., And U.S. Patent No. 3,896,088 to Raynolds, et al., Describe fluorinated oil-staining release agents that impart some degree of water or oil repellency to a substrate without detrimentally impacting the stain removal during washing Basically, these patents describe polymers comprising both fluorinated repellent portions, and hydrophilic portions. It is claimed that such polymers exhibit a "scale" mechanism that exposes the fluorinated segment in air to provide resistance to staining and then exposes the hydrophilic segment in an aqueous environment to provide release of the stain. Such polymers typically exhibit lower repellency than traditional fluorochemicals, especially lower water repellency, and also suffer from a lack of wash durability. U.S. Patent No. 4,624,676 to White, et al., Discloses unique silicone compounds, such as organosiloxanes, which impart staining release properties to a substrate. Durability is demanded if these compounds crosslink. The compounds can self-crosslink or crosslink to the substrate, especially when appropriate catalysts are used. Such compounds can provide resistance to water-based stains, but rarely to oil-based stains. U.S. Patent No. 4,834,764 to Deiner, et al., Discloses the use of crosslinking resins, such as resins containing methylol or blocked diisocyanates, which improve the durability of fluoropolymers. Indeed, such resins increase the durability of fluoropolymers against washing. These resins are added to the aqueous treatment containing the fluoropolymer. However, although the durability of the dye-repelling properties is certainly increased, the release of acceptable dyeing does not result from this combination.

U.S. Patent No. 4,540,765 to Koemm, et al., Describes fluorochemical repellents that have been shown to have greater durability to washing than previous attempts. Normally, such polymers contain, within the polymer, certain crosslinkable portions. Examples of such crosslinkable moieties include methylol groups, blocked diisocyanate groups, epoxy groups, and the like. Such crosslinkable polymers certainly have greater durability against washing. As is the case with US Patent No. 4,834,764 to Deiner, durability is improved, but the release of acceptable staining is not observed. US Patent No. RE 28,914, to Marco discloses the use of carboxylated acrylic staining release polymers, fluoropolymers and aminoplast resins to produce a cellulose-containing fabric, which possesses good stain repellency and improved stain release. However, this treatment works only with substrates of cellulose-containing fabrics, which exclude most synthetic fibers. U.S. Patent No. 4,695,488 to Hisamoto, et al., Discloses a staining release composition comprising a polymer containing fluoroalkyl groups and alkoxy groups, a hydrophilic resin, and optionally a water and oil repellent. This composition is required to impart waterproofing to durable staining and release properties of staining to a substrate. However, it is described that the level of water and oil repellency is rather low, and the waterproofing test to the described stain is more indicative of the stain resistance than of the stain release. Even with so many attempts within this crowded field to provide the desired properties discussed above, there have been no durable washing treatments that impart acceptable levels of simultaneous water repellency, oil repellency, and stain release characteristics to certain surfaces, in fabrics particular, and most notably, fabrics containing cotton described, used, or suggested within this industry. Thus, none of the references described above suitably describes a surface having durably high levels of water and oil repellency and acceptable levels of stain release for and / or on a variety of substrates. The demands of the market and consumer have shown that it would be desirable to supply various stain resistant substrates with as many common staining materials as possible and simultaneously provide the substrates with improved staining removal characteristics using routine cleaning procedures appropriate for the substrates. These cleaning procedures may include washing, such as in an industrial or home washer, or spot cleaning procedures, such as are used for upholstery. In addition, various other routine cleaning procedures are contemplated, such as those employed for carpet cleaning and dry cleaning. Thus, despite an old need and consumer demand for substrates that have durable repellency and stain release characteristics, previous attempts have shown deficiencies of such an objective.

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide novel compositions that impart durable oil repellency properties to washing, water repellency, and dye resistance, and release of dye simultaneously to a substrate. It is also an object of the present invention to describe a substrate that exhibits durably high levels of water and oil repellency and acceptable levels of stain release during and after the standard washing process, such as industrial or household washers, dry cleaning or other typical surface and / or substrate cleaning methods. It is still another object of the present invention to describe a method for treating a substrate to obtain durably high levels of oil and water repellency and acceptable dye release properties. Other objects of this invention include, without limitation, the application of such novel compositions to certain substrates of the fabric that impart such durable properties to washing thereto either through typical dipping, filling, depletion or other similar application procedures, or through methods of applying the dryer at home. Accordingly, this invention encompasses a composition for altering the surface energy of a substrate in response to a change in the substrate environment, the composition comprising: a high surface energy component, a low surface energy component, and a crosslinking component hydrophobic. More particularly, such invention encompasses a composition for imparting durable repellency and release of staining to a substrate, the composition comprising the resulting product of at least one hydrophilic staining release agent, at least one hydrophobic repellency reagent minus a hydrophobic crosslinking agent. In addition, a surface treatment composition of the fabric comprising at least one fluorinated polymer component is encompassed within this invention, wherein the composition imparts certain repellency and stain release properties to test substrates of polyester or cotton fabrics in terms of high and durable wash oil repellency ratings, water repellency ratings, spray classifications, and stain release classifications as discussed below. In such situations, it should be evident that the composition is defined in this way in terms of the properties imparted to such specific test fabrics, and thus the invention does not require such fabrics to be presented as part of the inventive composition. Other portions of this invention include specific fabric substrates, such as a fabric substrate comprised of at least 20% cotton fiber by weight of the total weight of the substrate, wherein the substrate exhibits an oil repellency rating of at least 4.0. when tested by the AATCC Test Method 118-2000; a water repellency rating of at least 4.0, when tested by 3M Water Repellency Test II (May 1992); a spray capacity of at least 70 when tested by the AATCC Test Method 22-2000; and a stain release classification for corn oil and mineral oil of at least 4.0 when tested by the AATCC Test Method 130-2000; wherein the properties are exhibited after the test cloth has been washed and dried according to Test Method AATCC 130-2000 after 20 washes. Alternatively, and also encompassed herein, is a fabric substrate comprised of at least 20% cotton fiber by weight of the total weight of the substrate, wherein the substrate exhibits a change in surface energy in response to a change in the environment of the substrate to the extent that on exposure to a temperature of about 25 degrees C the measured surface energy is less than about 20 millijoules per square meter, and up to exposure to a temperature of about 40 degrees C, the measured surface energy is greater than about 20 milli ols per square meter. Other fabric substrates are also provided within this invention, including, without limitation, although potentially preferred, a fabric substrate comprising the polyester fibers, wherein the substrate exhibits an oil repellency rating of at least 3.0 when Test by the AATCC Test Method 118-2000; a water repellency rating of at least 3.0 when tested by 3M Water Repellency Test II (May, 1992); a spray capacity of at least 50 when tested by the AATCC Test Method 22-2000; and a classification of the release of the stain for corn oil and mineral oil of at least 3.5 when tested by the AATCC Test Method 130-2000; wherein the properties are exhibited after the test cloth has been washed and dried according to the AATCC Test Method 130-2000 after 20 washes, as well as exhibiting the same surface energy modification properties as presented above in relation to cotton fiber fabrics. Additionally encompassed within this invention is a method that imparts durable repellency and release of staining to a substrate, the method comprising the steps of: (a) providing a substrate; (b) coating the substrate with a composition comprised of a hydrophilic stain release agent, a hydrophobic stain repellent agent, and a hydrophobic crosslinking agent; (c) heating the substrate to remove substantially all excess liquid from the coated substrate; and (d) optionally, further heating the coated substrate. Such inventive compositions, fabrics and methods are discussed in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graphic representation of the XPS Surface Chemical Analysis for a microdenier polyester tissue substrate, treated with the inventive chemical composition of the present invention and for various woven substrates of microdenier polyester treated with various competitive chemical compositions. The graph shows surface chemical analysis of fluorine, carbon and oxygen before the substrate is exposed to a change in its environment (that is, as received following treatment with chemicals), after the substrate is exposed to a change in its environment (i.e., a substrate was moistened with water for 1 hour at 40 ° C, then dried under vacuum), and then the substrate has been heated again (150 ° C for 5 minutes). Figure 2 is a graphical representation similar to Figure 1, except that the graph shows a surface chemical analysis of fluorine, carbon and oxygen before the substrate is exposed to a change in its environment (ie, "as received" following treatment with chemicals) and after the substrate has been washed and dried 10 times.

DETAILED DESCRIPTION OF THE INVENTION Definitions "Water repellency" and "oil repellency" are generally defined as the ability of a substrate to block water and oil from penetration into the substrate, respectively. For example, the substrate may be a tissue substrate that is capable of blocking water and oil from penetrating the fibers of the tissue substrate.

"Stain release" is generally defined as the degree to which a stained substrate focuses on its original unstained appearance, as a result of a careful procedure. As defined herein, high levels of stain resistance means an oil repellency rating of at least 3.0 when tested by the AATCC Test Method 118-2000, a water repellency rating of at least 1.0 when tested. test by the 3M Water Repellency Test II (May, 1992), and a spray capacity of at least 50 when tested by the AATCC Test Method 22-2000. The acceptable stain release, as described herein, means a classification for the release of corn oil and mineral oil of at least 3.0 when tested by the AATCC Test Method 130-2000. "Wash durability" is generally defined as the ability of a substrate to retain an acceptable level of a desired function through a reasonable number of standard wash cycles. More specifically, durability, as described herein, is intended to describe a substrate that maintains adequate properties of dye resistance, water repellency, oil repellency and spray capacity after a minimum of 10 wash cycles, more preferably after 20 wash cycles, and more preferably after 50 wash cycles, in accordance with Test Method AATCC 130-2000. This substrate can be a woven substrate, such as, for example, a woven polyester fabric. The terms "fluorocarbons", "fluoropolymers" and "fluorochemicals" can be used interchangeably herein and each represents a polymeric material containing at least one fluorinated segment. The term "filler" indicates that a liquid coating was applied to a substrate by passing the substrate through a bath and subsequently through press rolls. "Hydrophilic" is defined as having a strong affinity for, or the ability to absorb water. "Hydrophobic" is defined as lacking affinity for, or the ability to absorb water. "High surface energy" is defined as a surface energy equal to or greater than about 25 mJ / m2 at about 25 ° C as calculated from Fowkes two approaches of the component to solid surface energy (for additional information in the equation of Fowkes, see Industrial and Engi- neering Chemistry, 1964, Chapters 12, 40 and 56 by FM Fowkes). "Low surface energy" is defined as less than about 25 mJ / m2 at about 25 ° C as calculated from Fowkes, two approaches of the component to solid surface energy. A high energy surface describes a surface, such as cotton, that can spontaneously moisten (<90 ° of contact angles) by lower surface tension liquids, such as water. A surface of low surface energy, such as Teflon ™, does not spontaneously wet with water and maintains contact angles > 90 ° with liquids containing higher surface tensions (approximately,> 25mN / m.).

Compositions: The compositions useful for delivering a substrate with durability to staining and durable stain release are usually comprised of a hydrophilic stain release agent, a hydrophobic stain repellent, a hydrophobic crosslinking agent, and optionally, others. additives that impart several desirable attributes to the substrate. Within the scope of this invention, new chemical compositions are contemplated wherein the relative amount and chain length of each of the aforementioned chemical agents can be optimized to achieve the desired level of performance for different target substrates within a single chemical composition. . Hydrophilic staining release agents may include ethoxylated polyesters, sulphonated polyesters, ethoxylated nails, carboxylated acrylics, cellulose ethers or ethers, hydrolyzed polymaleic anhydride polymers, polyvinylalcohol polymers, polyacrylamide polymers, hydrophilic fluorinated staining release polymers, polymers of ethoxylated silicones, polyoxyethylene polymers, polyoxyethylene-polyoxypropylene copolymers and the like, or combinations thereof. Hydrophilic fluorinated staining release polymers may be preferred staining release agents. Potentially preferred non-limiting compounds of this type include ÜNIDYNE® TG-992, available from Daikin Corp., REPEARL® SR1100 available from Mitsubishi Corp., as well as ZONYL® 7910, available from DuPont. The treatment of a substrate with a hydrophilic staining release agent generally results in a surface exhibiting high surface energy. Hydrophobic stain repellency agents include waxes, silicones, certain hydrophobic resins, fluoropolymers and the like, or combinations thereof. The fluoropolymers can be preferred stain repellents. Non-limiting, potentially preferred compounds of this type include REPEARL® F8025 and REPEARL® F-89, both available from Mitsubishi Corp., as well as ZONYL® 7713, available from DuPont. The treatment of a substrate with a hydrophobic stain repellent agent generally results in a surface exhibiting a low surface energy. Hydrophobic crosslinking agents include those crosslinking agents that are insoluble in water. More specifically, the hydrophobic crosslinking agents may include monomers containing blocked isocyanates (such as blocked diisocyanates), polymers containing blocked isocyanates (such as blocked diisocyanates), epoxy containing compounds, and the like, or combinations thereof. Diisocyanate containing monomers or polymers containing diisocyanate may be the preferred crosslinking agents. However, monomers or polymers containing two or more blocked isocyanate compounds may be the most preferred crosslinking agents. A potentially preferred crosslinking agent is REPEARL® MF, also available from Mitsubishi Corp. Others include ARKOPHOB® DAN, available from Clariant, EPI-REZ® 5003, 55, available from Shell, and HYDROPHOBOL® XAN, available from DuPont. The total amount of the chemical composition applied to a substrate, as well as the proportions of each of the chemical agents comprising the chemical composition, can vary over a wide range. The total amount of a chemical composition applied to a substrate will generally depend on the composition of the substrate, the level of durability required for a given end-use application, and the cost of the chemical composition. As a general direct line, the total amount of the chemical solids applied to the substrate will be in the range of about 0.25% to about 10.0% by weight of the substrate. More preferably, the total amount of chemical solids applied to the substrate can be in the range of about 0.5% to about 5.0% by weight of the substrate. The typical solids ratios and concentration ratios of the repellency agent to the staining agent release from staining to the crosslinking agent can be in the range of about 10: 1: 0.1 to about 1: 10: 5., including all the proportions and relationships that may be found within this range. Preferably, the solid proportions and concentration ratios of the stain repellent agent to the stain release agent to the crosslinking agent can be in the range of about 5: 1: 0.1 to about 1: 5: 2. More preferably, the solid proportions and concentration ratios of the repellency agent to the staining release agent to the crosslinking agent can be 1: 2: 1. The proportion of the stain release agent to the stain repellent agent to the crosslinking agent can also vary based on the relative importance of each property that is modified. For example, high levels of repellency may be required for a given end-use application. As a result, the amount of the repellent agent, relative to the amount of the stain release agent, can be increased. Alternatively, higher levels of stain release can be estimated to be more important than high levels of stain repellency. In this case, the amount of the staining release agent can be increased, relative to the amount of the stain repellent agent. For the purpose of producing a more economical chemical composition, the type of the stain release agent, stain repellent agent, and crosslinking agent can be varied based on the final use of the substrate treated with the chemical composition. For example, you can produce a treated substrate that is not expected to find oil-based stains. Accordingly, the most economical repellent agents, such as silicones, can be used as a component of the chemical composition. The substrate of the present invention may include glass, fiberglass, metal, films, paper, plastic, stone, bricks, fabrics or combinations thereof. Glass, such as building or automobile windows, can benefit from the current invention. In addition to metal articles, such as bridges or car bodies can benefit from the current invention. Such articles could resist staining by common dirt and be cleaned by rain or the like. The films may include thermoplastic material, heat-hardened materials or combinations thereof. Suitable thermoplastic or thermoplastic materials include polyolefin, polyester, polyamide, polyurethane, acrylic, silicone, melamine compounds, polyvinyl acetate, polyvinyl alcohol, nitrile rubber, ionomers, polyvinyl chloride, polyvinylidene chloride, chloroisoprene, or combinations thereof. . The polyolefin can be polyethylene, polypropylene, ethylvinyl acetate, ethylmethyl acetate or combinations thereof. Woven substrates comprise a non-limiting, potentially preferred embodiment of the current invention. The woven substrates may be of any known construction, including a tile construction, a weft construction, an unframed construction, and the like, or combinations thereof. The woven substrates can have a fabric weight of between about 1 to about 55 ounces / yd2, and more preferably between about 2 and about 12 ounces / yd2. The fabric substrate material may be synthetic fiber, natural fiber, artificial fiber using natural constituents, inorganic fiber, glass fiber, or a mixture of any of the foregoing. By way of example only, the synthetic fibers can include polyester, acrylic, polyamide, polyolefin, polyaramide, polyurethane or mixtures thereof. More specifically, the polyester can include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof. The polyamide can include nylon 6, nylon 6, 6, or combinations thereof. The polyolefin may include polypropylene, polyethylene or combinations thereof. The polyaramide may include poly-p-phenyleneteteraphthalamide (ie, Kevlar®), poly-jn-phenyleneteraphthalamide (ie, Nomex®) or combinations thereof. Exemplary natural fibers include wool, cotton, linen, ramie, jute, linen, silk, hemp or mixtures thereof. Exemplary artificial materials that utilize natural constituents include regenerated cellulose (ie, rayon), lyocell or mixtures thereof. The tissue substrate may be formed from staple fiber, filament fiber, film fiber into strips, or combinations thereof. Fiber can be exposed to one or more texturing processes. The fiber can then be spun or otherwise combined into yarns, for example, by ring spinning, open end spinning, air jet spinning, vortex spinning or combinations thereof. Accordingly, the tissue substrate will generally be comprised of crosslinked fibers, cross-linked threads, loops or combinations thereof. The yarn substrate may be comprised of fibers or yarns of any size, including fibers or microdenier yarns (fibers or yarns having less than one denier per filament). The fibers or yarns may have deniers ranging from less than about 1 denier per filament to about 2000 denier per filament or, more preferably, from less than about 1 denier per filament to about 500 denier per filament. In addition, the fabric substrate may be partially or completely comprised of bicomponent or multicomponent fibers or yarns in various configurations such as, for example, islands at sea, core and sheath, side by side or pie configurations. Depending on the configuration of the bicomponent or multicomponent fibers or yarns, the fibers or yarns can be slit along their length by chemical or mechanical action. The tissue substrate can be printed or dyed for example, to create aesthetically attractive decorative designs on the substrate or to print information messages on the substrate. The tissue substrate can be colored by a variety of dyeing and / or printing techniques, such as high temperature jet dyeing with disperse dyes, thermosol dyeing, pad dyeing, transfer printing, screen printing, digital printing, printing inkjet, flexographic printing, or any other technique that is common in the art for comparable, comparable, traditional woven products. In addition, the fibers or yarns comprising the tissue substrate of the present invention can be dyed by suitable methods prior to the formation of the substrate, such as, for example, through package dyeing, solution dyeing, or beam dyeing, or They can be left undyed. In one embodiment, the tissue substrate can be printed with solvent-based dyes instead of water-based dyes. Solvent-based dyes may be more likely to uniformly wet the hydrophobic surfaces of the current invention. It is also contemplated that a composite material of the tissue substrate can be formed by combining one or more layers of the tissue substrate together. For example, it may be desirable to combine several layers of an open weft fabric substrate together to form a fabric substrate composite. The composite material may also include adhesive material or one or more layers of film. The composite material can then be treated with the chemical composition of the present invention to achieve a material that exhibits durable stain repellency and stain release performance characteristics. Alternatively, in yet another embodiment of the invention, the woven substrates comprising the composite can be treated with the chemical composition before being combined into a composite material. In a potentially preferred embodiment of the current invention, a consumer product with a limited shelf life can be treated with the minimum amount of chemicals to achieve the required properties. More specifically, a substrate such as a lightweight disposable polyester lab coat may only have about 0.25% to about 1.5% of the chemical solids applied to the substrate. Conversely, in another potentially preferred embodiment of the invention, a premium article with a longer shelf life can be treated with an amount close to the maximum of chemicals to achieve the desired level of durability. More specifically, a substrate, such as a first-grade cotton clothing article or a polyester / cotton blend workwear uniform, may have from about 1.0% to about 10.0% of the chemical solids applied to the substrate. The application of stain release agents, stain repellents and crosslinking to the tissue substrate can be achieved by a variety of application methods including dip coating, filler, spray, foam coating, depletion techniques or by any other technique by which a controlled amount of a liquid suspension can be applied to a tissue substrate. Employing one or more of these application techniques may allow the chemist to apply to the tissue substrate in a uniform manner. The chemical agents can be applied simultaneously or sequentially to the tissue substrate. For example, a stain release agent, stain repellent agent, and a hydrophobic crosslinking agent can be mixed together in a solution and then applied simultaneously to the tissue substrate by filling. After the application of the chemical agents to the tissue substrate, the treated substrate is generally exposed to a drying step to evaporate the excess liquid, leaving the solid active components on the surface of the treated substrate. Drying can be achieved by any technique normally used in production operations, such as dry heat from a tender frame, microwave energy, infrared heating, steam, superheated steam, autoclave, or the like, or any combination thereof. In yet another embodiment, a staining release agent can be applied to the tissue substrate, the substrate can be dried or left moist, and then a stain repellent and hydrophobic crosslinking agent can be applied on top of the release agent of staining, creating a sequential chemical treatment, stratified on the surface of the tissue substrate. It may be desirable to expose the treated substrate to an additional heating step to further improve the performance or durability of the chemical agents. This step can be referred to as a curing step. By way of example, additional heating can (a) allow discrete particles of the active components of the chemical agents to flow-melt together, resulting in layers of cohesive, uniform films; (b) induce the preferred alignment in certain segments of the chemical agents; (c) induce crosslinking reactions between chemical agents or between chemical agents and the substrate; or (d) combinations thereof. In many cases, for a tissue substrate to perform satisfactorily, despite end-use application, different attributes of durability to staining and durable staining release are desirable. Examples of such attributes include static protection, wrinkle resistance, reduction or elimination of shrinkage, desirable touch requirements (or feel), dye firmness requirements, odor control, flammability requirements, resistance to dry soiling, and the like. Unexpectedly, a tissue substrate treated according to the present invention actually exhibits anti-adhesion and antistatic properties, which is a desirable feature of the substrate, for example, during a garment cutting and sewing process. Accordingly, it may be desirable to treat the tissue substrate with chemical-containing finishes such as antimicrobial agents, antibacterial agents, antifungal agents, fire retardants, UV light inhibitors, antioxidants, coloring agents, lubricants, antistatic agents, fragrances and the like, or combinations thereof. Chemical application can be achieved by dip coating, filling, spraying, foam coating, or by any other technique whereby a controlled amount of a liquid suspension can be applied to a tissue substrate. Employing one or more of these application techniques may allow the chemist to apply to the tissue substrate in a uniform manner. Many chemical treatments can be incorporated simultaneously with the chemical composition of the current invention, or such treatments can be carried out prior to treatment with the chemical composition of the current invention. It is also possible, using appropriate techniques, to apply many chemical treatments after treatment with the chemical composition of the current invention. Additionally, the tissue substrate can also be treated by mechanical finishing techniques. For example, it may be desirable to expose the tissue substrate to mechanical treatment such as calendering, embossing, embossing, rainbow embossing or hologram printing, metal foil or film hologram printing, cloth metallization, heat setting, hydroentangling with water or air, sanforization, glazing, silky gloss, agamuzar, sanded, sanding, carduzado, shearing, diablado, decantado, fabric modeling through the use of water, air, laser or printed rolls, and the like, or combinations thereof. These mechanical treatments normally provide desirable effects to the tissue substrate that affects such properties as the appearance, strength and / or feel of the fabric. Depending on which mechanical treatment is used, advantages may be obtained by the treatment either before or after the chemistry of the current invention is applied. As an example, the benefits from sandblasting before chemical treatment and calendering after chemical treatment can be conceptualized. Within the scope of the present invention, you can also contemplate that asymmetric woven substrates can be created with surfaces having dual, functional attributes. For example, a tissue substrate having a first and a second surface can be produced so as to have a first hydrophobic surface and a second hydrophilic surface. Such a dual functional tissue substrate can be made for example by coating arabas surfaces of the tissue substrate with a hydrophilic staining release agent and then coating the first surface of the substrate with a hydrophobic stain repellent and a hydrophobic crosslinking agent. Chemical application methods include any of those previously discussed, such as spray coating, foam coating and the like. As a result, garments made in this way can provide increased protection from environmental or chemical assault by repelling liquids in the first surface of the garment and, at the same time, provide increased comfort to the wearer by absorbing moisture, such as perspiration, in the second surface of the garment.

DESCRIPTION OF THE PREFERRED MODALITY Compositions and Applications of Treatment of the Same to Fabric Substrates A) Fabric Application Procedures: All the examples provided below were treated according to one of the following procedures and are observed accordingly. 1) One step application procedure: 1. A piece of fabric approximately 35.56 cm x 45.72 cm (14 inches by 18 inches) was immersed in a bath containing the chemical composition comprising the desired chemical agents. 2. Unless stated otherwise, all chemical percentages (%) were% by weight based on the total weight of the prepared bath, and the equilibrium remains when the chemical percentages or grams of chemicals are given, are comprised of Water. In addition, the% of the chemical is based on the chemical as received from the manufacturer, so that if the composition contained 30% of the active component, then X% of this 30% of the composition was used. 3. After the fabric was wetted completely, the fabric was removed from the treatment bath and activated between press rolls at approximately 40 psi to obtain uniform acceleration generally between about 50 and about 90%. 4. The fabric was tensioned and nailed to a frame to retain the desired dimensions. 5. The pin frame was placed in a Despatch oven at a temperature between about 148.8 and about 204.4 degrees C (300 and about 400 degrees F) for between about 0.5 and about 5 minutes to dry and heat fix the fabric and to cure the finish. 6. Once removed from the oven, the cloth was removed from the frame of pins and allowed to equilibrate at room temperature before the test.

II) Two-stage application procedure: 1. The one-stage application procedure was repeated, except that instead of adding all the chemical agents to a chemical bath, one or more chemical agents comprising the chemical composition were applied in a manner separated to the fabric in a specific order as described below. 2. The fabric was immersed in a bath containing one or more of the chemical agents comprising the chemical composition. 3. After the fabric was completely wetted, the fabric was removed from the bath and activated between press rolls as described in the one-step application procedure. 4. The fabric was dried at about 148.8 degrees C for about 4 minutes in a Despatch oven. 5. The fabric was immersed in a fresh bath containing the remaining desired chemical agents comprising the chemical composition. 6. The fabric was dried and cured then as described in the one-step application procedure.

III) Alternative two-stage application procedure: 1. Approximately 100 grams of the fabric was placed in a Werner-Mathis laboratory dyeing machine. 2. Approximately 2 liters of water containing the desired chemicals are added to a jet dyeing machine. 3. The dyeing machine was closed, heated to approximately 130 degrees C, and kept at this temperature for approximately 30 minutes. The pressure increased, when the water heated to approximately 3 bars. 4: The dyeing machine was cooled to approximately 70 degrees C, and the treatment bath was drained. 5. The fabric was centrifuged in the dyeing machine to remove the excess liquor. 6. While still wet, the fabric was immersed in a treatment bath containing the desired chemical agents. Normally, the fabric was immersed for about 1 to about 10 seconds. 7. Once removed from this bath, the fabric was squeezed through pad rolls, placed on a pin frame and dried and cured as in the one step procedure described previously.

IV) Application procedure after curing: 1. The one-step application procedure was repeated, except instead of curing the hydrophobic cross-linking agent during a drying step, the fabric was dried and the chemical agents were cured as follows : (a) the fabric was cured in the first stage at 148.8 degrees C (300 degrees F) for approximately 5 minutes in a Despatch oven; (b) the fabric was then exposed to steam in a hot forming press set at 160 degrees C (320 degrees F) as follows: i) 5 seconds at high pressure ii) 10 seconds of drive steam iii) 5 seconds of push steam iv) 5 seconds of push vacuum; and (c) the fabric was then cured at 154.4 degrees C (310 degrees F) for 10 minutes (to simulate the process to garment manufacturers to cure the resin after permanent press cure).

V) Application Procedure of the Home Dryer: 1. A piece of 20.32 cm x 22.86 cm (8 inches by 9 inches) of the fabric was cut for the procedure, and a template of 11.43 cm x 15.24 cm (4.5 inches x 6 inches) was made and placed on top of the fabric. 2. A chemical composition was placed in a spray bottle and 2.5 grams of the solution was sprayed into the fabric through the opening in the template. 3. The treated fabric was placed in a Dryel® homemade dry cleaning bag obtained from Dryel® home dry cleaning equipment and placed in a home dryer for approximately 30 minutes at elevated setting. 4. The fabric sample was removed from the dryer and conditioned at room temperature for between about 15 and about 45 minutes before the test.

B) Treatment Compositions Used in the Present Example 1: A 200 gram bath containing the following chemicals was prepared: 1. 9 grams of Unidyne TG-992, a fluorinated hydrophilic staining release agent available from Daikin Corp; 2. 3 grams of Repearl F8025, a fluorinated stain repellent available from Mitsubishi Corp .; and 3. 3.6 grams of Repearl MF, a hydrophobic blocked diisocyanate crosslinking agent available from Mitsubishi Corp. A 100% microdenier polyester fabric was treated with this chemical composition according to the one step application procedure previously described. The moisture recovery of the chemical composition in the fabric was approximately 60%. The polyester fabric was obtained from Milliken & Company of Spartanburg, South Carolina. The fabric comprised of textured filament polyester warp yarns 1/140/200 deniers and textured filament polyester filled yarns 1/150/100 deniers woven together in a 2 by 2 right hand twill pattern having 175 yarns of warp and 80 filled yarns per inch of fabric (hereinafter referred to as "a polyester test cloth" specifically for this invention). The fabric was exposed to a melt finishing process, which involves lightly sanding the surface of the fabric, and subsequently dyeing with a jet. The finished fabric had a weight of approximately 6 ounces per square yard. The treated fabric was tested for water and oil repellency, scrub ability and corn oil and mineral oil stain release by the methods described above after 0 house washes ("AR" indicates "as received"), 10 washes Homemade, 20 home washes, 30 home washes, 40 home washes and 50 home washes. The results of the test are shown in Table IA.

Example 2: Example 1 was repeated, except the concentrations of the chemical agents were varied as follows: Example 2A: 8.0 grams of Unidyne TG-992, 2.4 grams of Repearl F8025, 3.0 grams of Repearl MF; Example 2B: 4.0 grams of ünidyne TG-992, 6 grams of Repearl F8025, 3.0 grams of Repearl MF; and Example 2C: 2.0 grams of ünidyne TG-992, 6 grams of Repearl F8025, 3.0 grams of Repearl MF. The test results are shown in the Table IA.

Example 3 (Comparative): Example 1 was repeated, except that a chemical agent of the chemical composition was removed from the bath as follows: Example 3A: Unidyne TG-992 was not used; Example 3B: Repearl F8025 was not used; and Example 3C: Repearl MF was not used. The test results are shown in the Table IA.

Example 4: Example 1 was repeated, except that some of the chemical agents of the chemical composition were replaced with alternative chemicals from various manufacturers, as follows: Example 4A: Repearl F8025 was replaced with 1% Unidyne TG-571 available from Daikin Corp; Example 4B: Repearl F8025 was replaced with 2% Zonyl 7713 available from DuPont; and Example 4C; Repearl F8025 was replaced with 3% Zonyl 7713, and 4.5% of ünidyne TG-992 was replaced with 1% Zonyl 7910 available from DuPont. The moisture recovery of the chemical composition in the fabric was approximately 60%. The test results are shown in Table IA.

Example 5: Two polyester fabrics, useful for blankets, were made by Milliken & Company and were treated with the following chemistry according to the procedure of application of a previously described step: 1. 4.5% of Unidyne TG-992; 2. 1% Repearl F8025; and 3. 1.8% Arkophob DAN (a hydrophobic crosslinking agent available from Clariant). The moisture recovery of the chemical composition in the fabric was approximately 75%. Example 5A includes treatment of a polyester cover fabric having a fabric made of linen and comprising yarns of flat yarn polyester yarn 56 T DB 1/200/136 deniers available from DuPont and yarns filled with polyester yarn flat 56T DB 2/150/68 deniers available from DuPont. The fabric was further comprised of 61 warp ends per inch of fabric and 45 yarns filled per inch of fabric and had a final fabric weight of approximately 8.75 ounces / square yard. Example 5B was the same as in Example 5 ?, except that the polyester cover fabric was treated with the inventive chemistry and then stamped by transfer. Example 5C included the treatment of a second polyester cover fabric having a failure fabric and comprising yarns of flat yarn polyester warp fb3 SDY 75/36 deniers available from Nanya and yarns filled with polyester yarn flat T -121 8/1 deniers available from DuPont. The fabric was further comprised of 164 warp ends per inch of fabric and 37 yarns filled per inch of fabric and had a final fabric weight of approximately 10.5 ounces / square yard. Example 5D was the same as Example 5C, except that the fabric of the polyester blankets was treated with the inventive chemistry and then stamped by transfer. The treated fabrics were tested for water and oil repellency, spray ability and release of corn oil and mineral oil stain by the methods previously described after 0 industrial washes ("AR" indicates "as received") and 5 industrial washes. The results of the test are shown in Table IB.

Example 6 (Comparative): Example 1 was repeated, except that each chemical agent of the chemical composition was replaced with various competitive stain release chemicals and / or stain repellents. Examples G and H were acquired garments (pants) which were tested together with the subsequent treated fabrics. The chemists used are as follows: Example 6A: 5.0% Scotchgard FC-5102 (stain repellent available from 3M). Example 6B: 5.0% Zonyl 7040 (stain repellent, available from DuPont) Example 6C: 8.0% Scotchgard L-18542 (stain repellent available from 3M) Example 6D: 5.0% Scotchgard FC-248 available 3M fluorinated stain release) Example 6E: 5.0% Zonyl 7910 (fluorinated stain release agent available from DuPont) Example 6F: 5.0% Scotchgard L-18369 (PM 490) (fluorinated stain release agent available from 3M) Example 6G: Stain Protective Pants (DuPont Teflon ™ on polyester / cotton blend garments) Example 6H: Nanocured Pants (100% cotton considered to be treated according to US Patent No. 6,379,753 assigned to Nanotex.) Example 61: 2.5% ünidyne TG-992 0.5% Reagent 901 0.25% zinc nitrate-hydrate 0.35% ünidyne TG-571 (Example 11 in US Patent No. 4,695,488 for Dáikin) Example 6J: 3.0% Repearl F8025 2.0% of Repearl SR-1100 (liberating agent) stain ration available from Mitsubishi Corp.) The test results are shown in the Table II.

Example 7 (Comparative): Example 1 was repeated, except that the polyester fabric was treated according to the two-step application procedure previously described. In the first stage of the procedure, 6.0 grams of PD-75, a carboxylated acrylic stain release agent available from Milliken & amp;; Company, and 0.5 grams of calcium acetate. In the second stage of application of the procedure, 6 grams of Repearl F8025, a fluorinated stain repellent, and 3.0 grams of Repearl MF were applied to the fabric. Treated fabrics were tested for water and oil repellency, spray ability and corn oil and mineral oil stain release by the previously described methods after 0 house washes ("AR" indicates "How it is received") 5 home washes , and 30 home washes. The test results are shown in Table III.

Example 8: Example 1 was repeated, except that the polyester fabric was tested according to the alternative two-step application procedure previously described. In the first stage of the process, 2% ünidyne TG-992 on the weight of the fabric and 1.0% of the acetic acid on the weight of the fabric in the dyeing machine were applied to the fabric. In the second stage of the procedure, 8.0% of Repearl F8025 and 9.6% of Repearl MF were applied subsequently to the fabric. The treated fabrics were tested for water and oil repellency, spray ability and corn oil and mineral oil stain release by the previously described methods after 0 house washes ("AR" indicates "How it is received"), 5 home washes and 30 home washes. The test results are shown in Table III.

Example 9: A 200 gram bath was made containing the following chemicals: a. 12 grams of ünidyne TG-992; b. 4 grams of Repearl F8025; c. 4 grams of Repearl MF; d. 16 grams of Freerez PFK, a permanent pressure resin available from Noveon, Inc .; and. 4 grams of Catalyst 531, a catalyst available from Omnova Solutions; and f. 4 grams of Atebin 1062, a softener available from Boehme Filatex. A 100% cotton fabric was treated with this chemical composition according to the one step application procedure described above. The moisture recovery of the chemical composition in the fabric was approximately 60%. The fabric was obtained from Milliken & Company of Spartanburg, South Carolina. The fabric was comprised of 20/1 denier ring spinning yarns and woven 11/1 denier open-end yarn-filled yarns together in a 3-by-1 left hand twill pattern having 118 yarns of warp and 54 threads filled per inch of fabric. The fabric was subsequently dyed through a continuous dyeing process, sanforized and then treated with the chemical composition. The finishing fabric had a weight of approximately 8 ounces per square yard (hereinafter referred to as "a test cotton fabric" specifically for this invention). The treated fabric was tested for water and oil repellency, dew ability, and corn oil and mineral oil stain release by the previously described methods after 0 house washes ("AR" indicates "as received") 10 home washes, 20 home washes, and 30 home washes. The test results are shown in Table IV.

Example 10: Example 9 was repeated, except that Repearl F8025 was replaced with Zonyl 7713 and Repearl MF was replaced with Hydrophobol XAN at varying concentrations as follows: Example 10A: 8.0 grams of ünidyne TG-992 4.0 grams of Zonyl 7713 4.0 grams of Hydrophobol XAN (a hydrophobic crosslinking agent available from DuPont); Example 10B: 6.0 grams of ünidyne TG-992 6.0 grams of Zonyl 7713 4.0 grams of Hydrophobol XAN; and Example 10C: 4.0 grams of ünidyne TG-992 8.0 grams of Zonyl 7713 4.0 grams of Hydrophobol XAN. The test results are shown in the Table IV.

Example 11 (Comparative): Example 9 was repeated, except that a chemical agent of the chemical composition was removed from the bath as follows: Example 11A: Unidyne TG-992 was not used; Example 11B: No stain repellent was used; Y Example 11C: The hydrophobic crosslinker was not used. The test results are shown in the Table IV.

Example 12 (Comparative): Example 9 was repeated, except that each chemical agent of the chemical composition was replaced with several competitive stain release and / or stain repellent chemicals. (These are the same chemicals and chemical quantities used in Example 6). Examples G and H were acquired garments (pants) which were tested with the others shown later. The chemicals used are as follows: Example 12A: 5.0% Scotchgard FC-5102; Example 12B: 5.0% of Zonyl 7040; Example 12C: 8.0% Scotchgard L-18542; Example 12D: 5.0% Scotchgard FC-248; Example 12E: 5.0% of Zonyl 7910; Example 12F: 5.0% Scotchgard L-18369 (MW 490); Example 12G: Protective Staining Pants (DuPont Teflon ™ in polyester / cotton blend pants); Example 12H: WanoCare pants (100% cotton considered to be treated according to US Patent No. 6,379,753 assigned to Nanotex.) Example 121: 2.5% ünidyne TG-992 0.5% of Reagent 901 0.25% zinc nitrate-hydrate 0.35% Unidyne TG-571 (Example 11 in US Patent No. 4,695,488 for Daikin) Example 12J: 3.0% Repearl F8025 2.0% Repearl SR-1100 The test results are shown in Table V.

Example 13: A fabric mixed with polyester and cotton was treated with the inventive chemistry of the current invention according to the one-step application process and the application procedures after the curing previously described. The fabric was obtained from illiken & Company of Spartanburg, South Carolina. The fabric comprised approximately 65% polyester yarn and approximately 35% cotton yarn. The warp yarns comprised 14.0 / 1 of 65/35 polyester / cotton yarns of open-end yarn with 3.30 multiple twists. The filled yarns comprised 12.0 / 1 of 65/35 polyester / cotton staple fibers of open end yarn with 3.25 multiple twists. The polyester staple fibers for the warp yarns and fillings had a denier of about 1.2. The warp threads and fillings were woven together in a 3 by 1 left hand twill pattern that has 100 warp threads and 47 threads filled per inch of fabric. The fabric was subsequently dyed through a continuous dyeing process and treated with inventive chemistry. The finished fabric had a weight of approximately 8.5 ounces per square yard. The inventive chemistry included the following formulations: Example 13A: was processed using the one-step application procedure 3.75% of Unidyne TG-992 1.25% of Zonyl 7713 (an available repellent of DuPont) 1.25% of Arkophob DAN 10% Permafresh MFX (a permanent pressure resin available from Omnova) 2.5% of the KR Catalyst (an available Omnova catalyst) 0.25% of Tebefoam (a defoamer available from Boehme Filatex) '0.5% of Mikon XLT (a softener available from Omnova) Example 13B: processed using a one-step application procedure 5.4% Unidyne TG-992 1.75% Zonyl 7713 2% Akorphob DAN 10% Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% Mykon XLT Example 13C: processed using the one stage application procedure 0.32% ünidyne TG-992 1.76% Arkophob DAN 3.87% Zonyl 7910 1.55% Repearl F8025 10% Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% of Mykon XLT Example 13D: processed using the one step application procedure of 5% Unidyne TG-992 1% Repearl F-89 3% Epi-Rez 5003 W55 (a hydrophobic crosslinking agent available from Shell) Example 13E: processed using the one step application procedure of Unidyne TG-992 1% Repearl F-89 2% Witcobond W-293 (a hydrophobic crosslinking agent available from Crompton) Example 13F: processed using the application procedure after of the cu ration; 5% ünidyne TG-992 1% Repearl F-89 3% Epi-Rez 5003 W55 5% Permafresh MFX 1.25% KR Catalyst 0.25% Tebefoam 0.5% Mykon XLT Example 13G: processed using application procedure after of healing; 5% of ünidyne TG-992 1% of Repearl F-89 2% of Witcobond W-293 5% of Permafresh MFX 1.25% of Catalyst KR 0.25% of Tebefoam 0.5% of Mykon XLT Example 13H: the same as 13F, plus the addition of: 1% Pluronic F-68 (a staining release agent available from BASF) Example 131: the same as Example 13G, plus the addition of: 1% Pluronic F-68 Example 13F included the same composition The chemical used in Example 13D, except that the permanent pressure resin was used together with other auxiliaries, and the composition was not completely cured to allow permanent wrinkles to be introduced into the fabric. This is known in the art as a resin treatment after curing. However, the fabric was completely cured to simulate the treatment in the garment manufacturing facilities before the test. Similarly, Example 13G included the same chemical composition used in Example 13E, except that the permanent pressure resin was added with other auxiliaries, and the composition was not completely cured to allow permanent wrinkles to be introduced into the garment using the resin treatment after the cure. The fabric was completely cured before the test. Example 13H includes the same chemical composition used in 13F, with the addition of a polyoxyethylene-polyoxypropylene copolymer (Pluronic F-68 from BASF). This was applied with the application method after the cure. Example 131 includes the same chemical composition used in 13Fr with the addition of a polyoxyethylene-polyoxypropylene copolymer (Pluronic F-68 from BASF). This was also applied with the application method after curing. Treated fabrics were tested for water and oil repellency, spray ability, and corn oil and mineral oil stain release by the previously described methods after 0 house washes ("AR" indicates "How it is received"), 5 washes Homemade, 10 home washes, 20 home washes and 30 home washes. The test results are shown in Table VI.

Example 14 (Comparative): Example 13 was repeated, except that each chemical agent of the chemical composition was replaced with various competitive stain release chemicals and / or stain repellents. Additionally, the fabric used for Example 14D was of slightly different construction than the fabric described in Example 13. The 14D fabric was also a 65/35 polyester / cotton blended fabric. However, the warp yarns comprised of polyester / cotton yarns of open end 16/1 yarn with 3.30 multiple twists. The filled yarns comprised of 65/35 polyester / cotton yarns of open end yarn 12.0 / 1. The polyester staple fibers for the filled and warp yarns had a denier of about 1.2. The filled and warp yarns were woven together in a 2 by 1 left hand twill pattern having 88 warp yarns and 46 fill yarns per inch of the fabric. The fabric was subsequently dyed through a continuous dyeing process and treated with inventive chemistry. The finishing fabric had a weight of approximately 7.2 ounces per square yard. The chemical compositions are as follows: Example 14A: processed using the one step application procedure 1.5% Zonyl 7910 18% Permafresh MFX 4.5% Catalyst KR I.25% Mykon XLT 0.5% Tebefoam 1868 0.35% progapol DAP-9 Example 14B: Processed using the method of applying a lid II.1% Scotchgard L-18369 2.2% Hydrophobol XAN 9% Permafresh MFX 2.2% Catalyst 531 1% Mykon NRW3 Example 14C: Processed using the One stage application procedure 6% Zonyl 7713 6% Zonyl 7714 2% Hipochem CSA 3% ültratex REP 1.5% Hydrophobol XAN 13% Freerez PFK 2.9% Catalyst KR Example 14D: Processed using the application procedure one stage 10% Zonyl S410 1% Atebin 1062 3% Ultratex REP 1% Hydrophobol XAN 15% Permafresh MFX 3.75% Catalyst 531 Example 14E: Protective Staining Pants (DuPont Teflon ™ in polyester blend pants /cotton); Example 14F: NanoCare pants (100% cotton considered to be treated according to US Patent No. 6,379,753 assigned to Nanotex.); Example 14G: processed using the application procedure after curing 8% Sctochgard L-18542 10% Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% Mykon XLT Example 14H: processed using the application procedure after curing 4% Scotchgard L-18542 10% Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% Mykon XLT The results of the test are shown in the Table VII.

Example 15: The fabric of Example 13 was treated using the following inventive chemical compositions: Example 15A: processed using the one step application procedure 3.75% Unidyne TG-992 1.25% Zonyl 7713 1.25% Arkophob DAN 10% Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% Mykon XLT Example 15B: processed using the one-step application procedure 5.4% Unidyne TG-992 1.75% Zonyl 7713 2% Arkophob DAN 10% Permafresh MFX 2.5 % of Catalyst KR 0.25% of Tebefoam 0.5% of Mykon XLT Example 15C: processed using the application procedure after curing 0.32% of ünidyne TG-992 1.76% of Arkophob DAN 3.87% of Zonyl 7910 1.55% of Repearl F8025 10% of Permafresh MFX 2.5% Catalyst KR 0.25% Tebefoam 0.5% Mykon XLT Example 15D: processed using the application procedure after curing 5% Unidyne TG-992 1% Repearl F-89 3% Epi-Rez 5003 55 Example 15E : indicted using the application procedure after curing 5% ünidyne TG-992; 1% Repearl F-89; 0.5% Epi-Rez 5003 55; 5% Permafresh MFX; 2% of Witcobond W-293 and 1.25% of Catalyst KR. 0.25% of Tebefoam 0.5% of Mykon XLT The fabrics were tested for water and oil repellency, spray ability and corn oil and mineral oil stain release by the methods previously described after 0 industrial washes, 5 industrial washes, 10 industrial washes, 20 industrial washes, and 30 industrial washes. The test results are shown in Table VIII.

Example 16 (Comparative): Example 16A: The fabric of Example 13 was treated with the application procedure after curing previously described using the following competitive chemistry: 4% Scotchgard L-18542 10% Permafresh MFX 2.5% Catalyst KR 0.25 % Tebefoam 0.5% Mykon XLT Example 16B: The fabric of Example 1 was treated with the previously described one stage application procedure using the following competitive chemistry: 10% Zonyl 7040 2.0% Reactant 901 1%, Free Cat (available from Noveon, Inc.) 0.4% Alkanol 6112 (a wetting agent) The fabric was tested after 0 industrial washes 5 industrial washes, 10 industrial washes, 20 industrial washes and 30 industrial washes. The test results are shown in Table VIII.

Example 17: A piece of nylon fabric was treated with the inventive chemistry of the current invention according to the application method of a previously described step. The fabric was obtained from Milliken & Company of Spartanburg, South Carolina. The warp yarns comprised nylon fibers 6.6 of 70/34 denier filament. The filled yarns comprised nylon 6,6 fibers of 2/070/66 denier filament. The fiber was purchased from DuPont. The warp yarns and fillings were woven together in a flat woven pattern having 106 warp yarns and 68 yarns filled per inch of the fabric. The fabric was subsequently dyed by jet and then the melt finish by exposure to light for mechanical sanding. The finishing fabric had a width of approximately 60 inches and a weight of approximately 4.8 ounces per yard. The inventive chemistry included the following formulation (% by weight in the bath): 1. 2% Zonyl 7910 2. 2% Repearl F8025 3. 1.5% Arkophob DAN. The moisture recovery of the chemical bath in the fabric was approximately 52%. The treated fabrics were tested for water and oil repellency, spray ability and corn oil and mineral oil stain release by the previously described methods after 0 house washes (WAR "indicates" As Received "), 5 household washes, and 10 home washes.The test results are shown in Table IX.

Example 18 (Comparative): Example 17 was repeated, except that each chemical agent of the chemical composition was replaced with various stain release chemicals and / or competitive stain repellents. The chemists used are as follows: Example 18A: 3.0% Zonyl 7713 and 1% Repearl MF; Example 18B: 3.0% of Scotchgard L-18369 and 1% of Hydrophobol XAN; and Example 18C: 6.0% Scotchgard L-18542 and 1.5% Repearl MF. The test results are also shown in Table IX.

Example 19: A piece of the Nomex® fabric was treated with the inventive chemistry of the current invention according to the one-step application procedure described previously. The fabric was obtained from illiken & Company of Spartanburg, South Carolina. The warp yarns and fillings comprised of Nomex® T-462 cut fiber of 38/2 deniers. The warp threads and fillings were woven together in a flat woven pattern that has 67 warp threads and 43 threads filled per inch of the fabric. The fabric was subsequently dyed piece by piece and then finished by conventional means. The finished fabric had a width of approximately 60 inches and a weight of approximately 4.5 ounces per yard. The inventive chemistry included the following formulation: Example 19A: 2% Unidyne TG-992 1% Zonyl 7713 1.5% Arkophob DAN Example 19B: 0.25% Unidyne TG-992 1.75% Zonyl 7910 2% Repearl F8025 1.5% from Arkophob DAN Example 19C: untreated fabric (control). The moisture recovery of the chemical bath in the fabric was approximately 93%. The treated fabrics were tested for water and oil repellency, spray ability and corn oil and mineral oil stain release by the previously described methods after 0 house washes ("AR" indicates "As Received") and after of 5 household washes. The test results are shown in Table X. Each of these exemplified substrates was then tested for various surface properties: C) Fabric Surface Analysis Procedures and Test Results: I) Description of Test Methods Followed: a) The Home Wash procedure subsequently undertaken to test the washing durability was conducted in accordance with Test Method AATCC 130-2000 , using wash procedure 1 (40.55 ° C (105 ° F wash)) and Tide® Rapid Solvent Power detergent. The Industrial Washing Procedure was conducted according to a standard procedure used by many facilities. large industrial laundry. The procedure is identified as one used for colored mixtures of woven substrates and uses the following process steps: Water Water level / 281bs Operation Time (Min) Water temperature load Supply (° F) Suspension 16/1 165 Low 30 mL Express Enj ague 2/1 150 Elevated 340 mL Horizon Rinse 2/1 135 Elevated 350 mL Choice MP Rinse 2/1 120 Elevated Sour 4/1 Frió Ba or 15 mL P. Sour Extract 2 Ba o The load size for the industrial wash procedure was determined to be 80% machine capacity (28 pounds load on a 35 pound machine). The total wash cycle time was approximately 33 minutes. The time shown, for example, as "16/1" indicates that the washing time was 16 minutes and the draining time was 1 minute. The chemicals used for washing were obtained from Washing Systems Inc. The chemists were Choice MP, a concentrated non-ionic surfactant, Horizon, a silicate phosphate builder, Express, an alkali compound, and Sour, an acidic compound. The pH range of the wash cycle was maintained in a range between approximately 10.2 and 10.8. b) The Spray Capacity Test was conducted in accordance with AATCC Test Method 22-2000 (American Association of Textile Chemists and Colorists). The classification scale is as follows: 100 - No adhesion or wetting of the upper surface 90 - Adherence or slight random wetting of the upper surface 80 - Wetting of the upper surface at sprinkling points 70 - Partial wetting of the total upper surface 50 - Complete humidification of the total of the lower surface. 0 - Complete humidification of the total of the upper and lower surfaces. c) The Stain Release was determined using the AATCC Test Method 130-2000. The staining agents used in the Stain Release tests were corn oil (CO) and mineral oil (MI). The rating scale is 1-5, with "1" indicating the most deficient grade of stain removal, and "5" indicating the best degree of stain removal. Generally, a classification of approximately 3.0 is the minimum acceptable level of staining for attire and normal use. d) Water repellency was tested according to Test 3 of Water Repellency 3M (May, 1992). The rating scale is 0-10, with "0" indicating the most deficient degree of repellency (substrates having higher surface energy) and "10" indicating the best degree of repellency (substrates having lower surface energy). The 3M Water Repellency Test scale is: 0 is 0% Isopropanol, 100% water (by weight) 1 is 10% IPA, 90% water 2 is 20% IPA, 80% water 3 is 30% of IPA, 70% of water 4 is 40% of IPA, 60% of water 5 is 50% of IPA, 50% of water 6 is 60% of IPA, 40% of water 7 is 70% of IPA, 30 % of water 8 is 80% of IPA, 20% of water 9 is 90% of IPA, 10% of water 10 is 100% of IPA e) Oil repellency was tested according to Test Method AATCC 118-2000. The rating scale is 0 - with '0' indicating the most deficient degree of repellency (substrates having higher surface energy) and "8" indicating the best degree of repellency (substrates having lower surface energy). The oil repellency scale is: • 0 is Nujol ™ Mineral Oil (the substrates are moistened with the oil) • 1 is Nujol ™ Mineral Oil • 2 is Nujol / n-hexadecane 65/35 (by volume) • 3 is n -hexadecane • 4 is n-tetradecane • 5 is n-dodecane • 6 is n-decane • 7 is n-octane • 8 is n-heptane f) Kawabata Hand Test A variety of characteristics were measured using the Kawabata Assessment System ("Kawabata System"). The Kawabata System was developed by Dr. Soo Kawabata, Professor of Polymer Chemistry at the University of Kyoto, Japan, as a scientific means to measure, in an objective and reproducible way, the "touch" of woven fabrics. This is achieved by measuring the basic mechanical properties that have been correlated with aesthetic properties in relation to touch (for example, fineness, fullness, rigidity, softness, flexibility and crimp), using a set of four highly specialized measuring devices that were specifically developed for use with the Kawabata System. These devices are as follows: Kawabata Strain and Tension Tester (KES FBI) Pure Kawabata Compression Tester (KES FB2) Kawabata Compression Tester (KES FB3) Kawabata Surface Tester (KES FB4) KES FBI is manufactured to 3 by Kato Iron Works Co., Ltd., Div. Of Instrumentation, Kyoto , Japan. KES FB4 (Kawabata Surface Tester) is manufactured by Kato Tekko Co., Ltd., Div Of Instrumentation, Kyoto, Japan. In each case, measurements were made according to the standard Kawabata Test Procedures, with four samples of 20.32 cm x 20.32 cm (8 inches x 8 inches) of each type of fabric being tested, and the average results. Care was taken to avoid bending, wrinkling, tension or otherwise manipulating the samples in a manner that would deform the sample. The fabrics were tested in their manufactured form (ie, they did not undergo subsequent bleaching). The die used to cut each sample is aligned with the threads in the fabric to improve the accuracy of the measurements. i) Measurements of Shear Effort The test equipment was established according to the instructions in the Kawabata manual. The Kawabata shear tester (KES FBI) was allowed to warm up for at least 15 minutes before being calibrated. The tester was set as follows: Sensitivity: 2 and X5 Sample width: 20 cm Shear Stress Weight: 195 g Tension Speed: .2 mm / s Elongation Sensitivity: 25 mm Shear test measures resistive forces when the fabric is given a constant tension force and subjected to a shear stress in the direction perpendicular to the constant tension force. Rigidity of Average Cutting Effort (G) [gf / (cm / deg)]. The average shear stiffness was measured in each of the warp and fill directions. A lower value of shear stiffness is indicative of a softer feel. Four samples were taken in each of the warp and fill directions, and are listed below. ii) Bending Measurements Bending Stiffness (B) - A lower value means that a fabric is less rigid. Four samples were taken in each of the warp and fill directions. iii) Compression Analysis The test equipment was established according to the instructions in the Kawabata manual. The Kawabata Compression Tester (KES FB3) was allowed to warm up for at least 15 minutes before calibrating. The tester was set as follows: Sensitivity: 2 and X5 Blow: 5 mm Compression Speed: 1 mm / 50 s Sample Size: 20 x 20 cm The compression test measures the resistive forces experienced by a plunger having a certain area surface when moving alternately towards and away from a sample of the fabric in a direction perpendicular to the fabric. The test finally measures the work done in the compression of the fabric (front direction) at a pre-established maximum force and the work done while the fabric is decompressed (reverse direction). Percent compressibility to 0.5 grams (COMP05). The higher the measure, the more compressible the fabric. Maximum thickness (TMAX). Thickness [mm] at maximum pressure (nominal is 50 gf / cm2). A higher TMAX indicates a higher fabric. Minimum Thickness (TMIN) Thickness at 0.5 g / sq cm. More is generally considered to be better. A higher TMIN indicates a higher fabric. Minimum Density - Density to TMIN (DMIN). Minor is generally considered to be better Tmin [g / g / cm3] Maximum Density - Density to TMAX (DMAX) Tmax [g / cm3] A lower value is generally considered to be better. Compression Work by Unit Area (WC) Energy to compress the fabric to 50 gf / cm2 [gf-cm / cm2]. More is generally considered to be better. Decompression Work by Unitary Area (WC) This is an indication of the elasticity of the fabric. A larger number indicates more elasticity (that is, a more elastic hand) that is generally considered to be better. iv) Surface Analysis The Test equipment was established according to the instructions in the Kawabata Manual. The Kawabata Surface Tester (KES FB4) was allowed to warm up for at least 15 minutes before calibrating. The tester was set as follows: Sensitivity 1: 2 and X5 Sensitivity 2: 2 and X5 Stress Weight: 480 g Surface Roughness Weight: 10 g Sample Size: 20 x 20 cm Surface test measures frictional properties and properties of geometric roughness of the surface of the fabric. Coefficient of Friction - (MIU) Average Coefficient of friction [without dimension]. This was tested in each of the warp and fill directions, a higher value indicates that the surface consists of more fiber ends and loops, which gives the fabric a soft, fluffy feel. Four samples were taken in each of the warp and fill directions, and are listed later. Surface roughness (SMD) Average deviation of the normal contactor displacement to the surface [micras]. Indicative of how rough the surface of the fabric is. A lower value indicates that a surface of the fabric has more ends of the fiber and loops that gives a fabric a softer, more comfortable feel. Four samples were taken in each of the warp and fill directions, and are listed later. g) The Dry Cleaning Test Method was conducted by placing a piece of 15.24 cm x 15.24 cm (6 inches x 6 inches) fabric in a 1 quart vessel with 250 ml of perchlorethylene. The vessel was shaken vigorously for 5 minutes. The cloth was then stirred and allowed to air dry for a minimum of 8 hours. This method is referred to below as "1 Dry Cleaning Method." H) The Static Test method was conducted by placing a piece of approximately 7.62 cm x 20.32 cm (3 inches by 8 inches) in cloth on a laboratory bench. The sample was rubbed vigorously (in one direction) 20 times with a new paper towel.A Simco F 300 Electrostatic Field meter was placed immediately about 2.54 cm (1 inch) out of the cloth, and the button was pressed to make Measurement The result obtained was recorded in kilovolts To obtain results after conditioning the fabric, the fabric sample was placed overnight at an environmentally controlled temperature at 21,111 degrees C (70 degrees F.) and 65% Relative Humidity The measurement was repeated in the conditioned sample i) Progressive and Reverse Contact Angles were measured using the following two instruments and procedures: i) Test Method d The Tensiometer: The tensiometer, as used herein, involves a gravimetric measurement of the installation forces when a solid is placed in contact with a test liquid (ilhelmy method). These interaction forces are a dynamic measure and reflect the interactions of the entire submerged article (wetted length). The forces are measured when the article is advanced in and out of a test liquid. From these measurements, both contact angles of progression and regression, respectively, can be calculated in an indirect way (Wilhelmy's equation). ii) Goniometer Test Method: The goniometry, as used herein, involves the optical observation of a located drop of test liquids in a solid substrate. The tangent angles are measured for each test liquid by providing the direct measurement of an "advanced" (static) contact angle. These angles reflect only the average forces imparted from the area under the fall (footprint) and not the volume of the article. These angle calculations can be used to determine the surface energies and corresponding components. Both Test Methods of the Goniometer and Tensiometer achieve similar results with the goniometer which is of a small area and a static measure. j) X-ray Photoelectron Spectroscopy (XPS) was used to perform the surface chemical analysis shown in Example 28 and in Figures 1 and 2. The XPS is described as follows: Since the first use of the XPS to detect surfaces Polymers, as described in The Journal of Polymer Science and Polymer Chemistry Ed. (1977, vol.15, p.2843) by DT Clark and H.R. Thomas, has become a standard quantitative tool for characterization. The energy analyzed electrons, photoemitted during the irradiation of a solid sample by monochromatic X-rays, exhibit sharp peaks that correspond to the binding energies of the nucleus-level electrons in the sample. The peaks of these binding energies can be used to identify the chemical constituents in the specimen. The average free electron path in solids is very short (? ~ 2.3 nm). For reference, see Macromolecules (1988, vol.21, p.2166) by W.S. Bhatia, D.H. Pan, and J.T. Koberstein. The effective sampling depth, Z of XPS can be calculated by Z = 3? cos9, where T is the angle between the normal surface and the electron path emitted to the analyzer. Then, the maximum depth that can be detected is approximately 7 nm at T = 0. For the typical polymeric atomic components, C, N and 0, optimized XPS can detect compositions of 0.2 atom atoms. XPS is also very sensitive to F and Si. Such quantitative information is very useful in understanding the surface behavior of the polymer. X-ray photoelectron (XPS) spectroscopy was used here to examine the chemical composition of the surfaces of the modified tissue, in addition, to evaluate the change of the surface chemical composition under different environmental situations. The XPS spectra were obtained using a Perkin-Elmer Model 5400 XPS spectrometer with an X-ray source Mg Ka (1253.6 eV), operated at 300 W and 14 kV DC, with an emission current of 25 mA. The size of the stain was 1.0 x 3.0 mm. The photoelectrons were analyzed in a hemispherical analyzer using a position sensitive detector.

II) Analysis Results: "N / A" or "NA" shown in the Tables indicates that the test data is not available for that article. The test results for Examples 1-4 are presented in Table ?? The results of Example 1 illustrate the durability of the inventive chemistry in the polyester fabric to maintain high levels of water and oil repellency while at the same time maintaining acceptable levels of stain release through at least 30 wash cycles. The results of Example 2 illustrate the versatility of inventive chemistry by having the ability to maximize the maximum stain repellency performance (ie, the dew ability improves with decreased amounts of Unidyne TG-992) at the cost of the performance of stain release (ie, the release of mineral oil decreases with smaller amounts of Unidyne TG-992) and, conversely, the ability to maximize maximum stain release performance (ie, mineral oil release is highest with higher amounts of Unidyne TG-992) at the cost of stain repellency performance (the spray capacity is lower with larger quantities of ünidyne TG-992). This versatility allows for inventive chemistry that is designed for specific end-use applications such as raincoats, where water repellency may be more desirable, or clothing for work, where the release of staining may be more desirable. The results of Comparative Example 3 illustrates the superior performance obtained by the unique combination of chemical agents described by the current invention. Without this unique combination, and as shown in Comparative Examples 3A-3C, repellency, spray classification, and stain release performance characteristics are not optimized. The results of Example 4 illustrate that alternative chemistries can be used for the fluorinated stain repellent and stain release agents, when combined proportionally with other chemical agents of the chemical composition, to provide durable repellency, dew ability, and release of staining through at least 30 wash cycles.

Table ?? - Microdenier Polyester Weave Substrate with Inventive and Comparative Treatments (Household Washing) Example Ex. 1 Ex. 2A Ex. 2B Ex. 2C Ex. 3A Ex. 3B Ex. 3C Oil Repellency: AR 5 6 6 6 6 5 N / A Water Repellency: AR 9 9 8 9 9 9 9 Dew Classification: AR 80 70 70 80 N / A 80 N / A Release of Corn Oil: o / 1 AR 4.5 4.5 4 2 4 5 5 Mineral Oil Release: 0/1 AR 5 4 4 1 N / A 5 N / A Oil Repellency: 10 washes 4 5 6 5 5 2 3 Water Repellency: 10 washes 7 8 8 7 6 5 5 Dew Classification: 10 washes 70 70 70 100 N / A 70 N / A Release of Corn Oil: 9/10 4.5 5 5 3.5 3.5 4.5 5 Mineral Oil Release: 9/10 4 4 1 1 N / A 4.5 N / A Oil Repellency: 20 washes 4 3 5 5 4 < 1 2 Water Repellency: 20 washes | 7 7 7 7 5 2 3 Dew Capacity: 20 washes 70 N / A N / A N / A N / A N / A N / A Release of Corn Oil: T / 20 4 N / A N / A N / A N / A 5 N / A Mineral Oil Release: 9/20 3.5 N / A N / A N / A N / A 4.5 N / A Oil Repellency: 30 washes 4 2 5 5 4 < eleven Water Repellency: 30 washes 6 4 5 5 4 < 1 3 Dew Capacity: 30 washes 70 50 70 90 N / A 50 N / A Release of Corn Oil: 29/30 4 4.5 4 4 N / A 5 5 Mineral Oil Release: 29/30 3 3.5 1 1 N / A 4.5 N / A Oil Repellency: 40 washes 4 N / A N / A N / A N / A N / A N / A Water Repellency: 40 washes 3 N / A N / A N / A N / A N / A N / A Dew Capacity: 40 washes N / A N / A N / A N / A N / A N / A N / A Corn Oil Release: 39/40 N / A N / A N / A N / A N / A N / A N / A Corn Oil Release: 39/40 N / A N / A N / A N / A N / A N / A N / A Oil Repellency: 50 washes 4 N / A N / A N / A N / A N / A N / A Water Repellency: 50 washes 3 N / A N / A N / A N / A N / A N / A Dew Capacity: 50 washes N / A N / A N / A N / A N / A N / A N / A Corn Oil Release: 49/50 N / A N / A N / A N / A N / A N / A N / A Corn Oil Release: 49/50 N / A N / A N / A N / A N / A N / A N / A Table IA (continued) - Microdenier Polyester Weave Substrate with Inventive Treatments (Household Wash) The test results for Example 5 are shown in Table IB. The results illustrate the durability and versatility of inventive chemistry in substrates, such as polyester cover fabrics, which have various constructions of fiber deniers. The results also illustrate the durability and versatility of fabric substrates comprised of flat (instead of textured) polyester and fabric substrates that have not been exposed to melt finishing processes.

Table IB - Polyester Coverage Fabric with Inventive Treatments (Industrial Washing) The test results for Comparative Example 6 are shown in Table II. The results illustrate that the inventive chemistry, shown as Example 1, provides for durable repellency, dew rating, and the release of staining through at least 30 home wash cycles on competitive chemistry, shown as Example 6A through 6J, provided herein for comparison on the same microdenxer polyester substrate.

Table II - Substrate of Mxcrodenier Polyester Fabric with Comparativial Treatments (Home Washing) Release of Mineral Oil: 9/10 4 1 1 5 4 4.5 Oil Repellency: 20 washes 4 5 5 5 0 N / A Water Repellency: 20 washes 7 5 7 3 0 N / A Dew Capacity: 20 washes 70 70 80 N / A 0 N / A Release of Corn Oil: i9 / 20 4 1 1 5 4 N / A Mineral Oil Release: i9 / 20 3.5 1 1 5 4 N / A Oil Repellency: 30 washes 4 4 5 5 0 N / A Water Repellency: 30 washes 4 4 7 3 0 N / A Spray Capacity: 30 washes 70 80 50 N / A 0 N / A Release of Corn Oil: 29/30 4 3.5 1 5 4 N / A Mineral Oil Release: 29/30 3 1 1 5 3.5 N / A Oil Repellency: 40 washes 4 N / A N / A N / A N / A N / A Water Repellency: 40 washes 3 N / A N / A N / A N / A N / A Dew Capacity: 40 washes N / A N / A N / A N / A N / A N / A Release of Corn Oil: 39/40 N / A N / A N / A N / A N / A N / A Mineral Oil Release: 39/40 N / A N / A N / A N / A N / A N / A N / A N / A N / A N / A N / A Oil Repellency: SO washed 4 N / A N / A N / A N / A N / A Water Repellency: 50 washes 3 N / A N / A N / A N / A N / A Dew Capacity: 60 washes N / A N / A N / A N / A N / A N / A Release of Corn Oil: 43/50 N / A N / A N / A N / A N / A N / A Mineral Oil Release: 49/50 N / A N / A N / A N / A N / A N / A Table II (continued) - Polyester Weave Substrate Microdenier with Comparative Treatments (Home Washing) The test results for Examples 7 (Comparative) and 8 (Inventive) are shown in Table III. The results for Example 7 illustrate the durability of the inventive chemistry in the polyester fabric to maintain high levels of water and oil repellency, while at the same time maintaining acceptable levels of stain release through at least 5 cycles of home washing. The results further show the versatility of inventive chemistry with various techniques and procedures of chemical application. The results of Example 8 illustrate the durability of the inventive chemistry in polyester fabric to maintain high levels of water and oil repellency while at the same time maintaining acceptable levels of stain release through 30 home wash cycles. The results further show that the alternative two-stage application procedure can provide more spray classification results, while maintaining high levels of corn oil repellency and release, rather than the one-step application procedure.

Table III - Polyester Tissue Substrate with Inventive and Comparative Treatments Using the Two-Stage Application Procedure (Household Washing) Example Ex. 7 Ex. 8 Oil Repellency: AR 6 6 Water Repellency: AR 6 7 Dew Capacity: AR N / A 100 Release of Corn Oil: 0/1 4 4 Release of Mineral Oil: 0/1 4 N / A > Oil Repellency: 5 Washes 5 6 Water Repellency: 5 Washes 7 6 Dew Capacity: 5 Washes N / A 100 Corn Oil Release: 4/5 4 5 Mineral Oil Release: 4/5 3.5 N / A Oil Repellency: 30 Washes N / A 5 Water Repellency: 30 Washes N / A 5 Dew Capacity: 30 Washes N / A 100 Release of Corn Oil: 29/30 N / A 4.5 Release of Mineral Oil: 29 / 30 N / A 1.5 The test results for Example 9, Example 10 and Comparative Example 11 are presented in Table IV. The results of Example 9 illustrate the durability of the inventive chemistry in cotton fabric to maintain high levels of water and oil repellency while at the same time maintaining acceptable levels of release of the paint through 30 home wash cycles. , as it is observed later. The results of Example 10 illustrate the versatility of inventive chemistry in having the ability to maximize the maximum stain repellency performance (ie, the dew rating improves by decreasing amounts of Unidyne TG-992) at the cost of release performance of staining (ie, the release of mineral oil decreases with smaller amounts of Unidyne TG-992), and conversely, the ability to maximize the yield of staining release (ie, release of mineral oil with increased amounts of Unidyne TG -992) to the degree of stain repellency performance (dew classification is lower with higher amounts of Unidyne TG-992). This versatility allows inventive chemistry to be designed for specific end-use applications such as raincoats, where water repellency may be more desirable, or work clothes, where the release of staining may be more desirable. The results of Example 11 illustrate the superior performance obtained by the unique combination of chemical agents described by the current invention. Without this unique combination, and as shown, for example in Examples 10A-10C, repellency characteristics, spray classification, and stain release performance are not optimized.

Table IV - Cotton Tissue Substrate with Inventive and Comparative Treatments (Home Washing) The test results for Comparative Example 12 and Inventive Example 9 are shown in Table V. The results illustrate that inventive chemistry provides durable repellency, dew classification, and stain release through at least 30 washes during chemistry. competitively provided in the present for comparison using the same substrate.

Table V - Cotton Tissue Substrate with Inventive and Comparative Treatments (Home Washing) Table V (Continued) - Cotton Fabric Substrate with Inventive and Comparative Treatments (Home Washing) Example Ex. 12F Ex. 12G Ex. 12H Ex. 121 Ex. 12J Oil Repellency: AR 5 4 2 3 4 Water Repellency: AR 5 3 4 6 7 Dew Capacity: AR 70 100 90 50 80 Release of Corn Oil: 0/1 5 3.5 1 4 1 Release of Mineral Oil: 0/1 5 3 1 4 1 Oil Repellency: "0 Washes 0 3 2 0 1 Water Repellency: 10 Washes 0 3 3 0 1 Dew Capacity: 10 Washes 50 50 50 0 50 Corn Oil Release: T / 10 4 3 1 4 4 Release of Mineral Oil: 9/10 3 1 1 3.5 1 Oil Repellency: 20 washes 0 3 2 0 0 Water Repellency: 20 Washes 0 3 3 0 0 Dew Capacity: 20 washes, 0 N / A 50 0 50 Corn Oil Release: 19/20 4 3 1 3 3 Release of Mineral Oil; 19/20 3 1 1 3 1 Oil Repellency: 30 Lavodos 0 N / AN / A 0 0 Water Repellency: 30 Lavodos 0 N / AN / A 0 0 Dew Capacity: 30 Lavodos 0 N / AN / A 0 50 Release of Corn Oil: 29/30 3 N / AN / A 3 3 Release of Mineral Oil: 29/30 2 N / AN / A 2 1 The test results for Example 13 are presented in Table VI. The results illustrate the durability of inventive chemistry in the fabric mixed with polyester and cotton to maintain high levels of water and oil repellency while at the same time maintaining acceptable levels of stain release through at least 30 wash cycles. Additional results show the versatility of inventive chemistry in applications where the permanent pressure resin is cured either completely during the finishing of the fabric or in applications where the resin is partially cured during the finishing of the fabric and then fully cured after of the manufacture of the garment to obtain durable garment wrinkles (ie, after curing). Both processes provide high levels of water and oil repellency, acceptable levels of stain release, and acceptable levels of spray classification.

Table VI - Substrate of Cotton and Polyester Mixture Fabric with Inventive Treatments (Home Washing) Example Ex. 13A Ex. 13B Ex. 13C Ex. 13D Ex. 13E Location of Production Test Production Production Lab Lab Location of the Sample Production Production Production Lab Lab Water Repellency AR 4 6 5 10 10 Water Repellency 5 Washes 4 5 5 9 9 Water Repellency 10 Washes 4 5 5 9 9 Water Repellency 20 Washes 3 4 4 7 6 Water Repellency 30 Washes 2 3 3 5 4 Oil Repellency AR 5 6 5 7 6 Oil Repellency 5 Washes 4 5 5 6 6 Oil Repellency 10 Washes 2 5 5 6 5 Repellency to Oil 20 Washes 1 4 3 5 4 Oil Repellency 30 Washes 1 2 2 4 2 Spray AR 70 80 80 70 70 Spray S Washes 70 90 80 70 70 Spray 10 Washes 70 80 70 70 70 Spray 20 Washes 70 70 80 70 70 Dew 30 Washes 70 70 70 70 50 Stain Release - Corn 0/1 0/2 3.5 / 4.0 4.0 / 4.5 4.0 / 4.5 5 / NA 5 / NA Stain Release - Corn 4/54/6 4.0 / 4.5 4.0 / 4.5 4.0 / 4.5 5 / NA 4.5 / NA Stain Release - Corn 9 / 09/1 4.0 / 4.5 3.5 / 4.5 3.0 / 3.5 5 / NA 4.5 / NA Stain Release - Corn 19/20 9/21 3.5 / 4.0 4.0 / 4.5 4.0 / 4.5 4 / NA 3.5 / NA Stain Release - Corn 29/3029/31 3.5 / 4.0 3.5 / 4.0 4.0 / 4.5 4 / NA 3.5 / NA Stain Release - Mineral 0/1 0/2 3.5 / 4.0 4.0 /4.5 4.0 / 4.5 5 / NA 4.5 / NA Stain Release - Mineral 4/54/6 4.0 / 4.5 4.0 / 4.5 3.5 / 4.5 - 5 / NA 4.5 / NA Libe Staining ration - Mineral 9/109/11 4.0 / 4.5 3.0 / 4.0 3.0 / 3.5 5 / NA 4.5 / NA Stain Release - Mineral 19/2019/21 3.0 / 3.5 4.0 / 4.5 4.0 / 4.5 4 / NA 3.5 / NA Stain Release - Mineral 29/30293131 3.0 / 3.5 3.0 / 3.5 4.0 / 4.5 4 / NA 3.5 / NA Table VI (Continued) - Substrate of Cotton and Polyester Mixing Fabric with Inventive Treatments (Home Washing) Example Ex. 13F Ex. 13G Ex. 13H Ex. 13 I Location of the Lab Lab Lab Test Sample Location Lab Lab Lab Lab Water Repellency AR 10 10 10 10 Water Repellency 5 Washes 8 7 8 6 Water Repellency 10 Washes 5 3 6 3 Water Repellency 20 Washes 2 2 2 2 Water Repellency 30 Washes 1 1 i 0 Oil Repellency AR 6 6 7 6 Oil Repellency 5 Washes 6 5 6 5 Oil Repellency 10 Washes 5 4 5 3 Oil Repellency 20 Washes 2 2 4 2 Oil Repellency 30 Washes 1 1 2 0 Rocío AR 80 80 70 70 Dew 5 Washes 70 70 70 70 Dew 10 Washes 70 70 70 70 Dew 20 Washes 70 50 70 50 Dew 30 Washes 50 50 50 50 Stain Release - Corn 0/1 4.5 4.5 4.5 5 Stain Release - Corn 4/5 4.5 5 5 4.5 Stain Release - Corn 9/10 3.5 4.5 4 3.5 Stain Release - Corn 19/20 3.5 3.5 4 3.5 Release of Staining - Corn 29/30 3 3 3.5 3.5 Stain Release - Mineral 0/1 4.5 4.5 4.5 4.5 Stain Release - Mineral 4/5 4.5 5 5 4 Stain Release - Mineral 9/10 4 4.5 4 3.5 Stain Release - Mineral 19/20 3.5 3.5 3.5 3.5 Releasing Staining - Mineral 29/30 3 3 3 3 The results of the test of Comparative Example 14 are shown in Table VII. The results illustrate that inventive chemistry, shows how Examples 13A to 13J, provide durable repellency, spray classification, and release of staining through at least 30 home washes over competitive chemistry, shown as in Example 13A through 14H , provided herein for comparison in the polyester-cotton blend substrate.

Table VII - Substrate of Polyester and Cotton Mixture Fabric with Comparative Treatments (Home Wash) Water Repellency 1D Washes 0 3 4 4 3.0 4.0 Water Repellency 20 Washes 0 3 4 2 2.0 2.0 Water Repellency 10 30 Washes 0 1 4 3 2.0 2.0 Oil Repellency AR 1 5 4 5 4.0 5.0 Oil Repellency S Washes 0 1 N / AN / AN / A 5.0 Oil Repellency 1D Washes 0 1 3 3 1.0 2.0 Oil Repellency 20 Washes 0 0 2 2 1.0 2.0 Oil Repellency 30 Washes 0 0 1 2 0.0 1.0 Roclo AR 0 80 100 100 100 90 Roclo 5 Washes 0 0 N / AN / AN / A 90 Roclo 10 Washes 0 0 90 90 80 70 15 20 Washes 0 0 80 90 70 70 Rocio 30 Washes 0 0 80 80 70 50 Stain release - Corn 0/1 0/2 3.5 / 4.0 4.0 / 3.5 N / AN / AN / A 4.0 / 4.5 Stain release - Corn 4/5 4/6 3.5 / 4.0 4.0 / 3.5 N / AN / A 1.0 / NA 2.5 / 3.0 Stain release - Corn 9/10 9/11 3.0 / 3.5 3.5 / NA N / AN / A 2.5 / NA 3.0 / NA Stain release -Maize 9/20 19/21 3.0 / 3.5 3.5 / NA N / AN / A 2.0 / NA 3.5 / NA Staining release 20 - Corn 29/30 29/31 3.0 / 3.5 3.5 / NA N / AN / A 2.0 / NA 3.0 / NA Stain Release -Mineral 0/1 0/2 3.5 / 3.5 N / AN / AN / AN / A 3.5 / 4.0 Stain Release - Mineral 4/5 4/6 3.5 / 3.5 N / AN / AN / A 1.5 / NA 1.0 / 1.5 Release of Stain - Mineral 9/109/11 3.0 / 3.5 N / AN / AN / A 2.0 / NA 2.5 / NA Release of Stain - Mineral 19/20 19/21 3.0 / 3.5 N / AN / AN / A 1.0 / NA 3.0 / NA Stain Release - Mineral 29/30 29/31 3.0 / 3.5 N / AN / AN / A 1.0 / NA 2.0 / NA Table VII (Continued) - Polyester and Cotton Blend Fabric Substrate with Comparative Treatments (Home Wash) Water Repellency AR 3 3 Water Repellency 5 Washes 4 4 Water Repellency 10 Washes 4 4 Water Repellency 20 Washes 3 3 Water Repellency 30 Washes N / AN / A Oil Repellency AR 5 5 Oil Repellency 5 Washes 5 5 Oil Repellency 10 Washes 5 5 Oil Repellency 20 Washes 5 4 Oil Repellency 30 Washes N / AN / A Spray AR 70. 70 Roclo 5 Washes 70 70 Rocio lo Washes 70 70 Dew 20 Washes 70 70 Dew 30 Washes N / AN / A Stain release - Corn.0 / 1 5 4.5 Stain release - Maize 4/5 4.5 4 Stain release - Corn 9/10 4. 4 Stain release - Corn 19/20 3.5 3.5 Stain release - Corn 29/30 N / A N / A Release of Staining - Mineral 0/1 5 4.5 Release of Staining - Mineral 4/5 5 4 Release of Staining -Mineral 9/10 4 3.5 Release of Staining - Mineral 19/20 4 3 Release of Staining - Mineral 29/30 N / AN / A The test results for Inventive Examples 15 and Comparative Examples 16 and 18 are shown in Table VIII and Table IX. The results for Example 15 illustrate the durability of the inventive chemistry in the polyester and cotton blend fabric to maintain high levels of water and oil repellency while at the same time maintaining high levels of stain release through minus 30 industrial wash cycles. The results also show the versatility of inventive chemistry by adding the permanent pressure resin to the fabric either before the inventive chemistry is fully cured or after the inventive chemistry is fully cured (ie, after the cure). Both processes provide high levels of water and oil repellency, acceptable levels of stain release, and acceptable levels of spray classification. The results also show the durability and effectiveness of the inventive chemistry used in Example 15A and 15B for the release of burnt motor oil ("BMO") stain on this polyester and cotton blend substrate after at least 30 washes. industrial The results of Comparative Example 16 illustrates the inventive chemistry, shown as Example 15A to 15E, provides durable repellency, spray classification and stain release through at least 30 industrial wash cycles on competitive chemistry, shown as Example 16A and 16B, provided herein for comparison on the same polyester-cotton blend substrate. The results of Example 17 illustrate the durability of inventive chemistry in a nylon fabric substrate through at least 10 home wash cycles when tested for spray classification and oil release by the methods described above. The results of Comparative Example 18 illustrate the superior performance of inventive chemistry in a nylon fabric substrate over competitive chemistry for dew classification and the release of corn oil and mineral through at least 10 home wash cycles.

Table VIII - Tissue Substrate with Inventive and Comparative Treatments (Industrial Washing) Example Ex. 15A Ex. 15B EJ. 15C Ex 15D Ex 15E Ex 16A 16B Location of Production Test Production Lab Lab Lab Lab Lab Location of the Sample Production Production Lab Lab Lab Lab Lab Water Repellency AR 6.0 5.0 10 10 10 3 7.5 Water Repellency 5 Washes 6.0 6.0 6.5 7 7.5 0 6.5 Water Repellency 10 Washes 5.0 5.0 4.5 6 6 0 6 Water Repellency 20 Washes 4.0 4.0 0 2.5 2.5 2.5 0 Water Repellency 30 Washes 2.0 2.0 0 2.5 O 0 0 Oil Repellency AR 6.0 5.0 7 6 6 5 5.5 Oil Repellency 5 Washes 5.0 5.0 5.5 5.5 6 1.5 4.5 Oil Repellency Washes 5.0 5.0 5 4.5 5 1.5 3.5 Oil Repellency 20 Washes 4.0 4.0 2.5 2 2 5 0 Oil Repellency 30 Washes 1.0 1.0 1 1.5 1.5 2 0 Roclo AR SO 80 70 70 70 50 100 Roclo 5 Wash 70 70 SO 50 50 50 25 Roclo 10 Wash 70 70 50 50 50 0 0 Roclo 20 Wash 50 70 50 50 50 0 0 Dew 30 Wash 50 70 50 50 O 0 0 Table IX - Nylon Tissue Substrate with Inventive and Comparative Treatments (Home Wash) The results of the test for Example 19 are shown in Table X. The results show the release of the mineral oil and improved corn oil on the untreated Nomex® fabric. The results further illustrate the durability of inventive chemistry in Nomex® fabric through at least 5 home wash cycles when tested for repellency, stain release, and spray classification by previo described methods.

Nomex® Fabric Substrate with Inventive Treatments (Home Washing) III): Additional Analyzes Through Modifications of the Test Methods Example 20: To illustrate that inventive chemistry additionally provides improved oil and water repellency, improved stain release, and improved spray classification on a variety of tissue substrate types, several other tissue substrates were treated with inventive chemistry using the one-step application procedure and comparing against the same tissue substrate in an untreated state. The chemical composition used for these tissue substrates was as follows: 1% Repearl F-89, a repellent agent, 5% ünidyne TG-992, a staining release agent; and 2% Witcobond W-293, a cross-linking agent.

Example 20A: A 100% acetate tissue substrate made by Milliken & Company was used to test water and oil repellency, spray classification, and release of mineral oil and corn stain by previo described methods. The acetate was constructed of a satin weft pattern of 191 by 50 and comprised of bright 75/19 denier acetate warp yarns (as opposed to no gloss) and shiny 150/38 denier filled yarns. The acetate had a moisture recovery of the chemical composition in the substrate of approximately 80%.

Example 20B: A 100% acrylic fabric substrate purchased from a fabric store was used to test oil and water repellency, spray classification and maize oil stain release and mineral oil by previo described methods. The acrylic had a felt construction and exhibited a moisture recovery of the chemical composition in the substrate of approximately 250%.

Example 20C: A 100% woolen tissue substrate, purchased from a fabric store used to test water and oil repellency, spray classification, and release of mineral oil and corn oil stain by methods previo described. The wool had a flat weft construction and exhibited a moisture recovery of the chemical composition in the substrate of approximately 80%.

Example 20D: A 100% silk tissue substrate, purchased from a fabric warehouse used to test water and oil repellency, spray classification, and mineral oil and corn oil stain release by methods previo described. The silk was pure silk having a woven construction similar to a taffeta fabric. The moisture recovery of the chemical composition in the substrate f e 'of approximately 100%. The test results are shown in Table XI. The results of Example 20A illustrate that the treated acetate, when compared to untreated acetate, exhibits improved water and oil repellency. The results of Example 20B illustrate that the treated acrylic, when compared to the untreated acrylic, exhibits improved oil repellency. The results of Example 20C illustrate that the treated wool, when compared to untreated wool, exhibits improved oil repellency and improved oil and mineral corn stain release. The results of Example 20D illustrate that the treated silk, when compared to untreated silk, exhibits improved oil and water repellency and improved spray classification.

Table XI - Other Tissue Substrates with Inventive Treatments Example 21: Example 1 was repeated, except that several other common laundry detergents were used instead of Quick Dissolving Tide®. The detergents used were: Example 21A: Mountain Spring Tide® Example 2IB: Cheer® Example 21C: Tide Free Liquid® Example 2ID: Era® Example 21E: All® Example 21F Downy® (in the washing machine) and Quick Dissolving Tide® Example 21G : Bounce®. { in the Dryer) and Quick Dissolving Tide® The results of the test are shown in Table XII. The results illustrate that excellent release of staining and acceptable levels of repellency and the ability to spray is obtained by using a variety of different detergents and fabric softeners on the polyester substrate.

Table XII - Substrate of Polyester Fabric of icrodenier with Inventive Treatments (Home Washing) Example Ex. 1 Ex. 21A Ex. 21 B Ex. 21 C Ex. 21D Ex. 21b Ex. 21 F Ex. 21 G Oil Repellency: AR 5 5 '5 5 5 5 5 5 Water Repellency: 6 AR 9 7 7 7 8 7 6 Dew Capacity: AR 80 70 70 70 70 70 70 70 Release of Corn Oil: o / 1 AR 4.5 4 4 4 N / A N / A 4 5 Mineral Oil Release: 0/1 AR 5 4 4 3.5 N / A N / A 4 4 Oil Repellency: 10 washes 4 1 1 2. N / A N / A N / A N / A Water Repellency: 10 washes 7 1 2 3 N / A N / A N / A N / A Dew Capacity: 0 washes 70 50 50 70 N / A N / A N / A N / A Release of Corn Oil: 9/10 4.5 5 5 4 / A N / A N / A N / A Mineral Oil Release: 9/10 4 4 4 4 N / A N / A N / A N / A Oil Repellency: 20 washes 4 0 1 2 N / A N / A N / A N / A Water Repellency: 20 washes 7 2 2 3 N / A N / A N / A N / A Dew capacity: 20 washes 70 50 50 50 N / A N / A N / A N / A Release of Corn Oil: 9/20 4 4 4 5 N / A N / A N / A N / A Mineral Oil Release: 9/20 3.5 4 3.5 5 N / A N / A N / A N / A Example 22: To determine how inventive chemistry affects the feel (or feel) of the tissue substrate, several tissue substrates were treated as described below and then tested using the Kawabata Evaluation System. The tested substrates and the chemical compositions used are as follows: Example 22A: Example 1 was repeated Example 22B: Example 6B was repeated Example 22C: The tissue substrate described in Example 1 was not treated as a control. The test results are shown in Table XIII. The lower values for the Bending Stiffness are indicative of more soft touch. The results illustrate that inventive chemistry does not detrimentally affect the feel of the polyester fabric and can now slightly improve the feel when tested using the Kawabata measurements.

Table XIII - Kawabata Touch Test for Microdenier Polyester Tissue Substrate Average fold stiffness per unit per width: Fill 0.093 0.093 0.073 Average Cutting Stiffness Stiffness: Warp 0.622 0.884 0.536 Cutting Stress Rigidity: 0.498 0.614 0.392 Filling Stress Work (during extension): Warp 12.3 13.9 20.5 Tension work (during extension): Fill 6.3 6.4 13.2 Average Friction Coefficient: Warp 0.215 0.284 0.275 Average Friction Coefficient: Filler 0.236 0.311 0.280 Example 23: Durability for dry cleaning was tested on microdenier polyester fabric treated with the inventive chemical composition, as well as with various, competitive chemical compositions according to the dry cleaning procedure previously described. Treated fabrics were tested for oil and water repellency and spray classification before any dry cleaning cycles ("as received"), after 1 dry cleaning cycle, after 5 dry cleaning cycles and after 5 cycles of dry cleaning and ironing. The tested substrates were as follows: Example 23 ?: Example 1 was repeated Example 23B: Example 6B was repeated Example 23C: Example 6C was repeated The test results are shown in Table XIV. The results illustrate that inventive chemistry is able to withstand the dry cleaning process and the dry cleaning and ironing process and maintains the same level of durability through at least 5 dry cleaning cycles.

Table XIV - Microdenier Polyester Tissue Substrate with Inventive and Comparative Treatments (Dry Cleaning) Example Ex. 23A Ex. 23B Ex. 23C Ex. 23D Ex. 23E Ex. 23F Oil Repellency: AR 5 5 4 4 5 5 Water Repellency: AR 7 7 2 1 6 1 Dew capacity: AR 70 100 70 70 100 70 Oil Repellency: 1 Cycle 2 5 4 5 5 4 Water Repellency: 1 Cycle 3 8 1 2 5 2 Example 24: Another test was performed to determine the air permeability of microdenier polyester tissue substrate treated with the inventive chemistry of the current invention. The treated polyester fabric was compared with untreated polyester fabric and with the same fabric having a competitive composition applied thereto. The test was performed in accordance with Test Method ASTM D737-96 with air pressure at 125 Pa (Pascals), and the results are given in units "cfm" (cubic feet 'per minute). The tested tissue substrates and the chemistry used are as follows: Example 24A: Example 1 was repeated Example 24B: Example 6B was repeated Example 24C: The tissue substrate described in Example 1 was not treated as a control. The test results are not shown in Table XV. The results illustrate that air permeability was not significantly affected by the treatment with inventive chemistry. The results also show that air permeability was better with inventive chemistry when compared to the same fabric treated with competitive chemistry.

Table XV - Breathability of the Microdenier Polyester Stense Substrate, Inventive Example 25: Another test was performed to determine the effect that inventive chemistry has on the static charge for the microdenier polyester fabric substrate. The treated polyester fabric was compared with the untreated polyester fabric and with the same fabric having a competitive chemical composition applied thereto. The test was performed according to the procedure previously described. Results are given in "kV" (kilovolts) before home wash ("AR" means how it was received "), after 1 home wash cycle, after 5 home wash cycles, and after 5 home wash cycles and conditioning the substrate at 21.11 ° C (70 ° F) and 65% relative humidity ("RH"). "NR" indicates that the static load exceeds the meter's ability to measure the load. The chemistry used is as follows: Example 25A: Example 1 was repeated Example 25B: Example 6B was repeated Example 25C: The tissue substrate described in Example 1 was left untreated as a control. The test results are shown in Table XVI. The results illustrate that after 5 washes conditioning the polyester substrate treated with the inventive chemistry currently reduces the static charge in the substrate. The results also show that the polyester substrate treated with the inventive chemistry created less static charge than the same cloth treated with the competitive chemistry without washes and after 5 washes with conditioning. Additionally, the polyester substrate treated with the inventive chemistry created less static charge than the untreated polyester substrate after 1 wash and after 5 washes with conditioning. In addition, all the results, except for the polyester substrate treated with the inventive chemistry after 5 washes and conditioning, measured some degrees of static charge, which indicates that the substrates exhibit undesirable static grip properties. The only sample that exhibited no static grip was the polyester substrate treated with the inventive chemistry after 5 washes and conditioning. Since durable antistatic and anti-seize protection is difficult to achieve on polyester substrates, especially microdenier polyester substrates, these results show another advantage in using the inventive chemistry of the current invention in various substrates.

Table XVI - Static Load in Microdenier Polyester Textile Substrate Inventive Example 26: Progressive and receding contact angles were measured for a polyester substrate treated with various competitive chemical and inventive compositions using the previously described Tensiometer and Geniometer Test Methods. The chemical compositions were as follows: Example 26A: Example 1 was repeated on a polyester film and on the polyester / cotton blend fabric described in Example 13, and the contact angles were measured. Example 26B: Example 26A was repeated in the polyester film, with only the chemical staining release agent, 4.5% Unidyne TG-992, and the contact angles were measured. Example 26C: Example 26A was repeated in the polyester film, with only the chemical stain release agent, 1.5% Repearl F8025, and the contact angles were measured. Example 26D: Example 6B was repeated in the microdenier polyester fabric, and the contact angles were measured. Example 26E: Example 6C was repeated on a polyester film and on the polyester / cotton blend fabric of Example 13, and the contact angles were measured. Example 26F: The substrate described in Example 26A (polyester film) was left untreated as a control, and the contact angles were measured. The results of the test are shown in Table XVII. The results indicate improved staining resistance and improved staining release that is expected for the chemical composition of the current invention when compared to traditional fluorochemical repellents (Ex. 26B). The results also illustrate that improved aqueous stain resistance is expected when compared to newer repellents (Ex. 26C). In addition, the results also show that the progressive contact angle is dominated by Repearl F8025 (the chemical stain repellent agent), and the regression contact angle is dominated by ünidyne TG-992 (the chemical release agent), by What is provided is additional support of the additional composition by self-adapting the changes in its environment. Finally, the results show that the composition of the current invention produces similar results in both synthetic and natural fibers, as well as in films in addition to woven substrates.

Table XYII - Contact Angle Measurements for Microdense Polyester Fabric Substrate Inventive Example Ex 26A Ex 26B Ex 26C Ex 26D Ex 26E Ex 26F Progressive contact angle: Goniometer 143 106 117 N / A 110 81 Reverse Contact Angle: Goniometer 49 51 95 N / A 64 58 Progressive Contact Angle: Tensiometer 167 N / A N / A 167 159 N / A Regression Contact Angle: Tensiometer 109 N / AN / A 124 81 N / A Example 27: Using the regression and contact data shown in Example 26, the surface energy was calculated, both at 25 ° C and 40 ° C , for the microdenier polyester substrate treated with various inventive and competitive chemical compositions. The results given in units of milliliters per square meter. The surface energy at 40 ° C was determined, using the same measurement technique, but the sample was soaked in water for 1 hour at 40 ° C and dried under vacuum, before the test. The chemical compositions were as follows: Example 27 ?: Example 1 was repeated, and the surface energy was determined. Example 27B: Example 1 was repeated, with only the chemical staining release agent, 4.5% ünidyne TG-992, and the surface energy was determined. Example 27C: Example 1 was repeated, with only the stain repellent chemical, 1.5% Repearl F8025, and the surface energy was determined. Example 27D: Example 6D was repeated, and the surface energy was determined. Example 27E: Example 6E was repeated, and the surface energy was determined. Example 27F: Example 61 was repeated, and the surface energy was determined.

The test results are shown in Table XVIII. The results reflect the change in single surface energy obtained from the composition of the current invention, as a result of a change in the environment. The inventive chemical composition of the current invention is the composition showing the change from a low energy surface to a high energy surface as a result of environmental effects. This change in surface energy is representative of the requirements of a durable stain repellent composition and release of stained or treated surface.

Table XVIII - Surface Energy Measurements for Microdenier Polyester Fabric Substrate Inventive Example 28: Surface chemical analyzes for fluorine, carbon and oxygen were performed on microdenier polyester fabric treated with the inventive chemistry of the current invention and with various XPS analytical techniques using competitive chemistry. The chemical compositions applied to the fabric were as follows: Example 28A: Example 6C was repeated. Example 28B: Example 1 was repeated. Example 28C: Example 61 was repeated. Example 28D: Example 6D was repeated. Example 28E: Example 6B was repeated. The test results for Example 28 are shown in Table XIX and in Figures 1-3.

Table XIX - Surface Chemical Analysis for Microdenier Foliester Fabric Substrate Inventive Example Ex. 28A Ex-28B Ex. 28C Ex. 28D Ex. 28E Hot Air 187.78 ° C (370 degrees F) as received:% Fluorine 39.1 44.76 40.54 36.52 52.85% Carbon 43.18 45.96 49.49 48.44 39.45% Oxygen 14.03 9.29 9.97 13.77 4.71 Wet in 40 degrees C of water dui before 1 hour / vacuum drying% of Fluor 38.64 37.83 31.16 27.52 52.59% of Carbon 43.13 50.36 58.06 55.86 42.49% of Oxygen 14.55 11.19 10.77 16.62 4.92 Reheated to 150 degrees C% Fluorine 36.97 44.82 45.04 N / A N / A% Carbon 44.79 45.42 45.87 N / A N / A% Oxygen 14 9.77 9.09 N / A N / A After 10 washes:% Fluoride 40.53 36.89 24.4 8.86 40.41% Carbon 45.59 50.79 58.76 68.69 49.14% Oxygen 13.88 12.32 16.84 8.86 8.2% Fluoride loss. + 3.70% -17.60% -39.80% -75.70% -23.50% Detailed Drawing Description: As seen in Table XIX and Figure 1, the fluorine-containing segment and the oxygen-containing segment on the surface remain relatively constant for the treatment used for example 28A, despite the exposure of the samples to water or heat. However, the fluorine decreases, and the oxygen is increased for the treatment of Example 28B (inventive chemistry) when the sample is exposed to water and returns to essentially the original values after heating the sample. Unbound by theory, this may indicate that, in the presence of water and especially at 40 ° C, the ethylene oxide segment of Unidyne TG-992 hydrates and swells sufficiently to predominate over the fluorinated segment. This may explain the surface energy changes that are shown to occur, as well as the excellent stain repellency and stain release of the chemical composition of the current invention. In the subsequent heating, the polymer summarizes its original configuration. Figure 1 further illustrates that Example 28A and 28E do not show the environmental response to water at 40 ° C as shown for Example 28B. Examples 28C and 28D show an environmental response similar to Example 28B (inventive chemistry). However, as seen in Figure 2, considerably more fluorine is lost from Example 28C and 28D than from Example 28B (inventive chemistry) after 10 house washes. This is especially true for Example 28D and indicates a lack of durability for these treatments.

IV) Additional Analysis of Different Types of Fabrics Example 29: A clothing fabric comprised of approximately 65% polyester fiber and approximately 35% wool fiber was tested using inventive chemistry and competitive chemistry according to the Home Dryer Application Procedure previously described (and generally exemplified within of US Patents Nos. 5, 630,828, 5,591,236 and / or 5,951,716). The treated fabrics were tested for release of corn oil stain, water repellency, and oil repellency as previously described. An untreated control fabric was also tested. The chemical compositions used for the treatment were as follows: Example 29A: An untreated piece of cloth (control) . Example 29B: 5% Unidyne TG-992 Example 29C: 5% Unidyne TG-992 1% Repearl F-89 The test results are shown in Table XX. The results indicate that the release of stain and stain repellent chemistry can be added to a tissue substrate using the Application Procedure of the Home Dryer to provide corn oil stain release properties and water and oil repellency. The results also show the versatility and ease with which such chemistry can be applied to a substrate to obtain such release characteristics and stain repellency.

Table XX - Wool and Polyester Mixture Substrate with Inventive and Comparative Treatments Applied by the Application Method of the Home Dryer Therefore, although it has been known to use the fluorocarbon polymers and hydrophilic stain release polymers, together or separately, to obtain water and oil repellency and performance characteristics of stain release in a substrate, it has proved difficult to obtain those characteristics simultaneously and with permanent durability after exposure to repeated home and industrial washing cycles. Because polymers have a tendency to work against each other and to wash out the substrate during washing, it has been surprising to find chemical stain repellents, chemical release agents, and hydrophobic crosslinking agents that work well. , together as shown in Examples 1 to 18. The concentration of the respective chemical agents comprising the chemical composition used to treat a substrate, in combination with the unique ratio of the chemical agents to each other, and the careful selection of the agents Chemicals, all seem to play a significant role in determining the success of the process and the product, particularly with respect to durability. In an o. Further preferred embodiments of the invention, the chemical composition can be applied to the substrate in a one-step application process, a two-step application process, or in an alternative two-stage application process as previously described. Indeed, as shown in the Examples, polyamides, polyaramides, polyesters, cottons and polyester-cotton blend substrates, when treated according to the present invention, have all produced improved performance with respect to durable water and water repellency. Oil and characteristics of durable stain release. Accordingly, the treated substrate of the present invention has many applicable uses for incorporation into clothing items, such as outerwear (e.g., waterproof), workwear (e.g., uniforms), custom clothing (e.g. , shirts, pants and other garments); curtain table linen (for example, linen fabrics for tables and napkins); residual upholstery; commercial upholstery; car upholstery; carpeted outer fabrics (e.g., outside furniture, awnings, boat covers, and grill covers) and any other article where it is desirable to manufacture a substrate that has durable water and oil repellency and durable dye release characteristics. These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the scope of the invention described in the appended claims.

Claims (34)

1. CLAIMS 1. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising the combination of: (a) a staining release agent; (b) a stain repellent agent; and (c) a kind of hydrophobic crosslinking. The composition of claim 1, wherein the concentration ratio of (a): (b): (c) is in the range of about 10: 1: 0.1 to about 1: 10: 5 parts by weight. 3. The composition of claim 2, wherein the concentration ratio is between about 5: 1: 0.1 and about 1: 5: 2. 4. The composition of claim 3, wherein the concentration ratio is about 1: 2: 1 parts by weight. 5. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising mixing: (a) a staining release agent; (b) a stain repellent agent; and (c) a kind of hydrophobic crosslinking containing isocyanate. The composition of claim 5, wherein the concentration ratio (a): (b): (c) is about 1: 2: 1 parts by weight. 7. A composition made by combining: a staining release agent, the staining release agent is selected from the group consisting of: ethoxylated polyesters, sulphonated polyesters, ethoxylated nylons, carboxylated acrylics, cellulose ethers, esters, hydrolyzed polymaleic anhydrides , polyvinylalcohol polymers, polyaralimide polymers, hydrophilic fluorinated polymers, ethoxylated silicone polymers, polyoxyethylene polymers, and polyoxyethylene-polyoxypropylene copolymers; a repellent agent; and a kind of hydrophobic crosslinking containing isocyanate. 8. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising: (a) a fluorinated staining release polymer; (b) a stain repellent agent; and (c) a kind of hydrophobic crosslinking. 9. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising: a staining release agent; a stain repellent agent; and a kind of hydrophobic crosslinking containing epoxy. 10. A composition comprising: (a) a fluorinated staining release polymer; (b) a stain repellent agent; and (c) a kind of hydrophobic crosslinking containing isocyanate. 11. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising the combination of: (a) a fluorinated staining release polymer; (b) a fluorinated stain repellent agent; Y (c) a kind of hydrophobic crosslinking containing isocyanate. 12. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising: (a) a fluorinated acrylate-containing polymer; (b) a fluorinated urethane-containing polymer; and (c) a type of isocyanate-containing crosslinking. 13. A composition comprising: (a) a stain release agent, (b) a stain repellent agent, (c) a species of hydrophobic crosslinking, and (d) a fire retardant composition. 14. A composition for imparting stain release and durable repellency to a substrate, the composition comprising: (a) a stain release agent, (b) a stain repellent agent, (c) a kind of hydrophobic crosslinking, and (d) an antimicrobial compound. 15. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising a blend prepared by combining (a) a fluorocarbon-containing polymer adapted to impart the staining release properties to the substrate, the fluorocarbon-containing polymer that it has a non-esterified primary chain, (b) a stain repellent agent, and (c) a kind of hydrophobic crosslinking. 16. A composition made by combining: a stain release agent, the staining release agent having active groups selected from the group consisting of: ethoxylated polyesters, sulphonated polyesters, ethoxylated nylons, carboxylated acrylics, cellulose ethers, hydrolysed polymaleic anhydrides, polyvinylalcohol polymers, polyacrylamide polymers, fluorinated polymers hydrophilic, ethoxylated silicone polymers, polyoxyethylene polymers and polyoxyethylene-polyoxypropylene copolymers; a repellent agent containing fluorocarbon; and a kind of blocked, hydrophobic isocyanate crosslinking. The composition of claim 16, further comprising: a fire retardant composition. 18. The composition of claim 16, further comprising: an antimicrobial compound. 19. A composition for imparting durable repellency and release of staining to a substrate, the composition comprising: (a) a fluorocarbon-containing copolymer adapted to impart staining release properties to the substrate, the fluorocarbon-containing copolymer having a primary polymer chain which is not esterified, the fluorocarbon-containing copolymer is selected from the group consisting of: fluoroalkyl acrylates, fluoroarylates and fluorinated substituted urethanes; (b) a stain repellent agent; and (c) a hydrophobic crosslinking agent. The composition of claim 19, wherein in addition the hydrophobic crosslinking agent comprises an isocyanate-containing species. The composition of claim 20, wherein the source of the isocyanate-containing species is a blocked isocyanate. 22. A composition consisting essentially of: a first species containing fluorocarbon adapted to impart the release of staining, the first species containing fluorocarbon is selected from the group consisting of: ethoxylated polyesters, sulfonated polyesters, ethoxylated nylons, carboxylated acrylics, ethers of cellulose, esters, hydrolyzed polymaleic anhydrides, polyvinylalcohol polymers, polyacrylamide polymers, hydrophilic fluorinated polymers, ethoxylated silicone polymers, polyoxyethylene polymers, and polyoxyethylene-polyoxypropylene copolymers; a second species containing fluorocarbon adapted to impart durable repellency, the second species containing fluorocarbon is selected from the group consisting of: waxes, silicones, hydrophobic resins and fluoropolymers; and a kind of crosslinking, the crosslinking species selected from the group consisting of: monomers with blocked isocyanates, aromatic diisocyanates, blocked diisocyanates, polymers containing blocked isocyanates, epoxy containing compounds, epoxy resins, diisocyanate containing monomers, and polymers that contain diisocyanate. 23. The composition of claim 22, wherein the first fluorocarbon-containing species comprises an acrylate. The composition of claim 22, wherein the second fluorocarbon-containing species comprises a fluorinated substituted urethane. The composition of claim 22, wherein the crosslinking species comprises an aromatic diisocyanate. 26. The composition of claim 22, wherein the crosslinking species comprises an epoxide resin. 27. A composition adapted for application to a tissue substrate, the composition comprising: a first fluorocarbon acrylate polymer species adapted to impart stain release, the first species of fluorocarbon acrylate has attached ethylene oxide groups; a second species containing fluorinated urethane adapted to impart durable repellency; and a species that contains isocyanate. 28. A composition consisting essentially of: a first fluorocarbon-containing species adapted to impart stain release, the first fluorocarbon-containing species is selected from the group consisting of: ethoxylated polyesters, sulfonated polyesters, ethoxylated nylons, carboxylated acrylics, ethers of cellulose, esters, hydrolyzed polymaleic anhydrides, polyvinylalcohol polymers, polyacrylamide polymers, hydrophilic fluorinated polymers, ethoxylated silicone polymers, polyoxyethylene polymers, and polyoxyethylene-polyoxypropylene copolymers; a second species containing fluorocarbon adapted to impart durable repellency, the second species containing fluorocarbon is selected from the group consisting of: waxes, silicones, hydrophobic resins and fluoropolymers; and a kind of crosslinking, the crosslinking species selected from the group consisting of: monomers with blocked isocyanates, aromatic diisocyanates, blocked diisocyanates, blocked isocyanate containing polymers, epoxy containing compounds, epoxy resins, diisocyanate containing monomers, and polymers that they contain diisocyanate. 29. The composition of claim 28, wherein the fluorocarbon-containing species comprises an acrylate. The composition of claim 28, wherein the second fluorocarbon-containing species comprises a fluorinated substituted urethane. The composition of claim 28, wherein the crosslinking species comprises an aromatic diisocyanate. 32. The composition of claim 28, wherein the crosslinking species comprises an epoxide resin. 33. A composition adapted for application to a tissue substrate, the composition comprising: a first fluorocarbon acrylate polymer species adapted to impart the release of staining, the first species of fluorocarbon acrylate having groups of ethylene oxide attached; a second species containing fluorinated urethane adapted to impart durable repellency; and a species that contains isocyanate. 34. A composition for imparting stain release, durable repellency, and flame retardancy to a substrate, the composition comprising the combination of: (a) a stain release agent, (b) a stain repellent agent, (c) ) a hydrophobic crosslinking agent, and (d) a fire retardant composition.