Patent Publication Number: US-2021172114-A1

Title: Methods for use of aqueous polyurethane dispersions and articles made thereby

Description:
FIELD OF THE INVENTION 
     The present invention relates to methods for use of aqueous polyurethane dispersions in improving localized shaping and/or support functionalities, shape retention, stay and/or comfort of apparel and other fabric articles. 
     BACKGROUND OF THE INVENTION 
     A shaping garment is designed to temporarily alter the wearer&#39;s body shape to achieve a more fashionable figure. In recent years, fashion trends have tended to embrace clothing and apparel designs that increasingly accentuate natural curves of the human body, and the shape wear has been a growing trend in the market. The primary application has been in women&#39;s apparel, such as inner wear, lingerie, jeans and woven pants. Many women consumers look for a comfortable garment that enhances her shape while highlighting her best features, for example, a shaping jean that can slim the tummy, tighten the thigh and lift the buttock. Such a garment improves the appearance and self-esteem of the wearer. 
     Current techniques for shaping primarily use different yarn loop structures with long float stitch, higher denier or high draft of elastic fiber; or to apply a special silhouette pattern in strategically selected areas. Other common practice includes introducing second layers of fabric or pad sewn with base fabric, or selecting the fabrics with different elasticity and sewing together in different positions. See for example, U.S. Pat. Nos. 7,950,069, 7,341,500, and 7,945,970, WO2013/154445 A1, U.S. Patent Application Publication Nos. 2010/0064409A1 and 2011/0214216A1, GB2477754A and EP 0519135B1. In one design, a rigid panel is added inside of the jean in front of the belly to help slenderize the stomach. In another, a piece of padding or sponge is inserted into trousers to lift and enhance a visual buttock profile of the wearer. However, all these designs and methods compromise the wearers&#39; comfort and often are visible from the garment surface. 
     Polyurethanes (including polyurethaneureas) can be used as adhesives for various substrates, including textile fabrics. Typically, such polyurethanes are either fully formed non-reactive polymers or reactive isocyanate-terminated prepolymers. Such reactive polyurethane adhesives often require extended curing time to develop adequate bonding strength, which can be a disadvantage in manufacturing processes. In addition, the isocyanate groups of the polyurethanes are known to be sensitive to moisture, which limits the storage stability and reduces the shelf life of the product incorporating such polyurethanes. Typically, such polymers, when fully formed, are either dissolved in a solvent (solvent borne), dispersed in water (water borne), or processed as thermoplastic solid materials (hot melt). Notably, solvent-based adhesives face ever-tightening health and environmental legislation aimed at reducing volatile organic compound (VOC) and hazardous air pollutant (HAP) emissions. Accordingly, alternatives to conventional solvent-based products are needed. 
     Hot-melt adhesives, although environmentally safe and easily applied as films, generally have high set and poor recovery when subject to repeated stretch cycles. Therefore, improvements are needed. 
     Many attempts have been made to develop water borne polyurethane adhesives to overcome these deficiencies. 
     U.S. Pat. No. 5,270,433 discloses an “adhesive composition comprising a substantially clear and solvent-free, aqueous, one-component polyurethane dispersion containing the reaction products of (a) a polyol mixture comprising polypropylene glycol, (b) a mixture of polyfunctional isocyanates comprising ααα 1 α 1 -tetramethyl xylene diisocyanate (TMXDI), (c) a functional component capable of salt formation in aqueous solution, and (d) optionally, a chain-extending agent.” The adhesive films from this composition have low recovery power and poor heat resistance in view of the unsymmetrical structure and steric hindrance of isocyanate groups on TMXDI, preventing the formation of strong inter-chain urea hydrogen bonds in the hard segments of the polymer. 
     U.S. Patent Application Publication No. 2004/0014880 A1 discloses an aqueous polyurethane dispersion for adhesive bonding in wet and dry laminations stated to have superior coatability, adhesive strength and heat resistance. This dispersion contains a substantial amount of organic solvent-methyl ethyl ketone (MEK). 
     U.S. Patent Application Publication No. 2003/0220463 A1 discloses a method for making a polyurethane dispersion that is free of organic solvent such as N-methylpyrrolidone (NMP). However, the composition is limited to a prepolymer having low free diisocyanate species, such as methylene bis(4-phenylisocyanate) (4,4′-MDI). The process to produce such a prepolymer with low free diisocyanate is complicated (as disclosed in U.S. Pat. No. 5,703,193). Such processing also requires short path distillation of the free diisocyanate and is thus not economical in producing a prepolymer for making a polyurethane dispersion. 
     U.S. Pat. No. 4,387,181 discloses a stable aqueous polyurethane dispersion, containing N-methylpyrrolidone (NMP) solvent, prepared by reaction of carboxylic group-containing oxime-blocked, isocyanate-terminated prepolymer and polyamine. The prepolymer is made by reaction of aromatic diisocyanates, such as 4,4′-diphenylmethanediisocyanate (MDI) or toluene diisocyanate (TDI), with polyether or polyester polyols and a dihydroxy alkanoic acid. The oxime-blocked isocyanate groups are capable of reacting with polyamine at 60 to 80° C., within 6 to 18 hours. The dispersion is stable in storage, and the film formed from the dispersion has good tensile properties. However, this dispersion still has organic solvent present and the longer curing time needed is unsuitable for fabric bonding and lamination in practice. 
     U.S. Pat. No. 5,563,208 describes an acetone process to prepare an essentially solvent-free aqueous polyurethane dispersion, comprising urethane prepolymers with blocked isocyanate groups and polyamines within the molecular weight range of 60 to 400 in a molar ratio of blocked isocyanate groups to primary and/or secondary amino groups of from 1:0.9 to 1:1.5. This dispersion is stable in storage at room temperatures and gives a heat-resistant binder in coating. It requires long curing time (up to 30 minutes), which is still not suitable for fabric bonding and adhesion. Furthermore, the acetone process requires an additional distillation step to remove the acetone from the dispersion, which makes this process less economical. 
     U.S. Pat. No. 6,586,523 describes an acetone process for preparing a self-crosslinking polyurethane dispersion for sizing agents, comprising a prepolymer with isocyanate groups partially blocked and partially extended, and excess polyfunctional compounds having molecular weights from 32 to 500 with primary or secondary amino and/or hydroxyl groups. This dispersion composition reduces the curing time to some degree, but still has deficiencies because an additional distillation step to remove the acetone is required. 
     U.S. Pat. No. 6,555,613 describes a solvent-free aqueous dispersion of a reactive polyurethane having a number average molecular weight (Mn) of from 800 to 14,000, a degree of branching of from 0.0 to 3.0 mol/kg, and an isocyanate functionality from 2.0 to 6.0 per mole. The polyurethane is made from a polyester polyol, a polyisocyanate and polyisocyanate adduct, with low molecular weight polyol and anion-forming units after neutralizing incorporated in the polymer chains, and with blocked isocyanate groups capable of further reactions for crosslinking. The result of such dispersion is a coating material that is hard, glossy and elastic, but such coating material does not have the elastomeric features and stretch/recovery properties required for an adhesive to be used with stretch fabrics. 
     Polymer compositions such as polyurethaneurea films and tapes comprising fully formed polyurethaneurea with blocked isocyanate end groups are disclosed in U.S. Pat. No. 7,240,371. These compositions are prepared from solvent-free systems of prepolymers comprising at least one polyether or polyester polyoyl, a mixture of MDI isomers and a diol. 
     U.S. Pat. No. 9,346,932 discloses aqueous polyurethane dispersions provided in solvent-free systems of a prepolymer comprising at least one polyether, polyester, or polycarbonate polyol, a mixture of MDI isomers, and a diol and shaped three dimensional articles formed therefrom. 
     Carmen, C. et al. disclose a method to add polymer composition on the edge of garments to form the garment edge bands and to add film on garments such as brassiere to form laminate fabrics in patent EP 2280619B1 and published U.S. Patent Application Publication No. 2009/0181599A1 discloses fabric laminates or fabric bands having multiple layered structures, including at least one fabric layer and at least one polymer layer that have been attached or bonded together. 
     Other examples of polymer compositions are polyurethane tapes such as those commercially available from Bemis, and polyolefin resins that can be formed into films such as those commercially available from ExxonMobil under the trade name VISTAMAXX. These films may be bonded to fabric with application of heat. 
     SUMMARY OF THE INVENTION 
     The inventors herein have found that application of an aqueous polyurethane dispersion comprising a prepolymer comprising a glycol, an isocyanate and a diol compound, and optionally 1-hexonal and further comprising water, a neutralizer, a surfactant, a defoamer, an antioxidant and/or a thickener can be applied at a selected intensity and/or at a selected location or selected locations of a fabric article to improving localized shaping and/or support functionalities, shape retention, stay and/or comfort of the fabric article. 
     Accordingly, an aspect of the present invention relates to a method for improving localized shaping and/or support functionalities of apparel and other fabric articles. The method comprises applying the aqueous polyurethane dispersion at a selected intensity and/or one or more selected locations of apparel or other fabric articles. The method further comprises curing of the aqueous polyurethane dispersion to the apparel or other fabric articles following application of the aqueous polyurethane dispersion at the selected intensity and/or selected one or more locations so that shaping and/or support is improved. 
     Another aspect of the present invention relates to a method for improving stay of apparel and other fabric articles. The method comprises applying the aqueous polyurethane dispersion at a selected intensity and/or at one or more selected locations of apparel or other fabric articles wherein stay of the apparel or other fabric articles is desired. The method further comprises curing of the apparel or other fabric articles following application of the aqueous polyurethane dispersion at the selected intensity and/or one or more locations so that stay of the apparel or other fabric articles is improved. 
     Another aspect of the present invention relates to a method for improving comfort of apparel and other fabric articles. The method comprises applying the aqueous polyurethane dispersion at a selected intensity and/or at one or more selected locations of apparel or other fabric articles wherein improved comfort of the apparel or other fabric articles is desired. The method further comprises curing of the apparel or other fabric articles following application of the aqueous polyurethane dispersion at the selected intensity and/or one or more locations so that comfort of the apparel or other fabric articles is improved. 
     Another aspect of the present invention relates to a method for improving shape retention of apparel and other fabric articles. The method comprises applying the aqueous polyurethane dispersion at a selected intensity and/or at one or more selected locations of apparel or other fabric articles wherein improved shape retention of the apparel or other fabric articles is desired. The method further comprises curing of the apparel or other fabric articles following application of the aqueous polyurethane dispersion at the selected intensity and/or one or more locations so that shape retention of the apparel or other fabric articles is improved. 
     Yet another aspect of the present invention relates to apparel and other fabric articles with an aqueous polyurethane dispersion applied and cured at a selected intensity and/or one or more selected locations which exhibit improved localized shaping and/or support functionalities, shape retention, stay and/or comfort. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Provided by this disclosure are methods for improving localized shaping and/or support functionalities, shape retention, stay and/or comfort of apparel and other fabric articles via application of an aqueous polyurethane dispersion at selected intensities and/or at one or more selected locations on the apparel or other fabric article. 
     By “improved”, “improving”, or “improvement”, as used herein, it is meant any enhancement detectable visually, physically or by quantification of localized shaping and/or support functionalities, shape retention, stay and/or comfort of apparel and other fabric articles with the applied aqueous polyurethane dispersion as compared to apparel and other fabric articles without the aqueous polyurethane dispersion. 
     By “intensity” as used herein, it meant that to include both application weight and design of the application pattern of the aqueous polymeric dispersion. 
     Aqueous polyurethane dispersions falling within the disclosure are provided from particular urethane prepolymers, which also are disclosed herein. The aqueous polyurethane dispersions and prepolymers do not contain an organic solvent or cosolvent, alkyl ethoxylates or organotin catalyst. 
     As used herein, the term “dispersion” refers to a system in which the disperse phase consists of finely divided particles, and the continuous phase can be a liquid, solid or gas. 
     As used herein, the term “aqueous polyurethane dispersion” refers to a composition containing at least a polyurethane or polyurethane urea polymer or prepolymer (such as the polyurethane prepolymer described herein) that has been dispersed in an aqueous medium, such as water, including de-ionized water. 
     A dried aqueous polyurethane dispersion, as used herein, is an aqueous polyurethane dispersion that has been subjected to curing or drying by any suitable method. The dried aqueous polyurethane dispersion may be in the form of a shaped article, e.g., a film. 
     As used herein, the term “solvent,” unless otherwise indicated, refers to a non-aqueous medium, wherein the non-aqueous medium includes organic solvents, including volatile organic solvents (such as acetone) and somewhat less volatile organic solvents (such as MEK, or NMP). 
     As used herein, the term “essentially solvent-free” or “essentially solvent-free system” refers to a composition or dispersion wherein the bulk of the composition or dispersed components has not been dissolved or dispersed in a solvent. 
     Prepolymers for use in the aqueous polyurethane dispersions used in the present invention comprise a glycol, an aliphatic diisocyanate and a diol. 
     Glycol components suitable as a starting material for preparing prepolymers used in the present invention include polycarbonates, and polyesters, polycarbonate glycols, polyether glycols, and polyester glycols. 
     Examples of polyether glycols that can be used include, but are not limited to, those glycols with two or more hydroxy groups, from ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran, or from condensation polymerization of a polyhydric alcohol, preferably a diol or diol mixtures, with less than 12 carbon atoms in each molecule, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polyether polyol is preferred, and a poly(tetramethylene ether) glycol of molecular weight of about 1,700 to about 2,100, such as Terathane® 1800 (Invista) with a functionality of 2, is particularly preferred for use in the prepolymers used in the present invention. 
     Examples of polyester glycols that can be used include those ester glycols with two or more hydroxy groups, produced by condensation polymerization of aliphatic polycarboxylic acids and polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Example of suitable polyols for preparing the polyester polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polyester polyol with a melting temperature of about 5° C. to about 50° C. is preferred. 
     Examples of polycarbonate glycols that can be used include those carbonate glycols with two or more hydroxy groups, produced by condensation polymerization of phosgene, chloroformic acid ester, dialkyl carbonate or diallyl carbonate and aliphatic polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule. Examples of suitable polyols for preparing the polycarbonate polyols are diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polycarbonate polyol with a melting temperature of about 5° C. to about 50° C. is preferred. 
     In one nonlimiting embodiment, the prepolymer contains at least 65%, or at least 71%, or at least 72% of the glycol, based upon total weight of the prepolymer. 
     The isocyanate component suitable as another starting materials for making prepolymers useful in the present invention is a dicyclohexylmethane diisocyanate such as Vestanate® H12MD1 (Evonik). 
     In one nonlimiting embodiment, the prepolymer contains at least 10%, or at least 22%, or at least 24% of the isocyanate, based upon total weight of the prepolymer. 
     Diols suitable as further starting materials for preparing prepolymers disclosed herein, include at least one diol with two hydroxy groups capable of reacting with the isocyanate and at least one carboxylic acid group capable of forming salt upon neutralization and incapable of reacting with the isocyanate. Examples of diols having a carboxylic acid group include, but are not limited to, 2,2-dimethylopropionic acid (DMPA) such as Bis-MPA (GEO), 2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and DMPA initiated caprolactones such as CAPA™ HC 1060 (Solvay). DMPA is preferred. 
     In one nonlimiting embodiment, the prepolymer may contain at least 1%, or at least 2.2%, or at least 2.4% of the diol, based upon total weight of the prepolymer. 
     In one nonlimiting embodiment, the prepolymer further comprises a monofunctional alcohol including methanols, ethanols, propanols, butanols and 1-hexanol. In this nonlimiting embodiment, the prepolymer contains less than 1% or less than 0.5% of the 1-hexaonol, based upon total weight of the prepolymer. 
     The prepolymer can be prepared by mixing the glycol, isocyanate and diol together in one step and by reacting at temperatures of about 50° C. to about 100° C. for adequate time until all hydroxy groups are essentially consumed and a desired % NCO of the isocyanate group is achieved. Alternatively, this prepolymer can be made by charging molten glycol into a reactor at about 55° C. followed by addition of a DMPA solid powder with agitation and circulation until the diol solid particles are dispersed and dissolved in the glycol. Molten isocyanate is then charged into the reactor with continuous agitation and the capping reaction is allowed to take place at about 90° C. for about 240 minutes, still with continuous agitation. The formed viscous prepolymer is then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.97 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it is determined that the reaction is complete, the prepolymer temperature is maintained between 85° C. and 90° C. Significantly, the prepolymers are essentially solvent free and contain no alkyl ethoxylates or organotin catalysts. Preferred is that the reaction to prepare the prepolymer be carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions. 
     The prepolymer of the present invention is then used to produce an aqueous polyurethane dispersion comprising the prepolymer and water as well as a neutralizer, a surfactant, a defoamer, an antioxidant and/or a thickener. 
     In one nonlimiting embodiment, the prepolymer is added in an amount such that the final aqueous polyurethane dispersion contains at least 30% glycol, at least 10% isocyanate, and at least about 1% dial, based upon total weight of the aqueous polyurethane dispersion. 
     In one nonlimiting embodiment, the aqueous polyurethane dispersion further contains at least 50% water, at least 1% surfactant and/or thickener and/or less than 1% neutralizer, antioxidant, or defoamer. 
     Neutralizers used in these dispersions must be capable of converting the acid groups to salt groups. Examples include, but are not limited to, tertiary amines (such as triethylamine, N,N-diethylmethylamine, N-methylmorpholine, N,N-diisopropylethylamine, and triethanolamine) and alkali metal hydroxides (such as lithium, sodium and potassium hydroxides). Primary and/or secondary amines may be also used as the neutralizers for the acid groups. The degrees of neutralization are generally between about 60% to about 140%, for example, in the range of about 80% to about 120% of the acid groups. 
     Examples of surfactants include, but are not limited to, anionic, cationic, or nonionic dispersants or surfactants, such as alkyldiphenyloxide disulfonate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, ethoxylated nonyphenols, and lauryl pyridinium bromide. 
     Examples of suitable defoamers include, but are not limited to, mineral oils and/or silicone oils such as BYK 012 and Additive 65 (a silicone additive from Dow Corning), and Surfynol™ DF 110L (a high molecular weight acetylenic glycol non-ionic surfactant from Air Products &amp; Chemicals). 
     Examples of suitable thickeners include, but are not limited to, polyurethanes such as Tafigel PUR 61 by Munzing, hydrophobically-modified ethoxylate urethanes (HEUR), hydrophobically-modified alkali swellable emulsions (RASE), and hydrophobically-modified hydroxy-ethyl cellulose (HMHEC). 
     Examples of antioxidants include, but are not limited to, hindered phenols such as Irganox 245 (BASF) or Cyanox 1790 (Cytec). Additionally, diamines including ethylene diamine and similar materials can be used as a diamine chain extender in place of water. 
     In one nonlimiting embodiment, the dispersion is prepared by the addition of the prepolymer using a rotor/stator high speed disperser. The prepolymer as made above is transferred directly into the disperser head and dispersed under high shear forces into deionized water preferably containing at least a surfactant, a neutralizer, an anti-oxidant and/or a foam control agent. Slightly more prepolymer than required by the dispersion recipe is needed to compensate for loss in the transfer line and in the reactor. Once the addition of the prepolymer is complete, a thickener can be added. 
     Aqueous polyurethane dispersions for use in the present invention should be expected to have a solids content of from about 10% to about 50% by weight, for example from about 30% to about 45% by weight. The viscosity of aqueous polyurethane dispersions for use in the present invention may be varied in a broad range from about 10 centipoises to about 100,000 centipoises depending on the processing and application requirements. For example, in one nonlimiting embodiment, the viscosity is in the range of about 500 centipoises to about 30,000 centipoises. The viscosity may be varied by using an appropriate amount of thickening agent, such as from about 0 to about 5.0 wt %, based on the total weight of the aqueous polyurethane dispersion. 
     The aqueous polyurethane dispersion can be applied to selected locations of apparel or other fabric articles and/or at selected intensities by methods such as, but not limited to, padding, coating, printing, bonding, laminating, spraying and other application/treatment methods, and then cured (or dried) with a residence time of about 1 to about 5 minutes. 
     The aqueous polyurethane dispersion may be diluted to a desired solid content prior to application to the apparel or other fabric article. 
     These aqueous polyurethane dispersions when applied at selective intensities and/or selected locations of apparel and other fabric articles have now been found to be useful improving localized shaping and/or support functionalities, shape retention, stay and/or comfort of the apparel and other fabric articles. 
     Examples of apparel that can be improved using the dispersions and methods in accordance with the present invention, include but are not limited to: disposable undergarments, brassieres, panties, lingerie, swimwear, shapers, camisoles, hosiery, leggings, sleepwear, aprons, wetsuits, ties, scrubs, space suits, uniforms, hats, garters, sweatbands, belts, activewear, outerwear, rainwear, cold-weather jackets, pants, shillings, dresses, blouses, men&#39;s and women&#39;s tops, sweaters, corsets, vests, knickers, socks, knee highs, dresses, blouses, tuxedos, bisht, abaya, hijab, jilbab, thoub, Burka, cape, costumes, diving suit, kilt, kimono, jerseys, gowns, protective clothing, sari, sarong, skirts, spats, stola, suits, straitjacket, toga, tights, towel, uniform, veils, wetsuit, medical compression garments, bandages, suit interlinings, waistbands, and all components therein. 
     Examples of other fabric articles that can be improved using the dispersions and methods in accordance with the present invention include, but are not limited to, seating and seats, cushions, pads, footwear, footwear inserts, bedding, packaging protecting materials and automobile interiors. 
     In one nonlimiting embodiment, the inventors herein have now found that selective location of an aqueous polymeric dispersion on, for example, a garment improves fit and shaping in unexpected ways. More specifically, it has been found that applying the aqueous polymeric dispersion in one location on a garment can influence, trigger and/or guide the fit and shaping in other locations of the garment. Further such garments are more comfortable. Use of the aqueous polymeric dispersion in this manner provides for symmetric correction of dissimilar breast size/shape by selective application of the dispersion to locations of a bra or other supportive undergarment. In particular, printing of the dispersion on lower cup of a bra resulting in less visually discernible and less measurable, as determined by a 3-dimensional body scanner, difference between the two breasts/cups is a model with dissimilar size/shape of breasts. Further, for a bralette for a keyhole top or sheath dress such as available from Tommy Hilfiger, printing of the dispersion on the bra cup resulted in smoothing the keyhole and elimination of flipping of the keyhole on the back, a common issue with this design. In addition, printing of the dispersion on a bra at the bottom and side of the breast area provides push-in and push-up shaping on the breast. Printing of the dispersion on the tummy section of a legging resulted in the back waist adhering better. Accordingly, this use of the aqueous polymeric dispersions provides an invisible treatment which retains the elegant and simplistic design of the garment while avoiding the appearance of functional elements, provides designers and garment makers a means to create new and differentiated garments with improved functionality and enables viable mass customization of garments. 
     In another nonlimiting embodiment, the inventors herein have now found that location selective application of the aqueous polymeric dispersion, coupled with selected application weight and design of the application pattern, creates localized shaping and support functionality for garments. Further, such garments have improved comfort. Various selected patterns for application of the dispersion include, but are not limited to, dots, shapes such as triangles, circles, and rectangles, zigzags and/or lines depending upon what shaping and support functionality is desired. Such application of the aqueous polymeric dispersion as a dispersion provides for flexibility in designing graduated elastic modulus in garments and enables seamless garment technology with improved functional benefits while eliminating steps of cutting and sewing, layering, seaming and/or use of elastic bands. Accordingly, use of the aqueous polymeric dispersion in this manner gives flexibility to designers, reduces steps and saves time and saves money in production. In addition, apparel produced in accordance with this method may be thinner and lighter. Apparel produced in accordance with this method exhibits a smoother appearance, especially at any modulus interface. Further, printing of the aqueous polymeric dispersion at, for example, the thigh/calf/leg on leggings is expected to increase garment power for training and activities. 
     In another nonlimiting embodiment, the inventors herein have now found that selective application of the aqueous polymeric dispersion in strategic areas of the garment can result in garments staying in place during movement, exercise, and wear. For example, printing of the dispersion in the tummy area of, for example, leggings or yoga pants can result in support and shaping of tummy, better fit at the back waist, and improved stay-in-place of the garment during activity, all at the same time. Similarly, it has been found that selectively printing the dispersion at different places such as the band, the legging leg, the bra cup and wing, the seamless top/sport tank cup and straps results in improved stay-in place while still providing for the required stretch and/or recovery. Application at selected locations of the bra strap can eliminate the need for uncomfortable plastic strap adjusters while improving both function and comfort. This use thus provides for invisible, seamless, simplified, more flexible garment design while decreasing manufacture time. Further, selective application of the dispersion to edges, bands and hems of a garment reduces rolling of such bands, hems, and garment edges without making the garment more complex, thicker, heavier, expensive, and uncomfortable. 
     Further, the inventors herein have found that the ability of the aqueous polymeric dispersion to improve shape retention, stay, and comfort when applied at selected locations and/or intensity in accordance with the methods of the present invention has many useful applications beyond apparel. For example, application of the aqueous polymeric dispersion at selected locations and/or intensity improves comfort of seats, cushions, and pads. Unexpectedly, it was found that when modifying foam by padding the dispersion and then subjecting the foam to a static weight/pressure, increased resistance to compressive collapse, reduced rate of collapse, reduced extent of collapse, increased rate of recovery once the weight was removed, and increased extent of recovery were all observed. Such better compression resistance improves the lifetime of such cushions and pads. In addition, application of the aqueous polymeric dispersion on such fabric articles can reduce effects of vibration/shock and reduce packaging volume by creating thinner and better protective material. 
     Methods of the present invention can also be used to improve shape retention of, for example, footwear, inserts, and seating. 
     In addition, the methods of the present invention can be used to assist with items such as, but not limited to, footwear inserts, automobile fabrics, and bedding materials staying inplace. 
     As shown herein, application of the aqueous polymeric dispersion in accordance with the methods of the present invention allows for highly selective and precisely controlled amounts of enhancement in elastic modulus of apparel and other fabric articles and provides advantages to incumbent techniques such as PU dispersions, PU foam, fiberfill, spring cushions, cut/sewn fabric panels generally more broad and indiscriminate. 
     All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted. 
     Test Methods and Examples 
     The following Test Methods and Examples demonstrate the present invention and its capability for use. The invention is capable of other and different embodiments, and its several details are capable of modifications in various apparent respects, without departing from the scope and spirit of the present invention. Accordingly, the Test Methods and Examples are to be regarded as illustrative in nature and non-limiting. 
     Test Methods for Garments 
     Wear force Test: 
     Force sensors were used to capture and record the force on the body during wearing. The sensors were place between the garment and fit model and detected the force at various locations such as waist, back, shoulder, front, breast, under the bust, side of bust, ankle, knee, buttock and tummy. The garments with and without aqueous polyurethane dispersion treatment were compared. During the measurement, the model stood still or acted in repeating movements to mimic wearing motions that consumer would do in the garments. The change of force during the motion was used to analysis the comfort, support, shaping and stay. 
     3D Body Scanning: 
     A 3D body scanner was used to capture the silhouette of a live model with or without a garment. The change in silhouette showed the shaping effect of the aqueous polyurethane dispersion treated garment on several body regions. 
     Fit Model Review: 
     Professional fit model with experiences in garment fitting gave reviews of the garments after wearing. The comments include the garment fit, comfort, support, look, stay, shape retention and other expects regarding wearing experience. 
     Test Methods for Fabrics 
     Tensile Test: 
     A moving apparatus was used to fix fabrics at two ends and stretch the fabric to certain elongation. The force, modulus, and hysteresis during stretching and recovering was used to analyze the fabric elastic and recovery power which is critical to the garment shaping, supporting and comfort. 
     Wash Durability: 
     The aqueous polyurethane dispersion treated fabrics were exposed to multiple (up to 50 washes) washing and drying cycles to mimic the garment life-cycles. The washed and dried fabrics went through other tests as mentioned. The change before and after washing and drying was used to analyze the durability of the fabric shape and functions. 
     Fabric Hand Test: 
     Testing people were asked to touch and feel the fabrics blindly to examine the softness, smoothness and cooling expects of the fabric. 
     Testing Methods Used on Forms and Fiberfill Materials: 
     Compression and Recovery Test: 
     Thickness changes in material are measured during change of compression level by loading and unloading of a series of static weights. The material was laid between flat plate holders. The weight was loaded onto the top plate and maintained in place for a few minutes before adding more weight. After adding weight to the highest requirement, the weight was unloaded gradually at the same levels as loading. The thickness was measured to determine the compression resistance and percentage of recovery. 
     EXAMPLES 
     The following Examples describe nonlimiting embodiments of compositions used in the present invention. The invention is capable of other and different embodiments, and its several details are capable of modifications in various apparent respects, without departing from the scope and spirit of the present invention. Accordingly, the Examples are to be regarded as illustrative in nature and non-limiting. 
     In these examples, the following raw materials were used: 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Ingredient 
                 Chemical Name 
                 CAS # 
                 Tradename 
                 Vendor 
               
               
                   
               
             
            
               
                 Glycol 
                 PTMEG 
                 25190-06-1 
                 Terathane ® 
                 INVISTA 
               
               
                   
                   
                   
                 1800 
                   
               
               
                 Isocyanate 
                 Dicyclohexylmethane 
                 5124-30-1 
                 Vestanate 
                 Evonik 
               
               
                   
                 diisocyanate 
                   
                 H12MDI 
                   
               
               
                 DMPA 
                 Dimethylolpropionic 
                 4767-03-7 
                 D-MPA 
                 GEO 
               
               
                   
                 Acid 
                   
                   
                   
               
               
                 Neutralizer 
                 Triethylamine 
                 121-44-8 
                 TEA 
                 BASF 
               
               
                 Surfactant 
                 Alkyldiphenyloxide 
                 119345-04-9 
                 Dowfax 2A1 
                 Dow 
               
               
                   
                 Disulfonate 
                   
                   
                   
               
               
                 Defoamer 
                 mineral oil, silicone oil 
                 3173-53-3 
                 BYK 012 
                 BYK Additives &amp; 
               
               
                   
                   
                   
                   
                 Instruments 
               
               
                 Antioxidant 
                 hindered phenols 
                 36443-68-2 
                 Irganox 245 
                 BASF 
               
               
                 Thickener 
                 polyurethane 
                 Mixture 
                 Tafigel PUR 61 
                 Munzing 
               
               
                   
               
            
           
         
       
     
     Example 1: Prepolymer Preparation without 1-Hexanol 
     A polyurethane prepolymer was made using a polytetramethylene ether glycol, an aliphatic diisocyanate such as PICM (4,4′-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4′-MDI) and a diol containing a sterically hindered carboxylic acid group. More specifically, the following ingredients and unit quantities were used to make the prepolymer: 
     
       
         
           
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 Ingredient 
                 CAS Number 
                 Unit Quantity 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Terathane* 1800 
                 251090-06-1 
                 72.7806 
               
               
                 1-Hexanol 
                 111-27-3 
                 0.0000 
               
               
                 Vestanat* H12MDI 
                 5124-30-1 
                 24.7380 
               
               
                 DMPA 
                 4767-03-7 
                 2.4814 
               
               
                   
                 Prepolymer total 
                 100.0000 
               
               
                   
               
            
           
         
       
     
     The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions. 
     In this example, a 30 gallon reactor, jacketed with hot water and equipped with an agitator, was used. This reactor was heated to a temperature of about 55° C. A pre-determined weight of molten Terathane® 1800 glycol was charged into the reactor. Then, DMPA solid powder was added to the reactor with agitation and circulation, under nitrogen blanket, until the DMPA solid particles were dispersed and dissolved in glycol. 
     Molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to take place at 90° C. for 240 minutes, still with continuous agitation. The formed viscous prepolymer was then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.97 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it was determined that the reaction is complete, the prepolymer temperature was maintained between 85 and 90° C. 
     Example 2: Preparation of Aqueous Polymer Dispersion with Prepolymer of Example 1 
     The dispersion was prepared by the addition of the prepolymer of Example 1 using a rotor/stator high speed disperser. The prepolymer as made in Example 1 was transferred directly into the disperser head and dispersed under high shear forces into deionized water, containing a surfactant, a neutralizer, an anti-oxidant and a foam control agent. Slightly more prepolymer than required by the dispersion recipe was needed to compensate for loss in the transfer line and in the reactor. 
     The ingredients for making the dispersion and the composition of the dispersion are shown below in Table 3. 
     
       
         
           
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                 Ingredient 
                 CAS Number 
                 Unit Quantity 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Terathane* 1800 
                 251090-06-1 
                 30.1391 
               
               
                 Vestanat* H12MDI 
                 5124-30-1 
                 10.2442 
               
               
                 DMPA 
                 4767-03-7 
                 1.0276 
               
               
                 1-Hexanol 
                 111-27-3 
                 0.0000 
               
               
                 DI Water 
                 7732-18-5 
                 54.8093 
               
               
                 Dowfax 2A1 
                 119345-04-9 
                 1.2652 
               
               
                 Triethylamine 
                 121-44-8 
                 0.7830 
               
               
                 Irganox 245 
                 36443-68-2 
                 0.6051 
               
               
                 Tafigel PUR 61 
                 Mixture 
                 1.0000 
               
               
                 BYK 012 
                 Mixture 
                 0.1265 
               
               
                 Other 
                   
                 0.0000 
               
               
                   
                 Total 
                 100.0000 
               
               
                   
               
            
           
         
       
     
     In making a typical batch of 100 kg of the aqueous polymer dispersion, Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg) were mixed and dissolved in the deionized water (54.8093 kg). The triethylamine neutralizer (0.783 kg) was added to the above water mixture 5 minutes prior to the addition of the prepolymer. The prepolymer (41.4109 kg) maintained at a temperature between 85 and 90° C. was added into the water mixture with high speed dispersing. The addition rate (typically at about 1.5 kg/min or about 30 minutes) of the prepolymer should be controlled to allow the formation of uniform dispersion, and the temperature of the dispersion should be kept between 40 and 45° C. Once the addition of prepolymer was complete, mixing was continued for 60 minutes. Then, a thickener Tafigel PUR 61 (1.00 kg) was added and allowed to mix for another 60 minutes. The as-made dispersion was continuously agitated at low speed for 8 hours (or overnight) in the container to eliminate foams and to ensure the reaction had reached completion. The finished dispersion typically contains about 42% solids, with viscosity about 4000 centipoises and pH in the range of 7.0 to 8.5. Tenacity at break (T) is the maximum or breaking force of a filament expressed as force per unit cross-sectional area. The tenacity can be measured on an Instron model 1130 available from Instron of Canton, Mass, and is reported as grams per denier (grams per dtex). Filament tenacity at break (and elongation at break) can be measured according to ASTM D 885. 
     The dispersion was then filtered through 100 micron bag filters to remove big particles before packed for shipment. It is recommended to use 55 gallon metal drums with polyethylene liner inside to contain the dispersion for shipment. 
     Final product specifications were determined as shown in Table 4. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                 Parameters 
                 Aim 
                 ± Limits 
                 Method 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Prepolymer % NCO* 
                 3.00 
                 0.10 
                 Titration 
               
               
                 Dispersion Solids, % 
                 44.0 
                 2.0 
                 Microwave 
               
               
                 Dispersion Viscosity,  
                 4000 
                 1000 
                 RV Spindle #3/10 rpm  
               
               
                 cps** 
                   
                   
                 @ 25° C. 
               
               
                 Dispersion pH 
                 7.7 
                 0.7 
                   
               
            
           
           
               
               
            
               
                 Dispersion Filterability 
                 Passing through filter bags no  
               
               
                   
                 more than 100 microns 
               
               
                   
               
               
                 *Sampled 20-30 minutes before the prepolymer is dispersed. 
               
               
                 **Sampled and measured 24 hours after the dispersion is thickened. 
               
            
           
         
       
     
     Example 3: Preparation of Prepolymer with 1-Hexanol 
     The polyurethane prepolymer was made using a polytetramethylene ether glycol, 1-Hexanol, an aliphatic diisocyanate such as PICM (4,4′-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4′-MDI) and a diol containing a sterically hindered carboxylic acid group. Table 5 lists the ingredients and unit quantities used to make the prepolymer. 
     
       
         
           
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                 Ingredient 
                 CAS Number 
                 Unit Quantity 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Terathane* 1800 
                 251090-06-1 
                 72.4492 
               
               
                 1-Hexanol 
                 111-27-3 
                 0.4087 
               
               
                 Vestanat* H12MDI 
                 5124-30-1 
                 24.6607 
               
               
                 DMPA 
                 4767-03-7 
                 2.4814 
               
               
                   
                 Prepolymer total 
                 100.0000 
               
               
                   
               
            
           
         
       
     
     The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions. 
     In this example, a 30 gallon reactor, jacketed with hot water and equipped with an agitator, was used. This reactor was heated to a temperature of about 55° C. A pre-determined weight of molten Terathane® 1800 glycol was charged into the reactor. The 1-Hexanol was added second. Then, DMPA solid powder was added to the reactor with agitation and circulation, under nitrogen blanket, until the DMPA solid particles were dispersed and dissolved in glycol. 
     Molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to take place at 90° C. for 240 minutes, still with continuous agitation. The formed viscous prepolymer was then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.80 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it was determined that the reaction is complete, maintain the prepolymer temperature between 85 and 90° C. 
     Example 4: Preparation of Aqueous Polymer Dispersion with Prepolymer of Example 3 
     The dispersion was prepared by the addition of prepolymer of Example 3 using a rotor/stator high speed disperser. The prepolymer as made in Example 3 was transferred directly into the disperser head and dispersed under high shear forces into deionized water, containing a surfactant, a neutralizer, an anti-oxidant and a foam control agent. Slightly more prepolymer than required by the dispersion recipe is needed to compensate for loss in the transfer line and in the reactor. 
     Table 6 lists the ingredients used in making the dispersion and the composition of the dispersion. 
     
       
         
           
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                 Ingredient 
                 CAS Number 
                 Unit Quantity 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Terathane* 1800 
                 251090-06-1 
                 30.0000 
               
               
                 Vestanat* H12MDI 
                 5124-30-1 
                 10.2116 
               
               
                 DMPA 
                 4767-03-7 
                 1.0275 
               
               
                 1-Hexanol 
                 111-27-3 
                 0.1692 
               
               
                 DI Water 
                 7732-18-5 
                 54.8083 
               
               
                 Dowfax 2A1 
                 119345-04-9 
                 1.2652 
               
               
                 Triethylarnine 
                 121-44-8 
                 0.7866 
               
               
                 Irganox 245 
                 36443-68-2 
                 0.6051 
               
               
                 Tafigel PUR 61 
                 Mixture 
                 1.0000 
               
               
                 BYK 012 
                 Mixture 
                 0.1265 
               
               
                 Other 
                   
                 0.0000 
               
               
                   
                 Total 
                 100.0000 
               
               
                   
               
            
           
         
       
     
     In making a typical batch of this 100 kg dispersion Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg) were mixed and dissolved in the deionized water (54.8083 kg). The triethylamine neutralizer (0.7866 kg) was added to the above water mixture 5 minutes prior to the addition of the prepolymer. The prepolymer (41.4083 kg) maintained at a temperature between 85 and 90° C. was added into the water mixture with high speed dispersing. The addition rate (typically at about 1.5 kg/min or about 30 minutes) of the prepolymer should be controlled to allow the formation of uniform dispersion, and the temperature of the dispersion should be kept between 40 and 45° C. Once the addition of prepolymer was complete, mixing was continued for 60 minutes. Then, a thickener Tafigel PUR 61 (1.00 kg) was added and allowed to mix for another 60 minutes. The as-made dispersion was continuously agitated at low speed for 8 hours (or overnight) in the container to eliminate foams and to ensure the reaction had reached completion. The finished dispersion typically contains about 42% solids, with viscosity about 4000 centipoises and pH in the range of 7.0 to 8.5. 
     The dispersion is then filtered through 100 micron bag filters to remove big particles before packed for shipment. It is recommended to use 55 gallon metal drums with vented caps, and with a polyethylene liner inside to contain the dispersion for shipment. 
     Final product specifications were determined as shown in Table 7. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 7 
               
               
                   
               
               
                 Parameters 
                 Aim 
                 ± Limits 
                 Method 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Prepolymer % NCO* 
                 2.80 
                 0.10 
                 Titration 
               
               
                 Dispersion Solids, % 
                 44.0 
                 2.0 
                 Microwave 
               
               
                 Dispersion Viscosity,  
                 4000 
                 1000 
                 RV Spindle #3/10 rpm  
               
               
                 cps** 
                   
                   
                 @ 25° C. 
               
               
                 Dispersion pH 
                 7.7 
                 0.7 
                   
               
            
           
           
               
               
            
               
                 Dispersion Filterability 
                 Passing through filter bags no  
               
               
                   
                 more than 100 microns 
               
               
                   
               
               
                 *Sampled 20-30 minutes before the prepolymer is dispersed 
               
               
                 **Sampled and measured 24 hours after the dispersion is thickened.