KR20240110079A - Methods for use of aqueous polyurethane dispersions and articles made thereby - Google Patents

Abstract

Improving localized shaping and/or support functionality, shape memory, comfort and/or retention of clothing and other textile articles by applying a water-based polyurethane dispersion to selected strength and/or one or more selected locations of clothing or other textile articles. A method for doing so is provided. Garments and other textile articles having improved localized shaping and/or support functionality, shape memory comfort and/or retention made according to these methods are also provided.

Description

METHODS FOR USE OF AQUEOUS POLYURETHANE DISPERSIONS AND ARTICLES MADE THEREBY}

The present invention relates to methods for the use of aqueous polyurethane dispersions to improve the localized shaping and/or support functionality, shape memory, retention and/or comfort of clothing and other textile articles.

Shaping garments are designed to temporarily alter the wearer's body shape to achieve more sophisticated features. In recent years, fashion trends have tended to embrace clothing and clothing designs that increasingly emphasize the natural curves of the human body, and figure garments are a growing trend in the market. The main application has been in women's clothing such as innerwear, lingerie, jeans and woven trousers. Many female consumers are looking for comfortable clothing that enhances their figure while highlighting their best features—for example, shaping jeans that can slim the tummy, tighten the thighs, and lift the hips. Such clothing improves the wearer's appearance and self-esteem.

Current techniques for shaping mainly use long float stitches, different yarn loop structures with high denier or draft of high elastic fibers; Or, applying a special silhouette pattern to strategically selected areas. Other common practices include introducing a second layer of fabric or pad sewn into the base fabric, or selecting fabrics with different elastic properties and sewing them together in different locations. For example, US Patent No. 7,950,069, No. 7,341,500, and 7,945,970, international disclosure WO2013/154445 A1, US Patent Application 2010/0064409A1 and 2011/0214216a1 See EP 0519135B1. In one design, a rigid panel is added to the inside of the jean at the front of the stomach to help elongate the stomach. On the other hand, pieces of padding or sponge are inserted into the pants to lift and elevate the wearer's visual hip profile. However, all of these designs and methods compromise the wearer's comfort and are often visible on the garment surface.

Polyurethanes (including polyurethaneureas) can be used as adhesives on a variety of substrates, including textile fabrics. Typically, such polyurethanes are fully formed non-reactive polymers or reactive isocyanate-terminated prepolymers. Such reactive polyurethane adhesives often require extended cure times to develop adequate bond strength, which can be a weakness in the manufacturing process. Additionally, the isocyanate groups in polyurethanes are known to be sensitive to moisture, which limits storage stability and reduces the shelf life of products containing these polyurethanes. Typically, when fully formed, such polymers are dissolved in a solvent (solvosoluble), dispersed in water (waterborne), or processed into a thermoplastic solid material (hot melt). In particular, solvent-based adhesives are facing increasingly stringent health and environmental legislation aimed at reducing volatile organic compounds (VOC) and hazardous air pollutants (HAP) emissions. Therefore, alternatives to conventional solvent-based products are needed.

Hot-melt adhesives, although environmentally safe and easily applied as films, generally have high cure and poor recovery when subjected to repeated stretching cycles. Therefore, improvement is needed.

Many attempts have been made to develop waterborne polyurethane adhesives to overcome these deficiencies.

U.S. Patent No. 5,270,433 describes “(a) a polyol mixture comprising polypropylene glycol, (b) a mixture of polyfunctional isocyanates comprising ααα ₁ α ₁ -tetramethyl xylene diisocyanate (TMXDI), (c) in aqueous solution. "an adhesive composition comprising a substantially clean, solvent-free, aqueous, one-component polyurethane dispersion containing a functional ingredient capable of salt formation, and (d) optionally, the reaction product of a chain-extending agent." do. Adhesive films from this composition have low recovery properties and poor heat resistance in view of the asymmetric structure and steric hindrance of the isocyanate groups on TMXDI, preventing the formation of strong inter-chain urea hydrogen bonds in the hard segments of the polymer.

US Patent Application Publication No. 2004/0014880 A1 discloses an aqueous polyurethane dispersion for adhesive bonding in wet and dry lamination, which is said to have excellent coating properties, adhesive strength and heat resistance. This dispersion contains significant amounts of the organic solvent - methyl ethyl ketone (MEK).

US Patent Application Publication 2003/0220463 A1 discloses a process for preparing polyurethane dispersions without organic solvents such as N-methylpyrrolidone (NMP). However, this composition is limited to prepolymers with low free diisocyanate species, such as methylene bis(4-phenylisocyanate) (4,4'-MDI). The process for producing such prepolymers with low free diisocyanate (as disclosed in U.S. Pat. No. 5,703,193) is complex. Such processing also requires short path distillation of the free diisocyanate and is therefore not economical for producing prepolymers for making polyurethane dispersions.

U.S. Patent No. 4,387,181 discloses a stable aqueous polyurethane dispersion containing N-methylpyrrolidone (NMP) solvent prepared by reaction of a carboxyl group-containing oxime-blocked, isocyanate-terminated prepolymer and a polyamine. Begin. Prepolymers are prepared by reaction of polyether or polyester polyols and dihydroxy alkanoic acids with aromatic diisocyanates, such as 4,4'-diphenylmethanediisocyanate (MDI) or toluene diisocyanate (TDI). Oxime-blocked isocyanate groups can react with polyamines at 60 to 80° C. within 6 to 18 hours. The dispersion is stable on storage, and the film formed from the dispersion has excellent tensile properties. However, this dispersion still contains organic solvents and the longer curing times required make it unsuitable for fabric bonding and laminating in practice.

US Pat. No. 5,563,208 discloses urethane prepolymers with blocked isocyanate groups and polyamines in the molecular weight range of 60 to 400 at a molar ratio of blocked isocyanate groups to primary and/or secondary amino groups of 1:0.9 to 1:1.5. , describes an acetone process for preparing essentially solvent-free aqueous polyurethane dispersions. This dispersion is storage stable at room temperature and provides a heat-resistant binder in the coating. This requires a long curing time (up to 30 minutes), which is still not suitable for fabric bonding and bonding. Additionally, the present acetone process requires an additional distillation step to remove acetone from the dispersion, which makes the process less economical.

US Patent No. 6,586,523 is for sizing formulations comprising prepolymers with partially blocked and partially extended isocyanate groups and hypermultifunctional compounds with molecular weights from 32 to 500 with primary or secondary amino and/or hydroxyl groups. An acetone process for preparing self-crosslinking polyurethane dispersions is described. Although this dispersion composition reduces the cure time to some extent, it is still defective because it requires an additional distillation step to remove the acetone.

U.S. Patent No. 6,555,613 describes solvent-free aqueous dispersions of reactive polyurethanes having a number average molecular weight (Mn) of 800 to 14,000, a degree of branching of 0.0 to 3.0 mol/kg, and isocyanate functionality of 2.0 to 6.0 per mole. . The present polyurethanes are derived from polyester polyols, polyisocyanates and polyisocyanate adducts, having low molecular weight polyols and anion-forming units incorporated into the polymer chain after neutralization and having blocked isocyanate groups capable of further reaction for crosslinking. It is manufactured. The result of such a dispersion is a hard, shiny and elastic coating material, but such coating material does not have the elastomeric properties and stretch/recovery properties required for adhesives used with stretch fabrics.

Polymeric 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 diols.

U.S. Patent No. 9,346,932 discloses aqueous polyurethane dispersions provided in a solvent-free system of prepolymers comprising at least one polyether, polyester, or polycarbonate polyol, a mixture of MDI isomers, and a diol, and shaped 3s formed therefrom. Initiate dimensional goods.

Carmen, C. et al. disclose a method of adding a polymer composition on the edge of a garment to form a garment edge band and a film on a garment such as a bra to form a laminated fabric, and are described in European Patent EP 2280619B1 and published US Patent Application Publication No. 2009/0181599A1 discloses a fabric laminate or fabric band having a multi-layered structure comprising at least one fabric layer and at least one polymer layer 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 can be bonded to fabrics by application of heat.

Herein the inventors describe an aqueous polyurethane dispersion comprising a prepolymer comprising glycol, isocyanate and diol compounds, and optionally 1-hexonal, and further comprising water, neutralizing agents, surfactants, anti-foaming agents, antioxidants and/or thickening agents. It has been discovered that the application of water can be applied at a selected intensity and/or to a selected location or selected locations of the textile article to improve localized shaping and/or support functionality, shape memory, retention and/or comfort of the textile article.

Accordingly, aspects of the present invention relate to methods for improving localized shaping and/or support functionality of clothing and other textile articles. The method includes applying the aqueous polyurethane dispersion at a selected strength and/or at one or more selected locations on a garment or other textile article. The method further comprises curing the water-based polyurethane dispersion to the garment or other textile article following application of the water-based polyurethane dispersion at one or more locations selected and/or at a selected strength to improve shaping and/or support. do.

Another aspect of the invention relates to a method for improving the retention of clothing and other textile articles. The method includes applying the aqueous polyurethane dispersion at a selected strength and/or at one or more selected locations on clothing or other textile articles where retention of the clothing or other textile article is desired. The method further comprises curing the clothing or other textile article following application of the water-based polyurethane dispersion at one or more locations and/or strengths selected to improve retention of the clothing and other textile article.

Another aspect of the invention relates to a method for improving the comfort of clothing and other textile articles. The method includes applying the aqueous polyurethane dispersion at selected strengths and/or at one or more selected locations of clothing or other textile articles where improved comfort of clothing or other textile articles is desired. The method further includes curing the clothing or other textile article following application of the water-based polyurethane dispersion at one or more locations and/or strengths selected to improve the comfort of the clothing or other textile article.

Another aspect of the invention relates to a method for improving the shape memory of clothing and other textile articles. The method includes applying the aqueous polyurethane dispersion at selected strengths and/or at one or more selected locations of clothing or other textile articles where improved shape memory of clothing or other textile articles is desired. The method further comprises curing the clothing or other textile article following application of the water-based polyurethane dispersion at one or more locations and/or at an intensity selected to improve the shape memory of the clothing and other textile article.

Yet another aspect of the present invention has an aqueous polyurethane dispersion applied and cured at selected strengths and/or one or more selected locations that exhibit improved localized shaping and/or support functionality, shape memory, retention and/or comfort. It concerns clothing and other textile articles.

Localized shaping and/or support functionality, shape memory, retention and/or comfort of clothing and other textile articles through the application of a water-based polyurethane dispersion at one or more selected locations and/or selected intensities on clothing or other textile articles. Methods for improving are provided by this disclosure.

As used herein, “improved,” “improving,” or “improvement” means clothing and other textile articles with an applied water-based polyurethane dispersion when compared to clothing and other textile articles without the water-based polyurethane dispersion. means any visually, physically or quantifiable improvement in the localized shaping and/or support functionality, shape memory, retention and/or comfort of a textile article.

As used herein, “strength” is meant to include both the application weight of the aqueous polymer dispersion and the design of the application pattern.

Aqueous polyurethane dispersions encompassed within the present disclosure are provided from certain urethane prepolymers, which are also disclosed herein. The aqueous polyurethane dispersions and prepolymers do not contain organic solvents or co-solvents, alkyl ethoxylates or organotin catalysts.

As used herein, the term “dispersion” refers to a system in which the dispersed phase consists of finely ground particles and the continuous phase may be liquid, solid, or gas.

As used herein, the term “aqueous polyurethane dispersion” refers to at least a polyurethane or polyurethane urea polymer or prepolymer (such as the polyurethane prepolymer described herein) dispersed in an aqueous medium, such as water, including deionized water. ) refers to a composition containing.

As used herein, a dried aqueous polyurethane dispersion is an aqueous polyurethane dispersion that has been cured or staged by any suitable method. The dried aqueous polyurethane dispersion may be in the form of a shaped article, such as a film.

As used herein, the term "solvent", unless otherwise indicated, means that a non-aqueous medium can be an organic solvent, including a volatile organic solvent (such as acetone) and to some extent a low volatility organic solvent (such as MEK, or NMP). refers to a non-aqueous medium containing

As used herein, the term “essentially solvent-free” or “essentially solvent-free system” refers to a composition or dispersion in which the bulk of the composition or dispersed components are not dissolved or dispersed in a solvent.

Prepolymers for use in the aqueous polyurethane dispersions used in the present invention include glycols, aliphatic diisocyanates and diols.

Glycol components suitable as starting materials for making the 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 from ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran, or polyhydric alcohols, preferably is a diol or diol mixture having 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 Condensation polymerization of glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol Includes these glycols having two or more hydroxy groups. Linear, difunctional polyether polyols are preferred for use in the prepolymers used in the present invention, such as bifunctional poly(tetramethylene ether) with a molecular weight of about 1,700 to about 2,100, such as Terathane® 1800 (Invista). Glycol is particularly preferred.

Examples of polyester glycols that can be used include low molecular weight aliphatic polycarboxylic acids and polyols having up to 12 carbon atoms in each molecule, or these esters having two or more hydroxy groups produced by condensation polymerization of mixtures thereof. Contains glycol. 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. Examples of polyols suitable for preparing polyester polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1, They are 5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. Linear, difunctional polyester polyols having a melting temperature of about 5°C to about 50°C are preferred.

Examples of polycarbonate glycols that can be used are low molecular weight phosgene, chloroformic acid esters, dialkyl carbonates or diallyl carbonates and aliphatic polyols having up to 12 carbon atoms in each molecule, or mixtures thereof, by condensation polymerization. These carbonate glycols having two or more hydroxy groups are produced. Examples of polyols suitable for preparing polycarbonate polyols include diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl- They are 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. Linear, difunctional polycarbonate polyols having a melting temperature of about 5°C to about 50°C are preferred.

In one non-limiting embodiment, the prepolymer contains at least 65%, or at least 71%, or at least 72% glycol based on the total weight of the prepolymer.

Another suitable isocyanate component for preparing prepolymers useful in the present invention is dicyclohexylmethane diisocyanate such as Vestanate® H12MDI (Evonik).

In one non-limiting embodiment, the prepolymer contains at least 10%, or at least 22%, or at least 24% isocyanate based on the total weight of the prepolymer.

Diols suitable as additional starting materials for preparing the prepolymers disclosed herein include at least one having 2 hydroxy groups capable of reacting with isocyanates and at least one carboxylic acid group capable of forming salts upon neutralization and unable to react with isocyanates. Contains one dior. Examples of diols with carboxylic acid groups 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. Disclosed caprolactones include CAPA™ HC 1060 (Solvay). DMPA is preferred.

In one non-limiting embodiment, the prepolymer may contain at least 1%, or at least 2.2%, or at least 2.4% diol based on the total weight of the prepolymer.

In one non-limiting embodiment, the prepolymer further includes monofunctional alcohols including methanol, ethanol, propanol, butanol, and 1-hexanol. In this non-limiting embodiment, the prepolymer contains less than 1% or less than 0.5% 1-hexanol based on the total weight of the prepolymer.

The prepolymer is prepared in one step by mixing the glycol, isocyanate and diol together and reacting at a temperature of about 50° C. to about 100° C. for an appropriate time until the hydroxy groups are essentially consumed and the desired % NCO of the isocyanate groups is achieved. It can be manufactured by. Alternatively, this prepolymer can be prepared by charging molten glycol into a reactor at about 55° C. until the diol solid particles are dispersed and dissolved in the glycol, followed by addition of DMPA solid powder with agitation and circulation. The molten isocyanate is then charged into the reactor with continuous agitation and the capping reaction is allowed to occur at about 90° C. for about 240 minutes while continuing with continuous agitation. The viscous prepolymer formed is then sampled and the extent of reaction is determined by determining the weight percentage of isocyanate groups (%NCO) in the prepolymer through titrimetric methods. The theoretical value of %NCO after the reaction is complete is 2.97 assuming a glycol MW of 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 the reaction is determined to be complete, the prepolymer temperature is maintained between 85°C and 90°C. Significantly, the prepolymer is essentially solvent-free and contains no alkyl ethoxylates or organotin catalysts. The reaction to prepare the prepolymer is preferably carried out in a moisture-free, nitrogen-covered 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 neutralizing agents, surfactants, anti-foaming agents, antioxidants and/or thickening agents.

In one non-limiting embodiment, the prepolymer is in an amount such that the final aqueous polyurethane dispersion contains at least 30% glycol, at least 10% isocyanate, and at least about 1% diol based on the total weight of the aqueous polyurethane dispersion. is added.

In one non-limiting embodiment, the aqueous polyurethane dispersion further contains at least 50% water, at least 1% surfactant and/or thickener, and/or less than 1% neutralizing agent, antioxidant, or anti-foaming agent.

The neutralizing agent used in these dispersions must be capable of converting acidic groups into bases. Examples include, but are not limited to, tertiary amines (such as triethylamine, N,N-diemylbuckylamine, N-buckylmorpholine, N,N-diisopropylethylamine, and triethanolamine) and alkali metal hydroxides. Sides (such as lithium, sodium and potassium hydroxide). Primary and/or secondary amines may also be used as neutralizing agents for acidic groups. The degree of neutralization generally ranges from about 60% to about 140% of the acidic groups, for example from about 80% to about 120%.

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 nonylphenol. , and lauyl pyridinium bromide.

Examples of suitable antifoaming agents include, but are not limited to, mineral oils and/or silicone oils such as BYK 012 and Additive 65 (silicone additives from Dow Corning), and Surfynol™ DF 110L (high molecular weight acetylenic glycol non-) from Air Products & Chemicals. ionic surfactants).

Examples of suitable thickeners include, but are not limited to, polyurethanes such as Tafigel PUR 61 from Munzing, hydrophobically-modified ethoxylate urethanes (HEUR), hydrophobically-modified alkali swellable emulsions (HASE), and hydrophobically-modified Contains 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 may be used as diamine chain extenders in place of water. You can.

In one non-limiting embodiment, the dispersion is prepared by addition of the prepolymer using a rotor/stator high speed disperser. The prepolymer as prepared above is transferred directly into the disperser head and dispersed under high shear forces in deionized water, preferably containing at least surfactants, neutralizers, antioxidants and/or foam regulators. Slightly more prepolymer than required for the dispersion recipe is needed to compensate for losses in the transfer line and 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 can vary widely, from about 10 centipoise to about 100,000 centipoise, depending on processing and application requirements. For example, in one non-limiting embodiment, the viscosity ranges from about 500 centipoise to about 30,000 centipoise. Viscosity can be varied by using an appropriate amount of thickener, such as from about 0 to about 5.0 wt% based on the total weight of the aqueous polyurethane dispersion.

The present aqueous polyurethane dispersions can be applied to selected locations and/or at selected strengths on clothing or other textile articles by methods such as, but not limited to, padding, coating, printing, bonding, lamination, spraying and other application/treatment methods. and then cured (or dried) with a residence time of about 1 to about 5 minutes.

The present aqueous polyurethane dispersion may be diluted to the desired solids content prior to application to clothing or other textile articles.

These water-based polyurethane dispersions are useful for selective strength of clothing and other textile articles and/or for improving the localized shaping and/or support functionality, shape memory, retention and/or comfort of clothing and other textile articles when applied at selected locations. What will be done has now been revealed.

Garments that can be improved using the dispersions and methods according to the present invention include, but are not limited to: disposable underwear, bras, panties, lingerie, swimwear, shapers, camisoles, socks, leggings, sleepwear, aprons, wetsuits, Ties, scrubs, space suits, uniforms, hats, garters, sweatbands, belts, activewear, outerwear, raincoats, snow jackets, pants, shirts, dresses, blouses, men's and women's tops, sweaters, corsets, vests, knickers, socks, Knee-high socks, dresses, blouses, tuxedos, vistas, abaya, hijab, jilbab, toe, burka, cape, costumes, diving suits, kilts, kimonos, uniforms, gowns, protective clothing, saris, sarongs, skils, spats, stoles, Suits, straitjackets, togas, tights, towels, uniforms, veils, wetsuits, medical compression garments, bandages, suit stuffing, belts and all components therein.

Other textile articles that can be improved using the dispersions and methods according to the present invention include, but are not limited to, chairs and seats, cushions, pads, shoes, shoe inserts, beds, packaging protection materials and automobile interiors.

In one non-limiting embodiment, the inventors herein have now discovered that selective positioning of an aqueous polymer dispersion, for example on a garment, improves fit and shaping in unexpected ways. More specifically, it has been discovered that applying the present aqueous polymer dispersion to one location on a garment can influence, cause and/or guide the fit and shaping at other locations on the garment. Moreover, such clothing is more comfortable. The use of an aqueous polymer dispersion in this way provides symmetrical correction of different breast sizes/shapes by selective application of the dispersion to the position of a bra or other supportive undergarment. In particular, the printing of this dispersion on the lower cup of the bra makes the difference between the two breasts/cups virtually indistinguishable and barely measurable, as determined by a three-dimensional body scanner, which makes the difference between the two breasts/cups less noticeable. Ideal for having any size/shape. Additionally, in the case of bralettes for keyhole tops or sheath dresses, such as those available from Tommy Hilfiger, printing the dispersion on the bra cups results in smoothing out the keyhole and eliminating keyhole flipping, a common problem with this design. Additionally, printing of the dispersion on the bra at the bottom and sides of the breast area provides push-in and push-up shaping of the breast. Printing the dispersion on the stomach part of the leggings results in better adhesion to the back waist. Therefore, this use of aqueous polymer dispersions provides an invisible treatment that maintains the elegant and simple design of the garment while avoiding the appearance of functional elements, and allows designers and garment makers to create new and differentiated garments with improved functionality. It provides the means to make feasible mass customization of garments.

In another non-limiting embodiment, the inventors herein have now discovered that site-selective application of aqueous polymer dispersions combined with selected application weights and design of application patterns creates localized shaping and support functionality for garments. Additionally, such clothing improves comfort. Various selected patterns for application of the dispersion include, but are not limited to, points, shapes such as triangles, circles, and rectangles, zigzags and/or lines, depending on what shaping and support functionality is desired. Such application of the aqueous polymer dispersion as a dispersion provides flexibility in designing progressive elastic moduli in garments and has improved functionality benefits while eliminating the steps of cutting and sewing, layering, seaming and/or use of elastic bands. Enables smooth clothing technology. Therefore, the use of aqueous polymer dispersions viewed in this way provides flexibility to designers, reduces steps, saves time, and saves production costs. Additionally, clothing produced according to this method can be thinner and lighter. Garments produced according to this method exhibit a softer appearance, especially at the random modulus interface. Additionally, printing of this aqueous polymer dispersion on, for example, thighs/calfs/legs on leggings is expected to increase garment strength for training and activity.

In another non-limiting embodiment, the inventors herein have discovered that selective application of an aqueous polymer dispersion to strategic areas of a garment can enable the garment to remain in place during movement, exercise and wear. Printing of the present dispersion, for example on the tummy area of leggings or yoga pants, can result in support and shaping of the tummy, better fit at the back waist and improved in-situ retention of the garment during activation, all at the same time. Similarly, selectively printing these dispersions in different places, such as bands, legging legs, bra cups and wings, seamless top/sport tank cups and straps, provides improved in-situ design while still providing the necessary stretch and/or recovery. It has been found that maintenance occurs. Application at selected locations on the bra straps can eliminate the need for uncomfortable plastic strap adjusters while improving both function and comfort. This use thus provides an invisible, seamless, simplified and more flexible garment design while reducing manufacturing times. Additionally, selective application of the present dispersion to the edges, bands and hems of the garment reduces rolling of such bands, hems and garment edges without making the garment more complex, thicker, heavier, more expensive or uncomfortable.

Additionally, the inventors herein have discovered that the ability of aqueous polymer dispersions to improve shape memory, retention, and comfort when applied at selected locations and/or intensities according to the methods of the present invention has many useful applications beyond clothing. For example, application of this aqueous polymer dispersion at selected locations and/or intensities improves the comfort of seats, cushions, and pads. Unexpectedly, when modifying the foam by padding the dispersion and then subjecting the foam to static weight/pressure, there is increased resistance to compaction collapse, decreased rate of collapse, decreased degree of collapse, increased rate of recovery once the weight is removed, and increased recovery. It was revealed that all levels were observed. Such better compression resistance improves the life of such cushions and pads. Additionally, application of the present aqueous polymer dispersions on such textile articles can reduce the effects of vibration/shock and reduce packaging volume by creating a thinner, better protective material.

The method of the present invention can also be used to improve the shape memory of footwear, inserts and seating, for example.

Additionally, the method of the present invention can be used to assist items such as, but not limited to, shoe inserts, automotive fabrics, and bedding materials to stay in place.

As shown herein, the application of aqueous polymer dispersions according to the process of the invention allows a highly selective and precisely controlled amount of improvement in the elastic modulus of clothing and other textile articles and can be used in PU dispersions, PU foams, fiberfills, It offers advantages over current technologies such as spring cushioning and generally wider, indiscriminately cut/sewn fabric panels.

All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are exhaustive to the extent such disclosure is not inconsistent with the invention and for all jurisdictions in which such incorporation is permitted. are hereby incorporated by reference.

Test methods and examples

The following test methods and examples demonstrate the invention and its ability to be used. The invention is capable of other and different embodiments, and its several details can be modified in various obvious respects without departing from the scope and spirit of the invention. Accordingly, the test methods and examples should be regarded as illustrative in nature and not restrictive.

Test Methods for Clothing

Abrasion test:

A force sensor was used to capture and record forces on the body while worn. The sensors were positioned between the garment and the wearing model and detected forces at various locations: waist, back, shoulders, front, breasts, under the bust, sides of the bust, ankles, knees, hips and stomach. Garments treated with and without aqueous polyurethane dispersion treatment were compared. During the measurement, the model either stood still or made repeated movements to mimic the wearing motion a consumer might make on the garment. Changes in force during movement were used to analyze comfort, support, shaping and retention.

3D body scanning:

A 3D body scanner was used to capture the silhouette of a live model with or without clothing. Changes in silhouette demonstrated the shaping effect of garments treated with water-based polyurethane dispersions on several body areas.

Fit Model Review:

A professional fit model with experience in garment fitting provided a review of the garment after wearing it. Comments include garment fit, comfort, support, appearance, stay, shape memory and other expectations about the wearing experience.

Test Methods for Fabrics

Tensile Test:

A moving device was used to fix the fabric at the two ends and stretch the fabric to a certain elongation. Fabric elasticity and recovery, which are critical to garment shaping, support and comfort, were analyzed using force, modulus and hysteresis during stretching and recovery.

Washing Durability:

Aqueous polyurethane dispersion treated fabrics were exposed to multiple (up to 50 washes) washing and drying cycles to mimic the garment life-cycle. The washed and dried fabric was subjected to different tests as mentioned. The durability of fabric form and function was analyzed using changes before and after washing and drying.

Fabric hand test:

Testers were asked to blindly touch and feel the fabric to investigate its pliability, softness and cooling predictions.

Test methods used for morphology and fiberfill materials:

Compression and recovery tests:

Thickness changes in a material are measured during changes in compression level by loading and unloading a series of static weights. The material was placed between flat plate holders. A weight was loaded onto the top plate and held in place for a few minutes before adding more weight. After adding weight to the highest requirement, the weight was gradually unloaded at the same level as loading. Thickness was measured to determine compression resistance and recovery.

Example

The following examples describe non-limiting embodiments of the compositions used in the present invention. The invention is capable of other and different embodiments, and its several details can be modified in various obvious respects without departing from the scope and spirit of the invention. Accordingly, the examples should be regarded as illustrative in nature and not restrictive.

In these examples, the following raw materials were used:

Example 1: Preparation of prepolymer without 1-hexanol

Polyurethane prepolymers include polytetramethylene ether glycol, aliphatic diisocyanates such as PICM (4,4'-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4'-MDI) and diols containing sterically hindered carboxylic acid groups. It was manufactured using . More specifically, the following ingredients and unit amounts were used to prepare the prepolymer:

The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-covered atmosphere to avoid side reactions.

In this example, a 30 gallon reactor coated with hydrothermal water and equipped with an agitator was used. The reactor was heated to a temperature of approximately 55°C. A pre-determined weight of molten Terathane® 1800 glycol was charged into the reactor. DMPA solid powder was then added to the reactor with shaking and circulation under a nitrogen blanket until the DMPA solid particles were dispersed and dissolved in the glycol.

The molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to occur at about 90° C. for about 240 minutes while continuing with continuous agitation. The viscous prepolymer formed is then sampled and the extent of reaction is determined by determining the weight percentage of isocyanate groups (%NCO) in the prepolymer through titrimetric methods. The theoretical value of %NCO after the reaction is complete is 2.97 assuming a glycol MW of 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 the reaction was determined to be complete, the prepolymer temperature was maintained between 85 and 90°C.

Example 2: Preparation of aqueous polymer dispersions with the prepolymer of Example 1

The dispersion was prepared by addition of the prepolymer of Example 1 using a rotor/stator high speed disperser. The prepolymer as prepared in Example 1 is transferred directly into the disperser head and dispersed under high shear forces in deionized water containing surfactants, neutralizers, antioxidants and/or foam modifiers. Slightly more prepolymer than required for the dispersion recipe was needed to compensate for losses in the transfer line and reactor.

The ingredients for preparing the dispersion and the composition of the dispersion are shown in Table 3 below.

In preparing a typical batch of 100 kg of aqueous polymer dispersion, Dowfax 2A1 surfactant (1.2652 kg), anti-oxidant Irganox 245 (0.6051 kg), and foam modifier BYK-012 (0.1265 kg) were mixed and added to deionized water (54.8093 kg). kg) was dissolved. Triethylamine neutralizer (0.783 kg) was added to the water mixture 5 minutes prior to the addition of prepolymer. The prepolymer (41.4109 kg) maintained at a temperature between 85 and 90° C. was added into the water mixture with high-speed dispersion. The rate of prepolymer addition (typically about 1.5 kg/min or about 30 minutes) should be controlled to allow the formation of a uniform dispersion, and the temperature of the dispersion should be maintained between 40 and 45°C. Once the addition of prepolymer is complete, mixing continues for 60 minutes. Then the thickener Tafigel PUR 61 (1.00 kg) is added and allowed to mix for another 60 minutes. The resulting dispersion was continuously shaken at low speed in the vessel for 8 hours (or overnight) to remove foaming and ensure the reaction was complete. The finished dispersion typically contains about 42% solids, with a viscosity of about 4000 centipoise and a pH ranging from 7.0 to 8.5. The breaking force (T) is the maximum or breaking force of the filament expressed as force per unit cross-sectional area. Adhesion can be measured on an Instron Model 1130, available from Instron, Canton, Mass., and is reported in grams per denier (grams per dtex). Filament adhesion at break (and elongation at break) can be measured according to ASTM D 885.

The dispersion was then filtered through a 100 micron bag filter to remove large particles before packaging for shipping. For shipping, it is recommended to use a 55 gallon metal drum with an internal polyethylene liner to contain the dispersion.

Final product specifications were determined as shown in Table 4.

Example 3: Preparation of prepolymer from 1-hexanol

Polyurethane prepolymers include polytetramethylene ether glycol, 1 -hexanol, aliphatic diisocyanates such as PICM (4,4'-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4'-MDI) and sterically hindered It was prepared using a diol containing a carboxylic acid group. Table 5 lists the ingredients and unit amounts used to prepare the prepolymer.

The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-covered atmosphere to avoid side reactions.

In this example, a 30 gallon reactor coated with hydrothermal water and equipped with an agitator was used. The reactor was heated to a temperature of approximately 55°C. A pre-determined weight of molten Terathane® 1800 glycol was charged into the reactor. 1-Hexanol was added secondarily. DMPA solid powder was then added to the reactor with shaking and circulation under a nitrogen blanket until the DMPA solid particles were dispersed and dissolved in the glycol.

The molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to occur at about 90° C. for about 240 minutes while continuing with continuous agitation. The viscous prepolymer formed is then sampled and the extent of reaction is determined by determining the weight percentage of isocyanate groups (%NCO) in the prepolymer through titrimetric methods. The theoretical value of %NCO after reaction completion is 2.80 assuming a glycol MW of 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 at 85 to 90°C.

Example 4: Preparation of aqueous polymer dispersions with the prepolymer of Example 3

The dispersion was prepared by addition of the prepolymer of Example 3 using a rotor/stator high speed disperser. The prepolymer as prepared in Example 3 is transferred directly into the disperser head and dispersed under high shear forces in deionized water containing surfactants, neutralizers, antioxidants and/or foam modifiers. Slightly more prepolymer than required for the dispersion recipe was needed to compensate for losses in the transfer line and reactor.

Table 6 lists the ingredients used to prepare the dispersion and the composition of the dispersion.

To prepare a typical batch of 100 kg dispersion, Dowfax 2A1 surfactant (1.2652 kg), antioxidant Irganox 245 (0.6051 kg), and foam modifier BYK-012 (0.1265 kg) were mixed and dissolved in deionized water (54.8093 kg). It has been done. Triethylamine neutralizer (0.7866 kg) was added to the 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 dispersion. The rate of prepolymer addition (typically about 1.5 kg/min or about 30 minutes) should be controlled to allow the formation of a uniform dispersion, and the temperature of the dispersion should be maintained between 40 and 45°C. Once the addition of prepolymer is complete, mixing continues for 60 minutes. Then the thickener Tafigel PUR 61 (1.00 kg) is added and allowed to mix for another 60 minutes. The resulting dispersion was continuously shaken at low speed in the vessel for 8 hours (or overnight) to remove foaming and ensure the reaction was complete. The finished dispersion typically contains about 42% solids, with a viscosity of about 4000 centipoise and a pH ranging from 7.0 to 8.5.

The dispersion was then filtered through a 100 micron bag filter to remove large particles before packaging for shipping. For shipping, it is recommended to use a 55 gallon metal drum with an internal polyethylene liner and vented cap to contain the dispersion.

Final product specifications were determined as shown in Table 7.

Claims (10)

A method for improving localized shaping and/or support functionality, shape memory, comfort and/or retention of clothing and other textile articles, the method comprising the following steps:
applying the aqueous polyurethane dispersion at a selected strength and/or at one or more selected locations on the clothing or other textile article; and
Following application of said water-based polyurethane dispersion at selected strengths and/or at one or more selected locations to improve shaping and/or support, shape memory, comfort and/or retention of clothing and other textile articles, Curing the urethane dispersion. The method of claim 1, wherein the aqueous polyurethane dispersion comprises:
prepolymers containing glycol, isocyanate and diol compounds; and
Water, neutralizers, surfactants, anti-foaming agents, antioxidants or thickeners. 3. The method of claim 2, wherein the prepolymer further comprises 1 -hexonal. 3. The method of claim 2, wherein the isocyanate is dicyclohexylmethane diisocyanate. 3. The method of claim 2, wherein the prepolymer contains at least 70% glycol, at least 20% isocyanate, and at least 2% diol. The method of claim 3, wherein the prepolymer contains less than 1% -hexanol. 3. The method of claim 2, wherein the aqueous polyurethane dispersion comprises:
prepolymer; and
Water, neutralizer, surfactant, anti-foaming agent, antioxidant and thickener. 3. The method of claim 2, wherein the aqueous polyurethane dispersion contains at least 30% glycol, 10% isocyanate, and at least 1% diol. 9. The method of claim 8, wherein 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 anti-foaming agent. A textile article exhibiting improved localized shaping and/or support functionality, shape memory, comfort and/or retention produced according to the method of any one of claims 1 to 9.