WO2009129364A2 - Durable functionalization of polyolefin fibers and fabrics for moisture management and odor control - Google Patents

Abstract

In some respects, the invention relates to polyolefin fibers and fabrics that have durable functionality, including moisture-management capabilities and, in some instances, odor-control characteristics. The compositions and methods of the present invention may be applicable to polyolefin fibers (staple or filament), and fabrics including knits, wovens, and nonwovens. These functionalized fibers and fabrics are suitable for use in activewear garments, intimates, swimwear, career wear, work wear (e.g., uniforms and protective clothing), medical clothing, and technical clothing.

Description

DURABLE FUNCTIONALIZATION OF POLYOLEFIN FIBERS AND FABRICS FOR MOISTURE MANAGEMENT AND ODOR CONTROL

BACKGROUND

The present invention relates to polyolefϊn fibers and fabrics that have durable functionality, including moisture-management capabilities and, at least in some embodiments, odor-control characteristics. In some embodiments, the compositions and methods of the present invention may be applicable to polyolefϊn fibers (staple or filament) and fabrics including knits, wovens, and nonwovens. In some embodiments, these functionalized fibers and fabrics are suitable for use in activewear garments, intimates, swimwear, career wear, work wear (e.g., uniforms and protective clothing), medical clothing, and technical clothing.

Polyolefϊn fibers are manufactured fibers in which the fiber-forming substance is any long-chain synthetic polymer composed of at least 85% by weight of ethylene, propylene, or other olefin units. Polyolefin fibers can be multi- or filament and staple, tow, or film yarns. In some embodiments, the fibers are colorless and round in cross section. The cross section can be modified for different end uses. In some instances, their physical characteristics include a waxy feel and being colorless. These fibers traditionally have been used mainly for ropes, twines and utility fabrics. Polypropylene generally is the more favored polyolefin for general textile applications because of its higher melting point. The use of polypropylene has progressed rapidly since its introduction. A polyolefin fabric (e.g., a woven or a knit fabric) comprises at least 50% by weight of polyolefin fibers or other fabric-building elements (e.g., films, coatings, foams, sizes, finishes, etc.). Polyolefin fabrics are generally desirable for use in activewear and sportswear markets, especially for socks, thermal underwear, and fabric linings. They may also be useful in automotive applications, for example, as interior fabrics used in or on kick panels, package shelves, seats, truck liners, load decks, etc. Some home furnishing applications include indoor and outdoor carpets; carpet backing; upholstery and wall coverings; furniture and bedding construction fabrics. Some industrial applications include carpets, nonwoven fabrics, ropes, filter fabrics, bagging, and geotextiles.

One of the more recognizable properties of polyolefins is their strength in both wet and dry conditions. Polyolefins are also stain-, mildew-, abrasion-, and sunlight-resistant. Polyolefin fibers also are thought to provide good bulk and cover, while having low specific gravity. This generally means warmth without weight, which can be desirable in certain applications. The fibers have low moisture absorption, so they can wick moisture and dry quickly. Polyolefins generally do not dye well, but have the advantage of being colorfast, e.g., if composition- dyed. Polyolefins also have a low melting point, which can be problematic in treating the polyolefins so as to impart specific functionality.

One of the key performance criteria in modern sports and active outdoor wear is moisture management — the ability of a garment to transport moisture away from the skin to the garment's outer surface. To increase the use of polyolefins in such applications, it is necessary due to consumer demands that the polyolefins have a cotton-like feel, yet maintain their natural moisture repellency. A fabric's one-way moisture transport capacity and its overall moisture- management capacity are significantly correlated with perceptions of clammy and damp sensations, for example, with increased exercise time. In addition to sportswear and active wear, there is growing interest in the use of fabrics having optimal moisture-management characteristics in the flame-retardant apparel market. It is also desirable for the polyolefins, especially in active wear applications, to have odor-control capabilities. Providing these characteristics to polyolefins for use in these and other applications has heretofore proven challenging.

Because of their hydrophobic nature, meaning they have minimal moisture and/or water absorbency, surface treatments to provide these characteristics have not met with success. The applied finishes are not durable and easily wash off. This is believed to be due at least in part to the insufficient wet-pick-up of the finish on the polyolefin fabric. For instance, typical treatments that are used to provide moisture-management capabilities for polyester fabrics are finishing treatments involving polyurethane-based compounds. If these polyurethane-based compounds are used on polyolefin fabrics to impart the same characteristics, these compounds tend to wash away easily. It is believed that the polyolefin does not bond to the polyurethane compounds, and therefore, the treatment is not durable. It is also believed that the fabric is not able to pick up enough of the finishing treatment due to its hydrophobic nature. Moreover, it is believed that the polyurethane compounds are not able to form a network on the surface of the polyolefin because they crosslink to form the network at a higher temperature than the melting point of the polyolefin. Additionally, because polyolefins have a low melting point, any treatments that involve heating can modify the fiber properties to such an extent that the desirable properties of the fiber are no longer present.

Furthermore, efforts to combine moisture management and odor-control treatments have met with little success. Thus, combining the two functionalizations in such a way as to maintain the desirabilities of both can be challenging. SUMMARY

The present invention relates to polyolefin fibers and fabrics that have durable functionality, including moisture-management capabilities and, at least in some embodiments, odor-control characteristics. In one embodiment, the present invention provides a method of functionalizing a polyolefin substrate comprising: providing a polyolefin substrate; applying a durable moisture- management composition that comprises a hydrophilic networking agent to the polyolefin substrate with a minimum of about 60% WPU; and allowing at least a portion of the durable moisture-management composition to form a substantially continuous network on the surface of the polyolefin substrate so as to form a functionalized polyolefin substrate having moisture management characteristics.

In another embodiment, the present invention provides a functionalized polyolefin substrate having a substantially continuous network on a surface of the polyolefin substrate formed by a functionalization composition that comprises a networking agent. In another embodiment, the present invention provides a functionalization composition for treating polyolefin substrates comprising a hydrophilic networking agent and/or an odor- control agent.

In another embodiment, the present invention provides an apparel item comprising a functionalized polyolefin substrate having a substantially continuous network on its surface formed by a reaction comprising a functionalization composition that comprises a networking agent.

The features and advantages of the present invention will be readily apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to polyolefin fibers and fabrics that have durable functionality, including moisture-management capabilities and, at least in some embodiments, odor-control characteristics. Glossary of Some Terms

The term "durable" as used herein refers to the ability of a finish to retain its characteristics and remain inherent, to at least some degree, in a substrate through ordinary household washings for the life of the goods. More specifically, as used herein, the term refers to the durability of a functionalized finish on a substrate after at least 5 AATCC washes according to American Association of Textile Chemists and Colorists ("AATCC") Test Method

61-1996, Option 2A. The term "AATCC" washes as used herein similarly refers to this method.

An "elastic fiber" is one that will recover at least about 50%, more preferably at least about 60%, and even more preferably 70%, of its stretched length after the first pull and after the fourth to 100% strain (double the length). One suitable way to do this test is based on the International Bureau for Standardization of Manmade Fibers, BISFA 1998, chapter 7, option A. Under such a test, the fiber is placed between grips set 4 inches apart; the grips are then pulled apart at a rate of about 20 inches per minute to a distance of eight inches and then allowed to immediately recover.

The term "fiber," as used herein, refers to a material in which the length-to-diameter ratio is greater than about 10. Fiber is typically classified according to its diameter. Filament fiber is generally defined as having an individual fiber diameter greater than about 15 denier (17 dtex), usually a greater than about 30 denier (33 dtex). Fine denier fiber generally refers to fiber having a diameter of less than about 15 denier. Microdenier fibers are generally thought of as multifilament fibers having less than about 0.9 denier (1 dtex) per filament. "Filament fiber" or "filament fiber" means a single, continuous strand of material of indefinite (i.e., not predetermined) length, as opposed to a "staple fiber," which is a discontinuous strand of material of definite length (i.e., a strand which has been cut or otherwise divided into segments of a predetermined length).

The term "finish" or "finishing," as used herein, refers to chemical and other treatments used to modify the fabric to make it more capable of fulfilling its function. A finish may impart functionalization to a substrate. The term "functionalization" and its derivatives including "functionalities" or "functionality," as used herein, refer to a function imparted to a substrate that may be devised to make the substrate more suitable for a particular purpose, to give it some desirable property it would not otherwise possess, or to correct some defect in it. The term "hard yarn," as used herein, refers to a fiber that is not elastic as defined above.

It should be understood that despite being termed "nonelastic," these fibers are not necessarily rigid, and may have the ability to be stretched to some extent under a biasing force, and may exhibit some recovery when the biasing force is released after such stretching.

The term "hydrophilic networking agent," as used herein, refers to a hydrophilic composition that is used to impart moisture-management capabilities. The hydrophilic networking agent may comprise one or more hydrophilic compounds that are capable of forming a high molecular weight {e.g., 100,000 g/mol (daltons) or greater ) substantially continuous network on a polyolefin substrate.

The term "moisture management," as used herein, refers to the ability of a garment to transport moisture away from the skin to the garment's outer surface. It similarly refers more generally to the transfer of both water vapor and liquid by a substrate, for example, a fabric.

The term "odor control" refers to the odor control functionality of a substrate. Antibacterial properties are one set of the properties associated with odor control in substrates.

The term "odor-control agent," as used herein, refers to a treating agent that imparts odor- control capabilities to a substrate.

The term "polymer," as used herein, refers to a polymeric compound prepared by polymerizing monomers of the same or a different type. The generic term "polymer" encompasses homopolymers, copolymers, terpolymers, dendrimers, interpolymers, and oligomers. The term "polyolefin," as used herein, refers to a family of polymers (such as polyethylene and polypropylene) made from olefin monomers. Olefin monomers are made from alkenes. Olefins are also referred to as polyolefins. Polyethylene and polypropylene are examples of polyolefins. The terms "polyolefin" and "polyolefins" may be used generally herein to refer to all types of polyolefin substrates, including fibers, fabrics, and garments. The term "polyolefin fiber," as used herein, refers to a synthetic fiber group in which the fiber-forming substance is any long-chain synthetic polymer composed of about 85% or more by weight of ethylene, propylene, or other olefin units. The term "polyolefin fabric," as used herein, refers to any fabric (e.g., a woven or a knit fabric) that comprises about 50% or more by weight of polyolefin fibers or other fabric-building elements (e.g., films, coatings, foams, sizes, finishes, etc.). In some embodiments, a polyolefin fabric used in conjunction with this invention may be about 70% polyolefϊn-based hard yarn. The term "substantially continuous network," as used herein, refers to a high molecular weight (e.g., 100,000 g/mol (daltons) or greater) polymeric structure with a topology that includes crosslinks, branches, and chain interactions, such that there is little spatial discontinuity in two and sometimes three dimensions other than those expected from chain defects, such as unreacted groups or chain connections degraded due to thermal or mechanical effects. The presence of a substantially continuous network on a polyolefin fabric may be determined, for example, by a technique involving infrared analysis. At least in some instances, a substantially continuous network once formed should not dissolve in a solvent that dissolves the precursors used to form the substantially continuous network.

The term "substrate," as used herein, refers genetically to any base material, e.g., either a fiber or a fabric, on which processing is conducted for a chosen treatment. For instance, a substrate may include a fiber, fiber assembly, yarn, fabric or film to which another material is applied.

The term "treating agent" genetically refers to any component of a composition used in a treatment and does not imply any specific action by the treating agent. The term "treatment" genetically refers to any process such as chemical or heat treatment, laundering, or finishing steps. The term does not imply any particular treatment nor does it imply any particular action of the treatment upon the substrate.

The term "untreated fabric sample" refers to a sample of a fabric that does not have any finishing treatment thereon. The term "WPU" is an acronym for "wet pick up" and refers to the total amount of liquid, and optionally a treating agent carried by the liquid, applied to a substrate. WPU is usually determined as a percentage (%) of either the dry or conditioned weight of the substrate prior to processing. When a substrate is pre-wetted before the application of a treating agent, then the wet pick up of the treating agent may be a percentage of the total WPU and likely will depend on the concentration of the actual treating agent in the composition being applied to the substrate.

The term "yarn" includes both a filament fiber, as well as a number of staple fibers, twisted or otherwise joined together to form a continuous strand. All numbers disclosed herein are approximate values, regardless of whether the word

"about" or "approximate" is used in connection therewith. They may vary by some degree.

Additionally, whenever a numerical range with a lower limit, RL, and an upper limit, RU, is disclosed, any number and any included falling within the range disclosed is specifically disclosed.

Moreover, the indefinite articles "a" or "an," as used herein, are defined to mean one or more than one of the element that it introduces.

Detailed Description of Certain Embodiments of the Present Invention

In certain embodiments, the present invention provides methods and compositions relating to improved polyolefin substrates that have been functionalized so as to have improved durable moisture-management and/or odor-control characteristics.

In some embodiments, the methods of the present invention comprise treating a polyolefin substrate (e.g., a polyolefin fabric) with a hydrophilic networking treating agent to impart moisture-management characteristics. In some embodiments, this treatment of the polyolefin substrate may be combined with an odor control treatment either in a one-step or two- step treatment process. While not wishing to be limited by any particular theory, it is believed that the hydrophilic networking treating agents form a relatively high molecular weight, substantially continuous network that is bonded to the polyolefin substrate (e.g., by crosslinking of the agents to form a durable substantially continuous network), thereby imparting desirable durable moisture management, and optionally odor-control, capabilities to the polyolefin substrate. In some embodiments, the odor control agent may become part of the substantially continuous network formed by the hydrophilic networking agent; in other embodiments, the odor control agent may be part of another network. In some embodiments, the two networks can be applied separately, one on top of the other. In some instances, these do not need to have branching or bonding between the two networks.

There may be many potential advantages to the methods and compositions of the present invention, only some of which may be alluded to herein. One of the many potential advantages may be that polyolefin substrates having desirable durable functionalities are achieved. Additionally, in certain embodiments, multifunctional polyolefin fabrics may be provided. Perhaps more importantly and surprisingly, it is believed that no adverse effects on the polyolefin substrates may be observed as a result of the methods of the present invention. Thus, the polyolefin substrates may retain many of their desirable characteristics, such as strength and resiliency, while realizing improved moisture-management and optionally odor-control characteristics. Another potential advantage is that the polyolefin substrates treated in accordance with the methods of this invention may be used successfully in apparel applications, such as active wear, intimates, swimwear, career wear, work wear (uniforms and protective clothing), medical clothing, and other technical clothing. In some embodiments, durability of the functionalization of the polyolefin substrates may be maintained through about 5 AATCC washes. In other embodiments, durability of the functionalization may be maintained through about 5 to 30 AATCC washes.

Examples of Polyolefin Substrates Suitable for Use in Embodiments of the Present Invention

Polyolefin substrates that are suitable for use in the present invention include polyolefin fibers and any polyolefin fabrics that comprise about 50% or more by weight polyolefin fiber. If a fabric is used, the fabric structures of the fabrics that are suitable for use in the present invention can be knit, woven, or nonwoven. Knitted fabrics are preferred, at least in some embodiments. As previously mentioned, polyolefin fabrics generally comprise about 50% or more by weight of polyolefin fibers or other fabric building elements (e.g., films, coatings, foams, sizes, finishes, etc.). In certain embodiments, suitable polyolefin fabrics may comprise about 70% or more by weight polyolefin fiber. An example of a preferred polyolefin fabric may contain about 70% or more polyolefin hard yarn. Any suitable fiber may be blended with the polyolefins for use in the substrates.

Examples of suitable polyolefin fibers (that may be treated as described herein themselves or as components of fabric(s)) may include, but are not limited to: Ziegler-Natta catalyzed polypropylene homopolymers, polyethylene homopolymers, linear low density polyethylene, high density polyethylene, polyethylene copolymers, polypropylene copolymers, metallocene catalyzed polypropylene homopolymers, ethylene-propylene copolymers, rubber- modified polypropylene polymers, poly 4-methyl, 1-pentene, other high-melting point (>140°C) polyolefins, such as poly-4-methyl- 1-pentene, cyclic-olefin-copolymers, and syndiotactic polystyrene, and propylene copolymerized with other olefin monomers that increase the melting point of the polypropylene. Blends of these also are suitable. For instance, blends of these high- melting point polyolefins with amorphous polymers, such as atactic polystyrene and hydrogenated polystyrene, may also be suitable. Examples of other potential things that can be blended in the fiber with the polyolefins may include, but are not limited to, polyethylene terephthalate ("PET"); polybutylene terephthalate ("PBT"); polytrimethyl terephthalate ("PTT"); polyesters; polyester copolymers; Nylon 6; Nylon 6,6; acrylic; polycarbonates; polylactides; polyglycolides; and the like. Examples of other potential fibers that can be blended in the fabric with the polyolefins may include, but are not limited to, synthetic and organic fibers; PET; PBT; PTT; polyester; polyester copolymers; Nylon 6; Nylon 6,6; acrylic; cotton; wool; rayon; viscose; bamboo; polycarbonates; polylactides; polyglycolides; and the like.

Examples of olefin monomers include, but are not limited to propylene, isobutylene, 1 - butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1- tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 3 -methyl- 1 -butene, 3 -methyl- 1-pentene, 4- methyl- 1-pentene, 4, 6-dimethyl- 1-heptene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C4-C40 dienes, including but not limited to 1 ,3-butadiene, 1,3-pentadiene, 1,4- hexadiene, 1 ,5-hexadiene, 1 ,7-octadiene, 1 ,9-decadiene, other C4-C40 α-olefins, and the like. In certain embodiments, the α-olefin is propylene, 1 -butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. Although any hydrocarbon containing a vinyl group potentially may be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.

Yarns suitable for the present invention may be monofilament or multifilament. They may be monocomponent or multicomponent. In some instances, these yarns may comprise bicomponent fibers that comprise a sheath and a core formed from one or more polyolefins. Examples include bicomponent fibers having a sheath:core ratio of PE to PET of 50:50; 60:40; 70:30; 80:20; 90:10; etc. The denier range for a yarn made from the fibers may range from about 30 to about 600, and the number of filaments in a yarn may range from about 1 to about 400. In certain embodiments, the yarns that comprise the fibers used in the fabrics may be bare or covered yarns. Suitable covering technologies for covered yarns that can be used are: air-jet covering, core-spun-yarn covering, and others.

Additives may be included in the fibers if desired, provided that any such additives do not negatively impact the purposes of the present invention. For instance, additives for resistance to oxidation and UV exposure, for static dissipation, for odor control, for fiber coloring, spin finish, and other aids that are well known in the art may be used. The fibers could also contain dispersed particles for purposes such as (but not exclusive to) dyeability. These particles could be polymeric, clays, metal hydroxides, or the like. In some embodiments, the polyolefin substrate may comprise odor control compounds. This could be the case, for example, in embodiments where odor control agents, such as carbon, are added to the melt before spinning. The moisture management treatment can also be applied onto substrates that contain odor control additives. These can be odor absorbing additives such as cyclodextrin based, activated carbon based, and others or antibacterial additives such as silver based, copper based, triclosan based, nano-silver based, and others.

In some embodiments of the methods of the present invention, optionally, the polyolefm substrate can be dyed during the compounding step by adding suitable coloring compounds, including, but not limited to, pigments, organic, and inorganic particles. Polyolefm fabrics can also be dyed using standard textile dyeing processes well known to those skilled in the art. Several dye classes may be used. These include, but are not limited to, acid dyes, disperse dyes, reactive dyes, basic dyes, direct dyes, vat dyes and others known by experts in the art and dyeing technologies.

In some embodiments, the substrates also may comprise other fibers, including elastic fibers to provide stretch and elastic recovery properties. Suitable examples of elastic fibers include, but are not limited to, rubber filaments, elastoesters, lastols, spandex, "LYCRA " fibers (easily available from many global sources), bicomponent filaments, and "DOW XLA™" fibers, (available from The Dow Chemical Company, at many locations).

In some embodiments, the present invention provides apparel items suitable for a myriad of end uses that comprise a functionalized polyolefm substrate having a substantially continuous network on its surface formed by a reaction comprising a functionalization composition that comprises a networking agent.

Examples of Functionalization Compositions of the Present Invention

In some embodiments, the present invention provides durable moisture-management compositions comprising a hydrophilic networking treating agent and a solvent. In some embodiments, the present invention provides functionalization compositions for polyolefin substrates comprising a hydrophilic networking agent (which may include a solvent in its structure when purchased or made), a solvent for the composition, and optionally an odor- control agent.

In some embodiments, the compositions optionally may comprise a catalyst, a wetting agent (e.g., to improve fabric wetting with the composition), an optical brightener (for whites) to increase fabric whiteness, as well as other additives known in the textile art (assuming they do not negatively impact the composition or the durability of the functionalizations). Suitable catalysts include those catalysts that would be capable of interacting with the hydrophilic networking agent in such a manner as to facilitate formation of the substantially continuous network. Suitable wetting agents include those any suitable wetting agent that does not negatively impact durability of the treatment. Selection of a suitable wetting agent should be done carefully, taking into consideration at least the ionic character of the wetting agent and its ethylene oxide content. Nonionic ethoxylated wetting agents are preferred, in some instances. A preferred wetting agent may have an ethylene oxide content of about 60% to about 70% (by weight) Suitable optical brighteners include those that are suitable in textile applications. An example is TiO₂. Others designed for synthetic fibers may be used, such as those designed for polyesters. Note that the ionic character of these additives may affect durability and compatibility of the treatment.

The hydrophilic networking agents used in conjunction with the present invention may comprise one or more hydrophilic compounds that are capable of forming a relatively high molecular weight (e.g., 100,000 or greater) substantially continuous network on a polyolefin substrate. Suitable hydrophilic networking agents may include single components or combinations of several components. The agents may be polymeric or non-polymeric.

The hydrophilic networking agents suitable for use in the present invention preferably have two functionalities: hydrophilic functionalities and network forming functionalities. Preferred hydrophilic networking agents are reactive, and preferably, are crosslinkable. In some embodiments, it may be that a particular compound or combinations of compounds possess one of these characteristics. In other embodiments, it may be that a compound or a combination of compounds can be derivatized through a suitable reaction to obtain the desirable functionality so as to be useful as a hydrophilic networking agent. Compounds that can be used as or derivatized to be used hydrophilic networking agents according to this invention include, but are not limited to, polyethylene oxide or copolymers thereof; polyether-based polymers (e.g., low or high molecular weight, hydroxyl terminated, amine terminated, reactive or nonreactive, homopolymer or copolymer, and the like); polycarboxylic acids (low or high molecular weight, acid form or salt form, reactive or nonreactive, homopolymers or copolymers, and the like); polyurethanes (low or high molecular weight, hydroxyl terminated, amine terminated, reactive or nonreactive, homopolymer or copolymer, and the like); polyvinylalcohols and their copolymers; polysaccharides; cellulose or cellulosic monomers or polymers; natural or synthetic hydroxyl, carbonyl, amino, or thiol group containing polymers; ethoxylated polyesters; sulfonated polyesters; ethoxylated polyamides; ethoxylated polyethylenes; fatty acid alkanolamide; polysilicic acid; and polyorganosiloxanes. Mixtures of these may be suitable as well. These mixtures may include components that have differing molecular weights and/or differing hydrophylicities and concentrations of reactive sites. The combination may be beneficial. One may choose the combination of components based on these differing characteristics to achieve chosen synergistic results. Examples of preferred networking agents include polyurethanes and polyorganosiloxanes. One example of a preferred hydrophilic networking agent is hydrophilic polyurethane commercially available as "RUCO-PUR SLK" from Rudolf GmbH & Co. KG. In some embodiments, the networking agent may be present in a functionalization composition in an amount ranging from about 5% to about 60% by weight of the functionalization composition, and preferably about 10% to about 40% by weight, and more preferably about 20% to about 30%.

Suitable solvents for the functionalization compositions include aqueous solvents such as water (e.g., deionized water, tap water,) as well as other solvents that do not undesirably impact the hydrophilic networking agent and/or the optional odor-control agent. The amount of solvent used in a functionalization composition may range from about 5% to about 99% by weight of the functionalization composition.

Suitable odor-control agents include those compounds capable of imparting durable antimicrobial functionality to a polyolefin substrate. Suitable odor-control agents may have groups that can stop or delay bacterial growth through physical and electrochemical membrane disruption, or a biochemical pathway by interrupting the formation of vital enzymes used in energy production by bacteria. These odor-control agents preferably have reactive sites that can react with the substrate and/or with itself. Reactions of the compounds are believed to result in crosslinks being formed either between a fiber and the odor-control agent, between the molecules of the odor-control agent, or a combination of the two. If the odor-control agent is not reactive, then the odor-control agents can be co-applied with an additive that can form durable coating on the substrate, preventing the odor-control agent from washing away. Examples of suitable odor- control agents include such odor control compounds that include, but not limited to, silver zirconium phosphate, triclosan, nano silver, quaternary amine compounds, crosslinkable silyl quats, polyhexamethylene biguanide, and chitosan. Odor control agents can also be odor absorbers (e.g., cyclodextrin, activated carbon, and others) or odor neutralizing agents. Combinations of these may be suitable as well. Preferred odor-control agents are reactive and crosslinkable compounds. In some embodiments, the amount of an odor control agent to include in a functionalization composition could be from about 0.1% to about 15% based on the weight of the substrate. The exact amount to include will depend, inter alia, on the desired degree of performance.

Examples of Some Methods of the Present Invention

The substrates may be treated in any desirable order or fashion as recognized by one of ordinary skill in the art with the benefit of this disclosure. The fabric functionalization step could involve more than one step, depending on the technology employed and whether odor- control functionalization will be imparted.

In some embodiments, the present invention provides methods of functionalizing a polyolefin substrate comprising: providing a polyolefin substrate; applying a hydrophilic networking treating agent to the polyolefin substrate with a minimum of about 60% WPU; and allowing the hydrophilic networking treating agent to form a substantially continuous network on the surface of the polyolefin substrate. In some embodiments, these methods are wet-on-dry applications (i.e., the composition is wet and fabric is dry).

In some embodiments, the methods of the present invention may include applying an odor-control agent to the polyolefin substrate before, during, or after the step of applying a hydrophilic networking treating agent to the polyolefin substrate. If it is applied with the hydrophilic networking agent, then it may be considered a one-step process. If it is applied before or after the hydrophilic networking, then it may be considered to be a two-step process.

In additional embodiments, first a moisture-management treatment and then a combination moisture-management/odor-control treatment may be used. Illustrations of some examples of one-step processes and two-step processes are discussed below in the Examples section.

During functionalization, in some embodiments, a substrate may be impregnated (e.g., placed on or incorporated with) with a hydrophilic networking agent and/or an odor-control agent using padding, spray application, printing, exhaust processes, or a combination of these and other fabric treatments. It is preferred that a minimum of about 60% WPU be achieved. In some embodiments, the application temperature for these treatments can vary from room temperature to about 200⁰C. A preferred temperature range is about 100⁰C to about 150⁰C.

In the methods of the present invention, optionally, the polyolefin substrate may be wetted before application of the functionalization composition. In some embodiments, it may be useful to wet the fabric before the functionalization treatment to achieve a WPU of about 60% to about 100% or 120%, which may be useful for durability. The degree of composition penetration into the substrate may be an important consideration in the functionalization process as it is believed that the degree of fϊmctionalization correlates to the degree of composition penetration.

In some embodiments, discontinuous processes can be used (e.g., jet or over-flow or soft- flow or beam-autoclave or jig machines where fabric can be treated in rope or in open-width forms). Continuous processes similarly may be used if preferred, for example, those processes conducted in washing/scouring machines where a fabric is continuously treated in open-width or rope form. Also, tumble washing machines may be suitable where substrates can be treated in garment form. In addition, wetting also may be accomplished in a closed container (such as a cart used to transfer fabrics from one location to another in a textile mill) by holding the fabric for a desired amount of time in a wetting composition. The time required to have an effective wetting depends on the method and process used, as will be recognized by one skilled in the art with the benefit of this disclosure. The time allowed for the substrate to remain in contact with water or with the composition bath can be optimized for each process. Shorter residence times are preferred, but of course, not required. After optionally wetting the fabric, the functionalization treatment may be applied.

Examples of suitable equipment methodologies include, but are not limited to, a nip roller or several nip rollers for application of composition onto the substrate fabric to control WPU. In the functionalization step, in some embodiments, a single-dip and a single-nip process may be used. Several other options can also be used, including, but not limited to, centrifuging spraying, exhausting, coating (e.g., foam application). After wetting, it is believed that the fabric takes on some of the composition.

In some methods, a scouring step may be useful. Scouring may be considered a separate step from the wetting step, or it may be used as the wetting step. A suitable scouring process may include a warm wash in a scouring agent composition in a temperature range from about 20°C to about 95°C. Examples of suitable scouring agents include, but are not limited to, anionic, nonionic or cationic surfactants and/or polyether polymers (homopolymers and copolymers can be included). An example of a preferred scouring agent is a nonionic wetting agent. Continuous scouring processes are suitable. Another suitable scouring process may include a discontinuous process, such as a process employing jet or over-flow or soft-flow or beam-autoclave machines where the substrate fabric can be treated in rope or in open-width forms. Another suitable process includes a method employing tumble washing machines where the substrates can be treated in garment form. A preferred scouring process is a discontinuous process with a nonionic detergent formulation at a temperature range of about 7O⁰C to about 95⁰C for about 15 to about 45 minutes.

In some embodiments of the methods of the present invention, optionally, the polyolefin substrate can be dried. This may occur in any suitable drying process, including, but not limited to, those involving a stenter frame, a belt dryer, or a tumble dryer. The fabric can be treated in rope, open-width, or in garment form. In some embodiments, temperatures typically include a range of about 100⁰C to about 200⁰C, and the residence time may vary from less than 1 second to about 1000 sec. An example of suitable drying conditions include temperatures of about 110⁰C to about 14O⁰C and residence times of about 30 seconds to about 300 seconds in a stenter frame oven.

In some embodiments of the methods of the present invention, optionally, the polyolefin substrate may be subject to a low temperature heat setting process. Such processes may include low temperature heat setting processes, such as in stenter frame for open-width forms, and steamer processes for garments, open-width, or tubular forms. Typical temperatures may be in a range of about 100⁰C to about 150⁰C, and residence time varies from about less than 1 second to about 1000 seconds.

Drying can take place (but need not) at low, mild and high temperatures in a forced air oven, or in a tumble dryer, or by using heated cylinders. Curing can take place (but need not) at low, mild and high temperatures in a forced air oven, or in a tumble dryer, or by using heated cylinders. Drying and curing can take place at the same time or separately. For instance, in some embodiments, first drying, and then curing can take place. Drying and/or curing time may depend on several factors, including, but not limited to, the equipment, temperature, fabric moisture content, fabric structure, and other details. Shorter drying and/or curing times (less than 10 minutes) are preferred. In some embodiments of the methods of the present invention, optionally, the polyolefin substrate can be dyed during the compounding step by adding suitable coloring compounds, including, but not limited to, pigments, organic, and inorganic particles. Polyolefin fabrics (modified) can also be dyed using standard textile dyeing processes well known to those skilled in the art. Several dye classes may be used. These include, but are not limited to, acid dyes, disperse dyes, reactive dyes, basic dyes, direct dyes, vat dyes and others known by experts in the art and dyeing technologies.

All processing steps, including those mentioned herein as well as those that are known to those skilled in the art, may be performed before or after the functionalization if desired. The substrates may be treated in any desirable order or fashion, as recognized by one of ordinary skill in the art with the benefit of this disclosure. The fabric functionalization step could involve more than one step, depending on the technology employed. Examples of suitable treatment methodologies include, but are not limited to, the following methods: • Scouring → Heat Setting Fabric Functionalization - → Drying;

• Scouring → Heat Setting Fabric Functionalization - -» Drying — ÷ Heat

Setting;

• Heat Setting → Scouring Fabric Functionalization - →- Drying;

• Heat Setting → Scouring Fabric Functionalization - -» Drying — ÷ Heat Setting;

• Scouring → Heat Setting Dyeing → Fabric Functionalization - →- Drying

Heat Setting;

• Scouring → Heat Setting ^■ Dyeing → Fabric Functionalization - → Drying

Printing → Drying → Heat Setting; • Scouring → Heat Setting → Dyeing → Drying → Fabric Functionalization →

Heat Setting;

• Scouring → Heat Setting → Dyeing → Drying → Printing — > Drying →

Fabric Functionalization -→ Heat Setting;

• Scouring → Dyeing → Heat Setting → Fabric Functionalization → Drying → Heat Setting;

• Scouring → Dyeing → Heat Setting → Fabric Functionalization → Drying

→Printing — > Drying — >Heat Setting;

• Scouring → Dyeing —> Heat Setting→ Drying → Fabric Functionalization →

Heat Setting; or • Scouring → Dyeing → Heat Setting→ Drying → Printing — * Drying →

Fabric Functionalization → Heat Setting.

Examples of Some Articles of the Present Invention

In some embodiments, the present invention provides polyolefin substrates having a substantially continuous network on their surfaces formed by a reaction comprising a networking treating agent. The substantially continuous network is believed to provide improved moisture- management control characteristics for the polyolefin substrate. In some embodiments, the present invention provides apparel items comprising a polyolefin substrate having a substantially continuous network on its surface formed by a reaction comprising a networking treating agent. In some embodiments, these apparel items may further comprise an odor-control agent. To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given, hi no way should the following examples be read to limit, or define, the entire scope of the invention. Ratios, parts, and percentages are by weight unless otherwise stated.

EXAMPLES General Experimental Procedures, Testing Methods, and Equipment

Polyolefin fabric samples (8 inch x 12 inch: these are approximate dimensions) are cut and prepared to illustrate certain aspects of their durability. Table 3 describes the fabric samples in more detail. The fibers that are used in the fabrics are described in Table 2, and the resins used to make the fibers in Table 2 are described in Table 1. To treat the fabric samples, different concentrations of aqueous compositions are prepared. Each specific example discusses the specific compositions used in that example. The fabric samples described above are dipped into the compositions, and allowed to remain in an appropriate container, usually a glass beaker, for a predetermined amount of time. This is followed by a padding step to a pre-determined wet-pick-up ("WPU") level that can be calculated by using a laboratory weighing scale. In each example, the padding step is performed using a laboratory scale single dip, single nip padding machine, specifically Werner Mathis Horizontal Padding Machine, Type HF, available at multiple locations. After padding, the fabric samples are dried in a laboratory scale forced air stenter frame drying oven (Werner Mathis, Drying and Setting Unit, Type LTE, available at multiple locations) at a preset temperature for a predetermined amount of time. Drying and curing of the chemical finish on the fabric can occur simultaneously during the drying step. The resulting dried samples are then subjected to testing to examine certain aspects of durability, including wetting characteristics and antibacterial resistance.

Wash Test For the wash tests discussed below, American Association of Textile Chemists and

Colorists ("AATCC") Test Method 61-1996 is used for the fabric samples described above. AATCC Test Method 61-1996 is designed to evaluate the colorfastness and staining potential of fabrics under accelerated washing conditions that simulate five home washings. Option 2A of the testing method is used, which is designed for fabrics that are expected to withstand repeated low-temperature machine washings. In this test, fabric samples are washed under specified conditions to replicate five home washings. The samples are then evaluated for color change, staining, and abrasion. The conditions for the tests below are: • temperature of 49°C ±3⁰C;

• 50 steel balls;

• 0.15% AATCC Standard Reference Detergent, powdered, without an optical brightener;

• time is 45 minutes; and • standard post-laundering protocol.

Water Absorbency Test

AATCC Test Method 79-2000 is used. This test is intended, inter alia, to evaluate absorbency of bleached textiles. Using this test, five measurements of wetting time can be taken, and an average of the five can be recorded as wetting time in seconds. Using some judgment, wetting tests can be omitted for samples that have shown poor hydrophilic character. Wetting time is measured up to 600 seconds, although the actual testing method (AATCC) only delineated 60 seconds. After 600 seconds, the test can be stopped and the value recorded as greater than 600 seconds.

Microbiological Fabric Analysis American Society for Testing Materials ("ASTM") test method E2149-01 is considered to be a standard test method to measure odor control activity of immobilized antimicrobial agents under dynamic contact conditions. This test method is designed, inter alia, to evaluate the resistance of non-leaching antimicrobial treated specimens to the growth of microbes under dynamic contact conditions. This dynamic shake flask test is useful for routine quality control and screening tests in order to overcome difficulties in using classical antimicrobial test methods to evaluate substrate-bound antimicrobials, according to the ASTM method.

The antimicrobial activity of a substrate-bound antimicrobial is thought to be dependent upon direct contact of microbes with the active chemical agent. This test is designed to determine the antimicrobial activity of treated specimen by shaking samples of surface bound materials in a concentrated bacterial suspension for a one hour contact time or other contact times as desired. The suspension is serially diluted both before and after contact and cultured. The number of viable organisms in the suspension is determined and the percent reduction is calculated based on initial counts or on retrievals from appropriate untreated controls. This is all according to the ASTM method.

The percent reduction of the organisms resulting from contact with the specimen may be calculated by using the following formula. Results can be presented in either percent reduction when measuring colony forming units per milliliter (CFU/ml) or as a death rate constant when calculating mean loglO density of bacteria.

Reduction, % (CFU/ml)= [(B - A)/ B ] * 100 • Death Rate Constant (mean loglO density)= B - A where: A = CFU/ml (or mean loglO density of bacteria) for the flask containing the treated substrate after the specified contact time, and

B = "0" contact time CFU/ml (or mean loglO density of bacteria) for the flask used to determine "A" before the addition of the treated substrate.

In brief, the test is performed by first adding a 0.5 gram to 2 gram sample of treated fabric to a flask containing 50 mL of a buffered-saline composition according to the ASTM method. The flask is then inoculated with the challenge organism and shaken through mechanical means for a designated period of time. At specified time points, a sample of the composition is then removed and plated. Lastly, the plate is incubated, examined for microbial growth, and the number of colony forming units counted. The log reduction in organisms is measured by comparing the growth on the experimental plate to control plates with no antimicrobial treatment.

From the ASTM method, preparation of bacterial inoculum: Grow a fresh 18hr shake culture of bacteria insterile nutrient broth for each series of samples. Dilute the culture with the sterile buffer solution until the solution has an absorbance of 0.28 6 0.01 at 475 nm, as measured spectrophotometrically. This has a concentration of 1.5-3.0 3 108 CFU/ml. Dilute appropriately into sterile buffer solution to obtain a final concentration of 1.5-3.0 3 105 CFU/ml. This solution will be the working bacterial dilution. Fiber Samples

The production details of the fibers that are used are given below in Table 2. Table 1 lists the resin details used to make the fibers detailed in Table 2. Table 1. Resin Details

Table 2. Fiber Production Details

Fiber production details are given in Table 2. The 42d NG XLA is a 42 denier fiber having an 0.8 fiber profile. The spinneret die profile for forming the fibers is 3 : 1.

Fabric Samples

Descriptions of the fabrics that are used are given in Table 3. All of the fabric samples are made on a circular knitting machine. Machine gauge and fabric structure for each fabric are listed in Table 3. Polypropylene yarns are purchased from commercial yarn manufacturers: lply/45d denier/42 filament yarn available from Aquafil Dryarn Textile Yarns S.p.A. and 2 ply/ 45 denier/ 50 filament as well as 1 ply/ 45 denier/ 50 filament yarn available from Chemosvit Group. The hard yarn specifications for the polypropylene component are listed in Table 3. Similarly, the color of the composition dyed fibers, the ply, the denier, the filament number in the yarns, and the percentage (by weight) are also given in Table 3. The elastic fiber denier, type, and percentage (by weight) in the fabric sample described in Table 2 are provided below in Table 3. The elastic fiber is extended 3 times its original length (i.e., 3x draft) during the knitting process for all of the fabrics described in Table 3.

In addition, observed antibacterial performance and water absorbency times as are determined by the tests described above are given for each fabric are given in Table 3. These tests and results are for the fabrics in their untreated state.

TABLE 3. Description of Fabric Samples

Comparative Examples

These comparative examples illustrate certain moisture-management and odor control treatments. Comparative Examples 1 and 2 are performed by the suppliers (assumed to be) correctly, according to their recommended standards for the products cited. However, the applicants make no representation as to the accuracy of this information. The results are reported herein.

Comparative Example 1

Samples of fabric are sent to the supplier who treats the fabric with an odor control treatment and then tests the treated fabric for performance. This is an example of an odor control achieved by means of an antibacterial treatment of a polyolefin fabric. This example is performed by the supplier. Samples are sent to the supplier for treatment. The supplier's testing methodology and achieved results are reported here, which are assumed to be accurate and according to the supplier's recommended treatment methods and testing methods as described herein. As described above, when an odor-control agent is applied onto a substrate (e.g., a fabric sample), it is believed to form a durable polymeric network on the surface of the substrate. To illustrate this, an odor-control agent is applied to a fabric and then tested according to ASTM Test Method E2149-01, to determine the amount of Escherichia coli bacteria reduction in 1 hour. The specific odor-control agent used in this example is a crosslinkable silyl quat (specifically, octadecyl-amino dimethyl trimethoxysilyl propyl ammonium chloride, also known as "AEM 5700" (available from Aegis Environments Midland, MI USA, www.microbeshield.com). After curing, it is believed that the crosslinkable silyl quat monomers may form a durable siloxane polymer network on the substrate (e.g., the fiber and/or fabric surface). This network is believed to substantially immobilize the odor control part, specifically, the quaternary ammonium chain, providing a odor control property to the substrate.

In this example, Fabric 3 (see Table 3 above for description) is treated with the odor control composition, which is prepared as follows. The supplier prepares the compositions as follows. First a predetermined amount of water is added into a glass beaker, and then the crosslinkable silyl quat (specifically AEM 5700) is added slowly using mild agitation until the desired concentration is reached as described in Table 4 below. Approximately 0.1% by weight Dow Corning "Q2 5211" (wetting agent) available from Dow Corning, is added. The odor control composition is applied to the fabrics using a padding machine. For this example, the data generated on this example, a manually operated nip roller is used. The WPU is adjusted to a weight of 100% by dry weight of the fabric by adjusting the pressures of the nip rollers and using trial and error protocol by controlling the pressure between the nip rollers. The type is Dyna-Jet, Model BL-38. Drying and curing of the treated fabric is done simultaneously on a laboratory scale air-forced convection oven, specifically, VWR Forced Air Model 1350FMS. The temperature is 100⁰C and the drying/curing time is 10 minutes.

Table 4 shows the results of the microbial analysis according to ASTM E2149-01 (which is described above). As can be seen from Table 4, an improvement in bacteria reduction percentage (%) for the treated sample compared to the untreated fabric (shown in Table 3) can be observed.

Table 4. Microbiological Analysis Results

Comparative Example 2 This example relates to a moisture-management treatment of polyolefin fabrics. This example is performed by the supplier. Samples are sent to the supplier for treatment. The supplier's achieved results are reported here, which are assumed to be accurate and according to the supplier's recommended treatment methods and testing methods as described herein.

The moisture-management agent used is a hydrophilic polyurethane commercially available as "RUCO-PUR SLK" from Rudolf GmbH & Co. KG. The suggested application conditions from the supplier are followed, as described below. The observations are reported in Table 5 below.

Fabric 2 (see Table 3) is used for comparative example 2a, and Fabric 3 (see Table 3) is used for comparative example 2b. The formulation and conditions used in this example are according to the supplier recommendations for the specific fabrics used. The supplier prepares the composition as follows. First, a predetermined amount of water is added into a glass beaker, and then the RUCO-PUR SLK is added slowly using mild agitation until the desired concentration is achieved. The resulting composition is applied to the fabrics by a laboratory scale padding machine, as described above. The resulting WPU is 20% by weight of dry fabric. The sample is quickly placed on a lab stenter frame oven, as described above for simultaneous drying and curing. The drying/curing temperature is 120⁰C and the drying time is 1.5 minutes.

Table 5 shows the results of the water absorbency tests. As can be seen from this Table, the treated samples lost their water absorbency performance only after 5 washes. It should be noted that these washings are 4O⁰C home laundry washing using synthetic fiber settings on a home laundry machine, and the drying procedure is 7O⁰C tumble drying.

Table 5. Treatments on Fabric 2 and 3 with Hydrophilic Polyurethane

Comparative Example 3

This example relates to a combination of a moisture-management agent and odor control agent, and co-application of a composition comprising both onto a fabric substrate. These tests are performed by the inventors.

The moisture-management agent in this example is a hydrophilic, reactive compound also known as "AMMS-I" (available from Aegis Environments Midland, MI USA, www. microbeshield.com at multiple locations). The odor-control agent selected for this example is "AEM 5700." Fabric 3 (see Table 3) is used in this example. The formulation and conditions used in this example are those recommended by Aegis Environments. The composition is prepared as follows. First a predetermined amount of water is added to a glass beaker then AEM

5700 is added slowly using mild agitation until the final concentration is reached (see Table 6).

Then, AMMS-I is added slowly using mild agitation until the final concentration is reached. The mixture is allowed to set for 1 hour prior to padding the fabric. The padding is done on a lab padding machine, as described above in the general procedures description portion of the Examples section. The WPU is 100% by weight of dry fabric. Drying and curing are done on a laboratory scale stenter frame oven, as described above in the general procedures description portion of the Examples section. The drying temperature is 115⁰C, and the drying time is 4 minutes.

Table 6 shows the results of the water absorbency tests according to AATCC Test Method 79-1995. As can be seen from Table 6, the treated sample lost its water absorbency performance after only 3 washes (according to the AATCC 2A norm). The treated fabric showed more than 90% bacteria reduction after 3 washes, according to ASTM E2149-01 (Escherichia coli bacteria reduction in 1 hour).

Table 6. AMMS-I in Combination with AEM 5700

Examples Illustrating Certain Aspects of the Present Invention

Example 1

This example demonstrates durable moisture-management treatment of a polyolefin fabric with a hydrophilic polyurethane. The hydrophilic polyurethane selected for this example is RUCO-PUR SLK, described above. Note the different process conditions discussed as compared to comparative examples discussed above.

In this example, Fabric 1 (see Table 3) is used for examples Ia and Ib, and Fabric 4 (see Table 3) is used for examples Ic and Id, respectively. The treatment composition is prepared as follows. First, a predetermined amount of water is added into a glass beaker, and then RUCO- PUR SLK is added slowly using mild agitation during the addition until the final concentration is reached (see Table 7). The fabric samples are placed in the composition for 30 minutes, and then padded with a lab padding machine, as described above. The WPU is adjusted to 100% of the dry fabric weight. The sample is placed on a lab stenter frame oven, as described above. The drying temperature is 13O⁰C, and the drying time is 10 minutes for all samples. Table 7 shows the results of the water absorbency according to AATCC TM 79 described above. As can be seen from Table 7, there appears to be improved water absorbency time for these treated samples as compared to untreated fabrics (shown in Table 3) as well as those samples illustrated in Comparative Example 2, which is believed to be due, at least in part, to the fabric being saturated with the composition, higher wet pick up, and longer drying time. The water absorbency characteristics appear to be durable as indicated by the wetting times in successive washes.

Table 7. Treatments with Hydrophilic Polyurethane

Example 2

This example demonstrates a hydrophilic networking agent on two different polyolefin- based fabrics.

The durable hydrophilic networking agent comprises three components: "HYDROPERM ECO" (which is an aliphatic polyether amide composition that is an hydrophilizing agent with softener properties having a cationic or nonionic nature, available from Clariant), "HYDROPERM RPU LIQ" (an alkoxylate derivative in aqueous composition that is a thermoreactive polyurethane softener for cellulosic fibers, purchased from Clariant), and "ARKOPHOB SR LIQ" (aqueous polyurethane dispersion, purchased from Clariant Europe). After curing, it is believed that the compounds may react and form a durable polymeric network on the surface of the substrate, which may penetrate into the substrate at least to some degree. This network is believed to impart hydrophilic character to the substrate after treatment, enabling the substrate to have durable moisture-management characteristics.

In this example, Fabric 1 (see Table 3) is used for examples 2a and 2b, and Fabric 3 (see Table 3) is used for examples 2c and 2d. The hydrophilic networking agent is prepared as follows. First, a predetermined amount of water is added into a glass beaker. Next, the HYDROPERM ECO is added slowly with mild agitation during addition until the final concentration is reached (see Table 8); then ARKOPHOB SR LIQ is added slowly with mild agitation during addition to reach the desired concentration (as mentioned in Table 8). Next, HYDROPERM RPU LIQ is added slowly using mild agitation during addition until the concentration in Table 8 is reached. The fabrics are placed in the composition for 30 minutes. The fabrics are passed through a laboratory scale padding machine, as described above, where the WPU is 100% of the dry fabric weight. The sample is quickly placed on a lab stenter frame, as described above, for drying and curing. The drying/curing temperature is 13O⁰C, and the drying/curing time is 10 minutes for all samples.

Table 8 shows the results of the water absorbency tests according to AATCC TM 79. As can be seen from Table 8, there appears to be an improvement in water absorbency time for the treated samples as compared to untreated fabrics (shown in Table 3), and the performance appears to be relatively durable as indicated by the wetting time in successive washes.

Table 8. Treatments with Hydrophilic Polyurethane and Hydrophilic agents

Example 3

This example demonstrates the combination of a hydrophilic networking agent and odor- control agent on two different polyolefin fabrics.

The hydrophilic networking agent in this example is AMMS-I, described above. The odor-control agent selected for this example is AEM 5700, described above. In this example, Fabric 1 (from Table 3) is used for example 3a and 3b, and Fabric 2 (from Table 3) is used for examples 3c and 3d. The hydrophilic networking agent and the odor-control agent composition are prepared as follows. First, a predetermined amount of water is added into a container (e.g., a glass beaker); then AEM 5700 is added slowly with mild agitation during addition until the desired concentration is reached (see Table 9). Then, AMMS-I is added slowly with mild agitation during addition until the desired concentration is reached (Table 9). The composition pH is adjusted to 3 with diluted citric acid. The mixture is allowed to set for 1 hour prior to padding on the fabric. Intermittent mild agitation is used during the hold period. The fabric samples are placed in the composition for 30 minutes, and then are padded with a lab padding machine, as described above, where WPU is 100% of the dry fabric weight. The sample is quickly placed on a lab stenter frame for drying and curing, as described above. The drying/curing temperature is 13O⁰C, and the drying/curing time is 10 minutes for all samples.

Table 9 shows the results of the water absorbency according to AATCC TM 79. As can be seen from Table 9, there is improvement in water absorbency time for treated samples compared to untreated fabric (as shown in Table 3) as well as to comparative example 3 above, and the characteristics appear to be relatively durable as indicated by the successive washings.

Table 9. Treatments with Moisture-Management Agent in Combination with an

Odor-Control Agent

Example 4

This example demonstrates the synergy of a hydrophilic networking agent and odor- control agent on a polyolefin fabrics. In this example, the durable moisture-management agent is a hydrophilic polyurethane, specifically RUCO-PUR SLK₃ discussed previously. The odor-control agent is AEM 5700, discussed previously. In this example, Fabric 4 (Table 3) is used. This is an example of a two- step process. The RUCO-PUR SLK composition is prepared as in example 1, and the AEM 5700 composition is prepared as follows. First a predetermined amount of water is added into a glass beaker, and then the AEM 5700 is added slowly using mild agitation until the desired concentration is reached as described in Table 10 below. The fabric sample is placed in the RUCO-PUR SLK composition for 30 minutes, and then padded with a lab padding machine, as described above. The WPU is adjusted to 100% of the weight of the dry fabric. The sample is placed on a lab stenter frame oven for drying and curing, as described above. Drying and curing is done simultaneously on the stenter frame oven. The drying/curing temperature is 13O⁰C, and the drying/curing time is 10 minutes. This concludes the first step of this method. Next, the AEM 5700 odor-control agent is applied as follows. The fabric sample is placed in the AEM 5700 composition for 3-5 seconds and then padded with a lab padding machine, as described above. The WPU is adjusted to 100%. The sample is quickly placed on a lab stenter frame oven for drying and curing, as described above. Drying and curing take place simultaneously on the stenter frame oven. The drying/curing temperature is 13O⁰C, and the drying/curing time is 10 minutes. Table 10 shows the results of the water absorbency tests according to AATCC TM 79 and bacteria reduction according to ASTM E-2149-01. As can be seen from this Table, there appears to be improvement in water absorbency time for treated samples compared to untreated fabrics (shown in Table 3), and the performance appears to be durable.

Table 10. Water Absorbency and Microbiological Analysis Results

Example 5

This example also demonstrates moisture-management treatment of a polyolefin fabric. The method illustrated here is an example of a two-step method involving two moisture- management agents.

The moisture-management agent selected is a hydrophilic polyurethane, specifically RUCO-PUR SLK, and the hydrophilic HYDROPERM RPU LIQ (both discussed previously). In this example, Fabric 4 (see Table 3) is used.

The fabric sample is first treated with RUCO-PUR SLK to form a treated fabric, and then the treated fabric is re-treated with HYDROPERM RPU LIQ. Thus, this is a two step treatment method. The RUCO-PUR SLK composition is prepared as in Inventive Example 1 above. The HYDROPERM RPU LIQ composition is prepared by adding a predetermined amount of compound (see Table 1 1 for the amount) into a chosen amount of water. Mild agitation is applied during the addition.

The fabric sample is placed in the RUCO-PUR SLK composition for 3-5 seconds, then padded with a lab padding machine, as described above. The WPU is adjusted to 100% of the weight of the dry fabric. The sample is quickly placed on a lab stenter frame oven, as described above. The drying/curing temperature is 13O⁰C and the drying/curing time is 4 minutes (this concludes the first step). After the first step, the HYDROPERM RPU LIQ composition is applied. Table 11 shows the results of the water absorbency according to AATCC TM 79. As can be seen from this Table, there is an improvement in water absorbency time for treated samples compared to untreated fabrics (shown in Table 3), and the performance appears to be durable.

Table 11. Water Absorbency Results

Example 6 This example demonstrates durable moisture-management treatment of a polyolefm fabric. The method illustrated here is a one-step method.

The moisture-management agents selected for this example are RUCO-PUR SLK and HYDROPERM RPU LIQ that were discussed previously. In this example, Fabric 4 (see Table 3) is used. The fabric sample is treated with RUCO-PUR SLK and HYDROPERM RPU LIQ in a one-step treatment.

The RUCO-PUR SLK composition is prepared as in example 1, however, only 80% of the water listed there is used. A chosen amount (see Table 12) of HYDROPERM RPU LIQ is added to the RUCO-PUR SLK composition, and then a chosen amount of water is added. Mild agitation is applied during addition. The fabric sample is placed in the composition for 3-5 seconds, and then padded with a lab padding machine, as described above. The WPU is adjusted to 100% of the weight of the dry fabric. The sample is quickly placed on a lab stenter frame oven for drying and curing, as described above. The drying/curing temperature is 13O⁰C and the drying/curing time is 4 minutes.

Table 12 shows the results of the water absorbency according to AATCC TM 79. As can be seen from this Table, there is improvement in water absorbency time for treated samples compared to untreated fabrics, and the performance appears to be durable. Table 12. Water Absorbency Results

Example 7

This example demonstrates moisture-management treatment of a polyolefin fabπc on an industrial scale. The method illustrated here is an example of a two-step method involving two moisture-management agents. The moisture-management agent selected is a hydrophilic polyurethane, specifically

RUCO-PUR SLK, and the hydrophilic HYDROPERM RPU LIQ (both discussed previously). In this example, Fabric 2 (see Table 3) is used.

The fabric sample is first treated with RUCO-PUR SLK to form a treated fabric, and then the treated fabric is re-treated with HYDROPERM RPU LIQ. Thus, this is a two step treatment method. The RUCO-PUR SLK is prepared as follows. First, a predetermined amount of water is added into a empty water drum, and then the predetermined amount of RUCO-PUR SLK is added slowly using mild agitation until the desired concentration is achieved. The

HYDROPERM RPU LIQ composition is prepared by adding a predetermined amount of compound (see Table 1 1 for the amount) into a chosen amount of water. Mild agitation is applied during the addition.

The fabric sample is passed through RUCO-PUR SLK composition for 3-5 seconds, then padded with a industrial padding machine from BRUCKNER Textile Technologies GmbH & Co. KG. The WPU is adjusted to 100% of the weight of the dry fabric. The sample is passed through an industrial stenter frame also from BRUCKNER Textile Technologies GmbH & Co. KG. The drying/curing temperature is 13O⁰C and the drying/curing time is 2.15 minutes (this concludes the first step). After the first step, the HYDROPERM RPU LIQ composition is applied. Example 8

Table 13 shows the results of the water absorbency tests according to AATCC TM 79. As can be seen from this Table, there appears to be an improvement in water absorbency time for treated samples compared to untreated samples (shown in Table 3), and the performance appears to be durable. The condition of washing and drying the samples is as follows:

^■ temperature of 40⁰C ±3⁰C;

^■ sample size of 50 cm X 50 cm;

^■ 0.15% AATCC/ISO Standard Reference Detergent, powdered, without an optical brightener;

^■ time is 55 minutes;

^■ washing machine SIEMENS IQ 1400 program synthetic wash; and

^■ SIEMENS washing machine IQ 1400 program synthetic dry.

Table 13. Water Absorbency Results

Example 9

Example (wet-on-wet treatment). This example demonstrates durable moisture- management treatment of a polyolefin fabric. The method illustrated here is wet-on-wet treatment method. In this example, a navy colored single jersey polyolefin fabric is used. Other fabric details are given below in Table 14.

Table 14. Untreated Fabric Information

Wet-on-wet treatment method is performed as follows. Fabric is weighed and then soaked in water for about 30 minutes. Full saturation of fabric with water is accomplished. The soaking step is followed by a centrifuging step. Centrifuging is done in a washing machine, e.g., SIEMENS washing machine IQ 1400 program for synthetic fabrics. After centrifuge, the fabric is placed in a plastic sealable bag and sealed to stop moisture evaporation. Moisture content in the wet fabric after centrifuge is approximately 43%.

The moisture-management agent selected for this example is RUCO-PUR SLK. The RUCO-PUR SLK solution is prepared as follows. First, a predetermined amount of water is added into an empty container, and then predetermined amount of RUCO-PUR SLK is added slowly using mild agitation until the desired concentration is achieved. The concentration of RUCO-PUR SLK in the solution is 25%.

The treatment is as follows. The wet fabric sample is taken out of the sealable plastic bag and placed in the solution for 3-5 seconds, and then padded with a lab padding machine. RUCO PUR SLK solution wet pick up is 31.4% of the weight of the dry fabric weight. Note that total WPU in the fabric is 74.4% (includes moisture content after centrifuge and functional solution pick up) by the weight of dry fabric weight. The sample is quickly placed on a lab stenter frame oven for drying and curing. The drying/curing temperature is 130⁰C and the drying/curing time is about 2 minutes.

The treated sample is tested for moisture management durability by standard home laundry cycles. The condition of home laundry washing and drying is as follows:

^■ temperature of 40⁰C ±3⁰C;

^■ sample size of about 20 cm X 20 cm

^■ 0.15% AATCC/ISO Standard Reference Detergent, powdered, without an optical brightener;

^■ time is 55 minutes;

^■ SIEMENS washing machine IQ 1400 program synthetic wash; and

^■ SIEMENS washing machine IQ 1400 program synthetic tumble dry.

Below Table shows the results of the water absorbency according to AATCC TM 79. As can be seen from this Table 15, there appears to be an improvement in water absorbency time for treated samples compared to untreated fabrics (untreated fabric showed water absorbency time of >600 seconds), and the performance appears to be durable.

Table 15. Absorbency Tests

Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. In particular, every range of values (of the form, "from about a to about b," or, equivalently, "from approximately a to b," or, equivalently, "from approximately a-b") disclosed herein is to be understood as referring to the power set (the set of all subsets) of the respective range of values, and set forth every range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.

Claims

What is claimed is:

1. A method of functionalizing a polyolefin substrate comprising: providing a polyolefin substrate; applying a durable moisture-management composition that comprises a hydrophilic networking agent to the polyolefin substrate with a minimum of about 60% total WPU; and allowing at least a portion of the durable moisture-management composition to form a substantially continuous network on the surface of the polyolefin substrate so as to form a functionalized polyolefin substrate having moisture management characteristics.

2. The method of claim 1 further comprising applying an odor-control agent to the polyolefin substrate before, during, or after the step of applying the durable moisture- management composition to the polyolefin substrate.

3. The method of claim 4 wherein the odor-control agent comprises at least one odor-control agent selected from the group consisting of: silver zirconium phosphate; triclosan; nano silver; quaternary amine compounds; crosslinkable silyl quats; polyhexamethylene biguanide; chitosan; and combinations thereof.

4. The method of claim 1 wherein the polyolefin comprises a polyolefin selected from the group consisting of: Ziegler-Natta catalyzed polypropylene homopolymers; polyethylene homopolymers; linear low density polyethylene; high density polyethylene; polyethylene copolymers; polypropylene copolymers; metallocene catalyzed polypropylene homopolymers; ethylene-propylene copolymers; rubber-modified polypropylene polymers; poly 4-methyl, 1-pentene; a polyolefin having a melting point of 140°C or more; cyclic-olefin- copolymers; syndiotactic polystyrene; propylene copolymerized with an olefin monomer; and blends of these polyolefins.

5. The method of claim 1 wherein the polyolefin comprises at least one fiber selected from the group consisting of: a synthetic fiber; an organic fiber; polyethylene terephthalate ("PET"); polybutylene terephthalate ("PBT"); polytrimethyl terephthalate ("PTT"); a polyester copolymer; Nylon 6; Nylon 6,6; acrylic; cotton; wool; rayon; viscose; bamboo; a polycarbonate; a polylactide; a polyglycolide; an elastic fiber; a rubber filament; an elastoester; a lastol; a polyurethane-based fiber; a bicomponent fiber; and a crosslinked polyethylene fiber.

6. The method of claim 1 wherein the durable moisture-management composition further comprises at least one selected from the group consisting of: a solvent; a catalyst; a wetting agent; and an optical brightener.

7. The method of claim 1 wherein the hydrophilic networking agent is derivatized from or comprises a compound selected from the group consisting of: a polyethylene oxide; a polyether-based polymer; a polycarboxylic acid; a polyurethane; a polyvinylalcohol; a polysaccharide; cellulose; a natural or synthetic hydroxyl, carbonyl, amino, or thiol group containing polymer; an ethoxylated polyester; a sulfonated polyester; an ethoxylated polyamide; an ethoxylated polyethylene; a fatty acid alkanolamide; a polysilicic acid; a polyorganosiloxane; a copolymer thereof; and a mixture thereof.

8. The method of claim 1 wherein the step of applying a durable moisture- management composition that comprises a hydrophilic networking agent to the polyolefin substrate with a minimum of a 60% WPU is performed using a padding application, a spray application, a printing process, an exhaust process, or a combination of these.

9. The method of claim 1 further comprising a method selected from the group consisting of: scouring; heat setting; drying; printing; dyeing; and combinations thereof.

10. A functionalized polyolefin substrate having a substantially continuous network on a surface of the polyolefin substrate formed by a functionalization composition that comprises a networking agent.

11. The functionalized polyolefin substrate of claim 10 further comprising an odor- control agent.

12. The functionalized polyolefin substrate of claim 10 wherein the polyolefin substrate comprises a polyolefin selected from the group consisting of: Ziegler-Natta catalyzed polypropylene homopolymers; polyethylene homopolymers; linear low density polyethylene; high density polyethylene; polyethylene copolymers; polypropylene copolymers; metallocene catalyzed polypropylene homopolymers; ethylene-propylene copolymers; rubber-modified polypropylene polymers; poly 4-methyl, 1-pentene; a polyolefin having a melting point of 140⁰C or more; cyclic-olefin-copolymers; syndiotactic polystyrene; propylene copolymerized with an olefin monomer; and blends of these polyolefins.

13. The functionalized polyolefin substrate of claim 10 wherein the polyolefin substrate comprises at least one fiber selected from the group consisting of: a synthetic fiber; an organic fiber; polyethylene terephthalate ("PET"); polybutylene terephthalate ("PBT"); polytrimethyl terephthalate ("PTT"); a polyester copolymer; Nylon 6; Nylon 6,6; acrylic; cotton; wool; rayon; viscose; bamboo;; a polycarbonate; a polylactide; a polyglycolide; an elastic fiber; a rubber filament; an elastoester; a lastol; a polyurethane-based fiber; a bicomponent fiber; and a crosslinked polyethylene fiber.

14. The functionalized polyolefin substrate of claim 10 wherein the hydrophilic networking agent is derivatized from or comprises a compound selected from the group consisting of: a polyethylene oxide; a polyether-based polymer; a polycarboxylic acid; a polyurethane; a polyvinylalcohol; a polysaccharide; cellulose; a natural or synthetic hydroxyl, carbonyl, amino, or thiol group containing polymer; an ethoxylated polyester; a sulfonated polyester; an ethoxylated polyamide; an ethoxylated polyethylene; a fatty acid alkanolamide; a polysilicic acid; a polyorganosiloxane; a copolymer thereof; and a mixture thereof.

15. The functionalized polyolefin substrate of claim 11 wherein the odor-control agent comprises at least one odor-control agent selected from the group consisting of: silver zirconium phosphate; triclosan; nano silver; quaternary amine compounds; crosslinkable silyl quats; polyhexamethylene biguanide; chitosan; and combinations thereof.

16. A functionalization composition for treating polyolefin substrates comprising a hydrophilic networking agent and/or an odor-control agent.

17. The functionalization composition of claim 16 wherein the hydrophilic networking agent is derivatized from or comprises a compound selected from the group consisting of: a polyethylene oxide; a polyether-based polymer; a polycarboxylic acid; a polyurethane; a polyvinylalcohol; a polysaccharide; cellulose; a natural or synthetic hydroxyl, carbonyl, amino, or thiol group containing polymer; an ethoxylated polyester; a sulfonated polyester; an ethoxylated polyamide; an ethoxylated polyethylene; a fatty acid alkanolamide; a polysilicic acid; a polyorganosiloxane; a copolymer thereof; and a mixture thereof.

18. The functionalization composition of claim 17 wherein the odor-control agent comprises at least one odor-control agent selected from the group consisting of: silver zirconium phosphate; triclosan; nano silver; quaternary amine compounds; crosslinkable silyl quats; polyhexamethylene biguanide; chitosan; and combinations thereof.