JP2021502500A - Methods using aqueous polyurethane dispersions and products made thereby - Google Patents

Abstract

Local correction of garments and other fabrics at a selected strength and / or by applying an aqueous polyurethane dispersion to one or more selected positions of the garment or other fabrics. Methods of improving function and / or support function, shape retention, comfort and / or displacement are provided. Clothing and other fabric products with improved local correction and / or support, shape retention, comfort and / or slippage made according to these methods are also provided. [Selection diagram] None

Description

The present invention relates to a method of using an aqueous polyurethane dispersion that improves local correction and / or support, shape retention, displacement and / or comfort of clothing and other fabric products.

Corrective garments are designed to temporarily change the wearer's body shape to achieve a more fashionable body shape. In recent years, fashion trends have tended to adopt garment and garment designs that increasingly emphasize the natural curves of the human body, and correction wear is growing in the market. The main uses are women's clothing, such as innerwear, lingerie, jeans and textile pants. Many female consumers are looking for comfortable clothing that enhances her body shape while emphasizing her best features, such as corrective jeans that can slim her thighs, tighten her thighs and lift her buttocks. Such clothing enhances the wearer's appearance and self-esteem.

Current techniques for correction mainly use various yarn loop structures of long floats, higher denier or higher draft elastic fibers, or apply special silhouette patterns to strategically selected positions. To do. Other common methods include introducing a second layer of fabric or pad sewn to the base fabric, or selecting different elastic fabrics, and stitching at different positions. .. For example, US Pat. Nos. 7,950,069, 7,341,500, and 7,945,970, International Application Publication No. 2013/154445A1, US Patent Application Publication No. 2010/0064409A1 and See 2011/0214216A1, UK Patent Application Publication No. 2477754A, and European Patent No. 0519135B1. One design adds a stiff panel inside the jeans, in front of the abdomen, to help make the tummy thinner. In another, one pad or sponge is inserted into the trousers to lift and improve the wearer's visual buttock profile. However, all of these designs and methods impair the comfort of the wearer and are often visible from the surface of the garment.

Polyurethane (including polyurethane urea) can be used as an adhesive for various substrates including woven fabrics. Typically, such polyurethanes are either fully formed non-reactive polymers or reactive isocyanate-terminated prepolymers. Such reactive polyurethane adhesives often require a long curing time to develop adequate adhesive strength, which can be a disadvantage in the manufacturing process. In addition, the isocyanate groups of polyurethanes are known to react sensitively to moisture, which limits storage stability and shortens the shelf life of products incorporating such polyurethanes. Typically, such polymers, when fully formed, are either soluble in a solvent (solvent-mediated), dispersed in water (water-mediated), or treated as a thermoplastic solid material (hot melt). Is it? In particular, solvent-based adhesives face increasingly stringent health and environmental laws aimed at reducing emissions of volatile organic compounds (VOCs) and toxic air pollutants (HAPs). Therefore, alternatives to conventional solvent-based products are needed.

Hot melt adhesives are environmentally safe and easily applied as a film, but generally have a high degree of cure and a low recovery rate after repeated stretch cycles. Therefore, improvement is needed.

Many attempts have been made to develop water-based polyurethane adhesives to overcome these shortcomings.

US Pat. No. 5,270,433 states that "(a) a mixture of polyols containing polypropylene glycol, (b) a mixture of polyfunctional isocyanates containing ααα ₁ α ₁ -tetramethylxylene diisocyanate (TMXDI), (c) aqueous solution. Adhesive composition comprising a substantially clear, solvent-free aqueous one-component polyurethane dispersion comprising a functional component capable of forming a salt therein and (d), optionally, a chain extender, a reaction product. " Is disclosed. The adhesive film from this composition has low resilience and low heat resistance due to the asymmetric structure and steric hindrance of the isocyanate groups of TMXDI, and strong interchain urea hydrogen bonds are not formed in the hard segments of the polymer.

U.S. Patent Application Publication No. 2004/0014880A1 discloses an aqueous polyurethane dispersion for adhesive bonding in wet and dry laminates described as having excellent coating properties, adhesive strength and heat resistance. This dispersion contains a fairly large amount of organic solvent (methyl ethyl ketone (MEK)).

U.S. Patent Application Publication No. 2003/0220463A1 discloses a method for making polyurethane dispersions that are free of organic solvents such as N-methylpyrrolidone (NMP). However, the composition is limited to prepolymers low in free diisocyanate species, such as methylenebis (4-phenylisocyanate) (4,4'-MDI). The process of producing such prepolymers low in free diisocyanate (as disclosed in US Pat. No. 5,703,193) is complex. Such treatments also require short-path distillation of free diisocyanates and are therefore not economical to produce prepolymers for making polyurethane dispersions.

US Pat. No. 4,387,181 discloses a stable aqueous polyurethane dispersion containing an N-methylpyrrolidone (NMP) solvent prepared by the reaction of a carboxyl group-containing oxime-blocked isocyanate-terminated prepolymer with a polyamine. doing. Prepolymers are made by reacting aromatic diisocyanates, such as 4,4'-diphenylmethane diisocyanates (MDIs) or toluene diisocyanates (TDIs), with polyether or polyester polyols and dihydroxyalkanoic acids. The oxime-blocked isocyanate group can react with the polyamine at 60-80 ° C within 6-18 hours. The dispersion is stable during storage and the film formed from the dispersion has good tensile properties. However, this dispersion still contains an organic solvent and, given the long curing time required, is not really suitable for fabric bonding and laminating.

U.S. Pat. No. 5,563,208 describes an acetone process for preparing an essentially solvent-free aqueous polyurethane dispersion, a urethane prepolymer having a blocked isocyanate group and a molecular weight in the range of 60-400. Polyamines are contained in the blocked isocyanate groups at a ratio of 1: 0.9 to 1: 1.5 to the primary and / or secondary amino groups. This dispersion is stable when stored at room temperature and provides a heat resistant binder for the coating. The curing time is long (up to 30 minutes) and is not yet suitable for bonding and bonding fabrics. In addition, the acetone process requires an additional distillation step to remove acetone from the dispersion, which reduces the economics of this method.

US Pat. No. 6,586,523 describes a prepolymer having a partially blocked, partially extended isocyanate group and a molecular weight of 32 to having a primary or secondary amino group and / or a hydroxyl group. Described is an acetone process for preparing self-crosslinked polyurethane dispersions for sizing agents, including 500 excess polyfunctional compounds. Although this dispersion composition shortens the curing time to some extent, it still has drawbacks because it requires an additional distillation step to remove acetone.

US Pat. No. 6,555,613 has a number average molecular weight (Mn) of 800 to 14,000, a degree of branching of 0.0 to 3.0 mol / kg, and 2.0 to 6.0 per mole. A solvent-free aqueous dispersion of a reactive polyurethane having an isocyanate functional value is described. Polyurethanes are made from polyester polyols, polyisocyanates, and polyisocyanate adducts that have a blocked isocyanate group with a low molecular weight polyol and anion forming unit incorporated into the polymer chain after neutralization to allow further reactions for cross-linking. It is made. The result of such dispersion is a hard, shiny, elastic coating material, which is the characteristic of the elastomer and elasticity / elasticity required for adhesives used in stretch fabrics. Has no recovery characteristics.

Polymer compositions, such as polyurethane urea films and tapes containing fully formed polyurethane urea with blocked isocyanate end groups, are disclosed in US Pat. No. 7,240,371. These compositions are prepared from a solvent-free system of prepolymers containing at least one polyether or polyester polyoil, a mixture of MDI isomers, and a diol.

US Pat. No. 9,346,932 provides an aqueous polyurethane dispersion provided in a solvent-free system of prepolymers containing at least one polyether, polyester, or polycarbonate polyol, a mixture of MDI isomers, and a diol, and them. A three-dimensional polymer formed from polycarbonate is disclosed.

Carmen, C.I. Et al. Disclose in European Patent No. 2280619B1 a method of adding a polymeric composition to the rim of a garment to form a garment rim band and adding a film to the garment, eg, a brassiere, to form a laminated fabric. Published U.S. Patent Application Publication No. 2009/0181599A1 is a fabric laminate or strip having multiple layered structures, including at least one fabric layer attached or bonded to each other and at least one polymer layer. Is disclosed.

Other examples of polymer compositions are polyurethane tapes, such as those commercially available from Bemis, and polyolefin resins that can be formed on films, such as those commercially available from ExxonMobil under the trade name VISTAMAXX. These films can be adhered to the cloth by applying heat.

The inventors of the present disclosure include glycols, isocyanates and diol compounds, and optionally 1-hexanol, with water, neutralizers, surfactants, defoamers, antioxidants and / or thickeners. By applying an aqueous polyurethane dispersion further containing a prepolymer, it can be applied at a selected strength of the fabric product and / or at a selected position or multiple selected positions to the local correction function of the fabric product. And / or found to improve support function, shape retention, displacement and / or comfort.

Therefore, one aspect of the present invention relates to a method for improving the local correction and / or support function of clothing and other textile products. The method comprises applying an aqueous polyurethane dispersion at a selected strength and / or at one or more selected positions of clothing or other fabric products. This method cures and corrects the aqueous polyurethane dispersion after applying the aqueous polyurethane dispersion at a selected strength and / or to selected one or more positions of clothing or other fabric products. And / or further include improving support.

Another aspect of the invention relates to a method of improving misalignment of clothing and other textile products. This method comprises applying an aqueous polyurethane dispersion to a selected strength and / or to one or more selected positions of a garment or other textile product, the garment or other textile product. It is hoped that they will not shift. This method applies the aqueous polyurethane dispersion at a selected strength and / or to one or more positions of the garment or other fabric product and then cures to displace the garment or other fabric product. Including further improvement.

Another aspect of the invention relates to a method of improving the comfort of clothing and other textile products. This method comprises applying an aqueous polyurethane dispersion to a selected strength and / or to one or more selected positions of a garment or other textile product, the garment or other textile product. Improved comfort is desired. This method applies the aqueous polyurethane dispersion to a selected strength and / or to one or more positions of the garment or other fabric product and then cures it to make the garment or other fabric product comfortable. Includes further improvement.

Another aspect of the invention relates to a method of improving the shape retention of clothing and other textile products. This method comprises applying an aqueous polyurethane dispersion to a selected strength and / or to one or more selected positions of a garment or other textile product, the garment or other textile product. Improved shape retention is desired. This method applies the aqueous polyurethane dispersion to a selected strength and / or to one or more positions of the garment or other fabric product and then cures to retain the shape of the garment or other fabric product. Further includes improving sex.

Yet another aspect of the invention is that an aqueous polyurethane dispersion is applied and at selected strengths that exhibit improved local correction and / or support, shape retention, displacement and / or comfort. And / or with respect to clothing and other fabric products cured at one or more selected positions.

Topical in garments and other fabrics by applying the aqueous polyurethane dispersion at the selected strength and / or in one or more selected locations on the garment or other fabrics. A method of improving correction and / or support, shape retention, displacement and / or comfort is provided by this disclosure.

As used herein, "improved," "improved," or "improved" refers to clothing and other textiles that are visually, physically, or coated with an aqueous polyurethane dispersion. Means any improvement that can be detected by quantifying local correction and / or support, shape retention, displacement and / or comfort.

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

The aqueous polyurethane dispersions included in the present disclosure are provided from the specific urethane prepolymers also disclosed herein. Aqueous polyurethane dispersions and prepolymers are free of organic solvents, co-solvents, alkyl ethoxylates, and organotin catalysts.

As used in the present disclosure, the term "dispersion" refers to a system in which the dispersed phase consists of finely divided particles and the continuous phase can be liquid, solid, or gas.

As used herein, the term "aqueous polyurethane dispersion" refers to at least polyurethane, or polyurethane urea polymers or prepolymers (eg, polyurethane prepolymers as described herein) dispersed in an aqueous medium, such as water containing deionized water. Refers to a composition containing (polymer).

The dry aqueous polyurethane dispersion used in the present disclosure is an aqueous polyurethane dispersion cured or dried by any suitable method. The dry aqueous polyurethane dispersion may be in the form of a molded article, for example a film.

As used herein, the term "solvent" refers to a non-aqueous medium unless otherwise indicated, where the non-aqueous medium is a volatile organic solvent (eg, acetone) and a less volatile organic solvent (eg, MEK or NMP). ) Containing an organic solvent.

As used herein, the term "essentially solvent-free" or "essentially solvent-free" refers to a composition or dispersion in which most of the composition or dispersion is not dissolved or dispersed in the solvent.

The prepolymers used in the aqueous polyurethane dispersions used in the present invention include glycols, aliphatic diisocyanates and diols.

Suitable glycol components as starting materials for preparing the prepolymers used in the present invention include polycarbonate and polyesters, polycarbonate glycols, polyether glycols, and polyester glycols.

Examples of polyether glycols that can be used are from ring-opening polymerization and / or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetahydrofuran, and 3-methyl tetrahydrofuran, or from demultiplexing of polyhydric alcohols. Diols with two or more hydroxy groups, preferably diols 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, Examples include, but are not limited to, 1,10-decanediol and 1,12-dodecanediol. Linear bifunctional polyether polyols are preferred, and poly (tetramethylene ether) glycols having two functional groups with a molecular weight of about 1,700 to about 2,100, such as Terathane® 1800 (Invista), are described. Particularly preferred for use with the prepolymers used in the invention.

Examples of polyester glycols that can be used are ester glycols having two or more hydroxy groups produced by polycondensation of low molecular weight aliphatic polycarboxylic acids having 12 or less carbon atoms and polyols, or those. Can be mentioned. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandicarboxylic acid and dodecanedicarboxylic acid. Examples of suitable polyols for preparing 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 having a melting point of about 5 ° C to about 50 ° C is preferred.

Examples of polycarbonate glycols that can be used are low molecular weight phosgens, chloroformates, dialkyl carbonates, or two or more produced by polycondensation of diallyl carbonates with aliphatic polyols, each of which has 12 or less carbon atoms. Examples thereof include carbonate glycol having a hydroxy group, or a mixture thereof. Examples of suitable polyols for preparing 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 having a melting point of about 5 ° C. to about 50 ° C. is preferred.

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

A suitable isocyanate component as another starting material for making the prepolymers useful in the present invention is dicyclohexylmethane diisocyanate, such as Vestante® H12MD1 (Evonik).

In one non-limiting embodiment, the prepolymer comprises at least 10%, or at least 22%, or at least 24% isocyanate with respect to the total weight of the prepolymer.

Suitable diols as another starting material for the preparation of the prepolymers disclosed herein are at least one diol having two hydroxy groups capable of reacting with isocyanate, and forming a salt upon neutralization. It contains at least one carboxylic acid group that can but cannot react with isocyanates. Examples of diols having a carboxylic acid group include 2,2-dimethylpropionic acid (DMPA), such as Bis-MPA (GEO), 2,2-dimethylbutane acid, 2,2-dimethylvaleric acid, DMPA-initiated caprolactone, For example, CAP A ™ HC 1060 (Solvay) can be mentioned, but is not limited thereto. 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% of the diol with respect to the total weight of the prepolymer.

In one non-limiting embodiment, the prepolymer further comprises a monofunctional alcohol containing methanol, ethanol, propanol, butanol, and 1-hexanol. In this non-limiting embodiment, the prepolymer comprises less than 1% or less than 0.5% 1-hexanol with respect to the total weight of the prepolymer.

The prepolymer is by mixing glycols, isocyanates, and diols together in one step, and from about 50 ° C. until all hydroxyl groups are essentially consumed and the desired% NCO of isocyanate groups is achieved. It can be prepared by reacting at a temperature of about 100 ° C. for an appropriate period of time. Alternatively, the prepolymer can be made by placing the molten glycol in a reactor at about 55 ° C. and then adding the DMPA solid powder with stirring and circulation until the diol solid particles are dispersed and dissolved in the glycol. it can. Next, the molten isocyanate is placed in the reactor with continuous stirring, and the capping reaction can be carried out at about 90 ° C. for about 240 minutes while still continuously stirring. The viscous prepolymer formed is then sampled and the degree of reaction is measured by measuring the weight percent (% NCO) of the isocyanate groups of the prepolymer by a titration method. The theoretical value of% NCO after the reaction is complete is 2.97, assuming a glycol MW of 1800. If the measured% NCO value is higher than the theoretical value, the reaction needs to be continued until the theoretical value is reached or the% NCO number becomes constant. When it is determined that the reaction is complete, the temperature of the prepolymer is maintained at 85 ° C to 90 ° C. Importantly, prepolymers are essentially solvent-free and contain neither alkyl ethoxylates nor organotin catalysts. The reaction for preparing the prepolymer is preferably carried out in a water-free nitrogen atmosphere to avoid side reactions.

The prepolymer of the present invention is then used to produce an aqueous polyurethane dispersion containing the prepolymer and water as well as a neutralizing agent, a surfactant, a defoaming agent, an antioxidant and / or a thickener.

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

In one non-limiting embodiment, the aqueous polyurethane dispersion is at least 50% water, at least 1% surfactant and / or thickener, and / or less than 1% neutralizer, antioxidant or Further contains an antifoaming agent.

The neutralizer used in these dispersions must be able to convert acid groups to bases. Examples include tertiary amines (eg, triethylamine, N, N-diethylmethylamine, N-methylmorpholin, N, N-diisopropylethylamine, and triethanolamine) and alkali metal hydroxides (eg, lithium hydroxide). , Sodium hydroxide, and potassium hydroxide), but is not limited to these. Primary and / or secondary amines can also be used as acid group neutralizers. The degree of neutralization is generally in the range of about 60% to about 140% of acid groups, for example about 80% to about 120%.

Examples of surfactants are anionic, cationic or nonionic dispersants or surfactants such as alkyldiphenyloxide disulfonate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, nonylphenol ethoxylated, and laurylpyridinium. Bromide, but is not limited to these.

Examples of suitable defoamers are mineral oils and / or silicone oils such as BYK 012 and Adaptive 65 (a silicone additive from Dow Corning), and Surfactol ™ DF 110L (Air Products & Chemicals high molecular weight acetylene glycol nonionics). Sexual surfactants), but are not limited to these.

Examples of suitable thickeners include polyurethanes such as Munzing's Tafigel PUR 61, hydrophobized modified ethoxylate urethane (HEUR), hydrophobized modified alkali swelling emulsion (HASE), and hydrophobized modified hydroxyethyl cellulose (HMHEC). Can be mentioned.

Examples of antioxidants include, but are not limited to, hindered phenols such as Irganox 245 (BASF) or Cytec 1790 (Cytec). In addition, ethylenediamine and diamines containing similar materials can be used as diamine chain extenders instead of water.

In one non-limiting embodiment, the dispersion is prepared by adding a prepolymer using a rotor / stator high speed disperser. The prepared prepolymer described above is moved directly into the disperser head and dispersed under high shear in deionized water containing at least a surfactant, a neutralizer, an antioxidant and / or a foam control agent. .. A little more prepolymer is needed than is required in the dispersion recipe to compensate for the loss in the transport line and in the reactor. Once the prepolymer has been added, the thickener can be added.

It should be desired that the aqueous polyurethane dispersion used in the present invention has a solid content of about 10% to about 50% by weight, for example about 30% to about 45% by weight. The viscosity of the aqueous polyurethane dispersion used in the present invention can be varied in a wide range from about 10 cm pores to about 100,000 cm pores, depending on the requirements of treatment and application. For example, in one non-limiting embodiment, the viscosity ranges from about 500 centipores to about 30,000 centipores. The viscosity can be changed by using a suitable amount of thickener, eg, about 0 to about 5.0% by weight, based on the total weight of the aqueous polyurethane dispersion.

Aqueous polyurethane dispersions can be applied to selected locations of clothing or other fabric products by methods such as, but not limited to, padding, coating, printing, gluing, laminating, spraying, and other coating / processing methods. It can be applied and / or at the strength of choice and then cured (or dried) with a standing time of about 1 to about 5 minutes.

The aqueous polyurethane dispersion can be diluted to the desired solid content prior to application to clothing or other fabric products.

These aqueous polyurethane dispersions provide local correction function and / or support for garments and other fabric products when applied to the selective strength and / or location of the garment and other fabric products. It has been found to be useful in improving function, shape retention, displacement and / or comfort.

Examples of garments that can be improved using the dispersions and methods according to the invention include disposable underwear, brassieres, panties, lingerie, swimwear, shapers, camisole, socks, leggings, sleepwear, aprons, wet suits, ties, etc. Scrubs, space clothing, uniforms, hats, garters, sweat bands, belts, active wear, outerwear, rainwear, cold jackets, pants, shirts, dresses, blouses, men's and women's tops, sweaters, corsets, vests, nickers. , Socks, high socks, dresses, blouses, tuxedo, bishto, abaya, hijab, jilbab, tove, burka, cape, costume, diving suit, quilt, kimono, jersey, gown, protective clothing, sari, salon, skill, spats, stra , Suits, leggings, toga, tights, towels, uniforms, veils, wet suits, medical compression garments, bandages, suit cores, waistbands, and all components within them, but are limited to these. Not done.

Examples of other fabric products that can be improved using the dispersions and methods according to the invention include seating and seats, cushions, pads, footwear, footwear inserts, bedding, packaging protective materials and Examples include, but are not limited to, automobile interiors.

In one non-limiting embodiment, the inventors of the present disclosure have found, for example, that selective placement of an aqueous polymer dispersion on clothing improves fit and correction in unexpected ways. More specifically, it has been found that applying an aqueous polymer dispersion to one position of the garment can affect, induce, and / or induce the fit and correction of the garment at another position. Moreover, such clothing is more comfortable. The use of aqueous polymer dispersions in this manner provides symmetrical correction of different breast sizes / shapes by selectively applying the dispersion to the location of a bra or other supporting underwear. Specifically, the models have different breast sizes / shapes, but printing the dispersion on the lower cup of the bra makes it impossible to visually recognize the difference between the two breasts / cups, and a three-dimensional body scanner. It became difficult to measure with. In addition, for keyhole top or sheath dress bralettes available from Tommy Hilfiger, printing the dispersion on the bra cup will smooth the keyholes and eliminate the keyhole flipping, which is a common problem with this design. The result was that. In addition, printing dispersions on the bottom and sides of the bra's breast area provides indentation and uplift compensation in the breast. Printing the dispersion on the tummy of the leggings improved the adhesion of the back waist. Therefore, this application of aqueous polymer dispersion provides invisible processing that keeps the elegant and simple garment design while avoiding the appearance of functional elements, improving functionality for designers and garment makers. It provides a means of creating new differentiated garments and enables mass customization of garments.

In another non-limiting embodiment, the inventors of the present disclosure consider that a position-selective application of an aqueous polymer dispersion, coupled with a selected application weight and application pattern design, provides local correction function and support for clothing. I found that it produces Noh. In addition, such clothing has improved comfort. The various patterns selected for applying the dispersion include dots, shapes, such as triangles, circles, and rectangles, zigzags and / or lines, depending on which correction and support features the garment requires. However, it is not limited to these. Such application of an aqueous polymer dispersion as a dispersion allows flexible design of the gradual modulus of the garment, enhances functionality with seamless garment technology, and cuts, sews, overlays and sews. Eliminates the steps of attaching and / or using elastic bands. Therefore, the use of aqueous polymer dispersions in this way gives designers flexibility, reduces steps, saves time, and saves costs in production. Moreover, clothing produced according to this method can be thinner and lighter. Clothing produced in this way exhibits a smooth appearance, especially at any modulus boundary. In addition, printing of aqueous polymer dispersions, for example on the thighs / calves / legs of leggings, is expected to increase the ability of the garment for training and activity.

In another non-limiting embodiment, the inventors of the present disclosure selectively apply the aqueous polymer dispersion where it is important for garment policy to place the garment in place during movement, exercise, and wearing. It turns out that it can stay in place. For example, printing a dispersion over the tummy area of leggings or yoga pants simultaneously provides tummy support and correction, a better fit for the back waist, and improved clothing during activity that stays in place. Is done. Similarly, selective printing of the dispersion on various locations, such as bands, leggings legs, bra cups and wings, seamless top / sports tank cups and straps, from a given position with the required stretch and / or recovery. It was found that the result of improvement is that it does not shift. Applying to selected locations on the bra straps can eliminate the need for unpleasant plastic strap adjusters while improving both functionality and comfort. Therefore, this application allows for invisible, seamless, simplified and more flexible garment design while reducing manufacturing time. In addition, selective application of the dispersion to the hem, rim, and hem of the garment makes the garment more complex, thick, heavy, expensive, and without discomfort, such garment rim, rim, and hem. Reduces the roundness of.

In addition, the inventors of the present invention have the ability of aqueous polymer dispersions to improve shape retention, displacement, and comfort when applied in positions and / or strengths selected according to the methods of the invention. It has been found that it has many useful uses other than clothing. For example, application of the aqueous polymer dispersion at selected locations and / or strength improves the comfort of seats, cushions, and pads. Unexpectedly, changing the foam by padding the dispersion and exposing the foam to static weight / pressure increases resistance to compressive decay, reduces decay rate, decreases degree of decay, weight. It was found that an increase in the recovery rate and an increase in the degree of recovery were all observed after the removal of. Such better compression resistance improves the life of such cushions and pads. In addition, application of the aqueous polymer dispersion to such fabric products can reduce the packaging volume by reducing the effects of vibration / impact and creating thinner and better protective materials.

The methods of the invention can also be used, for example, to improve the shape retention of footwear, inserts, and seats.

In addition, the methods of the invention can be used to help keep items such as footwear inserts, automotive fabrics, and bedding materials in place, but not limited to these.

As shown herein, the application of an aqueous polymer dispersion according to the method of the invention enhances the modulus of elasticity of clothing and other fabric products in highly selective and precisely controlled amounts. It can provide advantages to existing technologies, such as PU dispersions, PU foams, fiber fillers, spring cushions, and generally more widely indiscriminate cut / sewn fabric panels.

All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are to the extent that such disclosure is consistent with the present invention, and such. All permissions that are allowed to be included are fully included by reference.

Test Methods and Examples The following test methods and examples demonstrate the present invention and its ability to be used. The present invention may have other different embodiments, some of which may be modified in various obvious ways without departing from the scope and gist of the invention. Therefore, the test methods and examples should be considered exemplary in nature and non-limiting.

Clothes test method Abrasion force test:
A force sensor was used to capture and record the force exerted on the body when worn. Sensors were placed between the garment and the wearing model to detect force in various positions, such as waist, back, shoulders, front, chest, under the bust, sides of the bust, ankles, knees, buttocks, and abdomen. Clothing with and without aqueous polyurethane dispersion treatment was compared. During the measurement, the model acted stationary or in repetitive motions, mimicking the wearing motions that consumers would perform in clothing. The changes in force during motion were used to analyze comfort, support, correction, and deviation.

3D body scan:
A 3D body scanner was used to capture the silhouette of a live model with or without clothing. The change in silhouette showed a correction effect on some body areas of the aqueous polyurethane dispersion-treated garment.

Evaluation of wearing model:
Professional wearing models with experience wearing clothing performed a garment evaluation after wearing. Comments include other expectations regarding the fit, comfort, support, appearance, slippage, shape retention, and wearing experience of the garment.

Fabric test method Tensile test:
A moving device was used to secure the fabric at the two ends and stretch the fabric to a certain stretch. Stretch and recovery forces, modulus, and hysteresis were used to analyze fabric elasticity and resilience, which are important for garment correction, support, and comfort.

Washing durability:
Aqueous polyurethane dispersion treated fabrics were exposed to multiple wash and dry cycles (up to 50 washes) to mimic the life cycle of clothing. The washed and dried fabric as described above was subjected to another test. The changes before and after washing and drying were used to analyze the durability of fabric shape and function.

Cloth hand test:
Testers were asked to blindly touch and touch the fabric to investigate the softness, smoothness, and cooling expectations of the fabric.

Test methods used in shape and fiber filler materials:
Compression and recovery test:
Changes in material thickness are measured during changes in compression levels due to a series of static loading and unloading. The material was placed between the flat plate holders. The weight was placed on the top plate and held in place for a few minutes before adding more weight. After adding the weight to the maximum requirement, the weight was gradually removed at the same level as it was placed. The thickness was measured and the compression resistance and recovery rate were measured.

The following examples describe non-limiting embodiments of the compositions used in the present invention. The present invention may have other different embodiments, some of which may be modified in various obvious ways without departing from the scope and gist of the invention. Therefore, the examples should be considered exemplary in nature and non-limiting.

In these examples, the following raw materials were used:

Example 1: Preparation of prepolymers without 1-hexanol Polyurethane prepolymers are polytetramethylene ether glycols, aliphatic diisocyanates such as PICM (4,5'-methylenebis (cyclohexylisocyanate), 4,4'-DMI. It was made using a hydrogenated version) and a diol containing a sterically impaired carboxylic acid group. More specifically, the following components and unit amounts were used to make prepolymers.

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

In this example, a 30 gallon reactor jacketed with warm water and equipped with a stirrer was used. The reactor was heated to a temperature of about 55 ° C. A predetermined weight of molten Terathane® 1800 glycol was charged into the reactor. The DMPA solid powder was then added to the reactor with stirring and circulation in a nitrogen atmosphere until the DMPA solid particles were dispersed and dissolved in the glycol.

Next, the molten PICM was placed in the reactor with continuous stirring, and the capping reaction was carried out at 90 ° C. for 240 minutes with continuous stirring. The viscous prepolymer formed was then sampled and the degree of reaction was measured by measuring the weight percent (% NCO) of the isocyanate groups of the prepolymer by a titration method. The theoretical value of% NCO after the reaction is complete is 2.97, assuming a glycol MW of 1800. If the measured% NCO value is higher than the theoretical value, the reaction needs to be continued until the theoretical value is reached or the% NCO number becomes constant. When it was determined that the reaction was complete, the temperature of the prepolymer was maintained at 85-90 ° C.

Example 2: Preparation of Aqueous Polymer Dispersion Using Prepolymer of Example 1 A dispersion was prepared by adding the prepolymer of Example 1 using a rotor / stator high-speed disperser. The prepolymer prepared in Example 1 was moved directly into the disperser head and dispersed in deionized water containing a surfactant, a neutralizing agent, an antioxidant, and a foam control agent under high shearing force. A little more prepolymer was needed than was required in the dispersion recipe to compensate for the losses in the transport line and in the reactor.

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

When making a typical batch of 100 kg of aqueous polymer dispersion, Dowfax 2A1 surfactant (1.2652 kg), antioxidant Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg). Was mixed and dissolved in deionized water (54.8093 kg). Five minutes before adding the prepolymer, a triethylamine neutralizer (0.783 kg) was added to the water mixture above. A prepolymer (41.4109 kg) maintained at a temperature of 85-90 ° C. was added to the aqueous mixture with fast dispersion. It is necessary to control the rate of addition of the prepolymer (usually about 1.5 kg / min or about 30 min) to form a uniform dispersion, and the temperature of the dispersion should be maintained at 40-45 ° C. .. Once the prepolymer addition was complete, mixing was continued for 60 minutes. Next, the thickener Tafigel PUR 61 (1.00 kg) was added and mixed for an additional 60 minutes. The dispersion during production was continuously stirred in a container at low speed for 8 hours (or overnight) to remove bubbles and confirmed that the reaction was reliably completed. The finished dispersion typically contains about 42% solids, has a viscosity of about 4000 centipoise, and has a pH in the range of 7.0 to 8.5. The strength at break (T) is the maximum force or breaking force of the filament expressed as the force per unit cross-sectional area. Intensity can be measured with the Instrument model 1130 available from the Instrument of Canton, Mass and is reported as the number of grams per denier (the number of grams per dtex). The strength of the filament at break (and the 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 transport. It is recommended to use a 55 gallon metal drum with an internal polyethylene liner to accommodate the dispersion for transportation.

The final product specifications were determined as shown in Table 4.

Example 3: Preparation of Prepolymer with 1-Hexanol Polyurethane prepolymers include polytetramethylene ether glycol, 1-hexanol, aliphatic diisocyanates such as PICM (4,54'-methylenebis (cyclohexyl isocyanate), 4,4'. -Hydrogenated version of DMI), and made using diols containing sterically impaired carboxylic acid groups. Table 5 shows the components and unit amounts used in the preparation of the prepolymer.

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

In this example, a 30 gallon reactor jacketed with warm water and equipped with a stirrer was used. The reactor was heated to a temperature of about 55 ° C. A predetermined weight of molten Terathane® 1800 glycol was charged into the reactor. 1-Hexanol was added second. The DMPA solid powder was then added to the reactor with stirring and circulation in a nitrogen atmosphere until the DMPA solid particles were dispersed and dissolved in the glycol.

Next, the molten PICM was placed in the reactor with continuous stirring, and the capping reaction was carried out at 90 ° C. for 240 minutes with continuous stirring. The viscous prepolymer formed was then sampled and the degree of reaction was measured by measuring the weight percent (% NCO) of the isocyanate groups of the prepolymer by a titration method. The theoretical value of% NCO after the reaction is complete is 2.80, assuming a glycol MW of 1800. If the measured% NCO value is higher than the theoretical value, the reaction needs to be continued until the theoretical value is reached or the% NCO number becomes constant. When it is determined that the reaction is complete, the temperature of the prepolymer is maintained at 85-90 ° C.

Example 4: Preparation of Aqueous Polymer Dispersion Using Prepolymer of Example 3 A dispersion was prepared by adding the prepolymer of Example 3 using a rotor / stator high speed disperser. The prepolymer prepared in Example 3 was directly transferred into the disperser head and dispersed in deionized water containing a surfactant, a neutralizing agent, an antioxidant, and a foam control agent under high shearing force. A little more prepolymer is needed than is required in the dispersion recipe to compensate for the loss in the transport line and in the reactor.

Table 6 shows the components used to make the dispersion and the composition of the dispersion.

When making a typical batch of this 100 kg dispersion, Dowfax 2A1 surfactant (1.2652 kg), antioxidant Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg). It was mixed and dissolved in deionized water (54.8083 kg). Five minutes before adding the prepolymer, a triethylamine neutralizer (0.7866 kg) was added to the above water mixture. A prepolymer (41.4083 kg) maintained at a temperature of 85-90 ° C. was added to the aqueous mixture with fast dispersion. It is necessary to control the rate of addition of the prepolymer (usually about 1.5 kg / min or about 30 min) to form a uniform dispersion, and the temperature of the dispersion should be maintained at 40-45 ° C. .. Once the prepolymer addition was complete, mixing was continued for 60 minutes. Next, the thickener Tafigel PUR 61 (1.00 kg) was added and mixed for an additional 60 minutes. The dispersion during production was continuously stirred in a container at low speed for 8 hours (or overnight) to remove bubbles and confirmed that the reaction was reliably completed. The finished dispersion typically contains about 42% solids, has a viscosity of about 4000 centipoise, and has a pH in the range of 7.0 to 8.5.

The dispersion was then filtered through a 100 micron bag filter to remove large particles before packaging for transport. It is recommended to use a 55 gallon metal drum with a ventilation cap and an internal polyethylene liner to accommodate the dispersion for transportation.

The final product specifications were determined as shown in Table 7.

Claims (10)

A method of improving local correction and / or support, shape retention, comfort and / or misalignment of clothing and other fabric products, said method.
Applying the aqueous polyurethane dispersion at a selected strength and / or at one or more selected positions of the garment or other fabric product.
The aqueous polyurethane dispersion has been selected for the garment and other fabric products to improve correction and / or support, shape retention, comfort and / or displacement of the garment and other fabric products. To cure the aqueous polyurethane dispersion and / or after application to one or more selected locations with high strength.
Including methods. The aqueous polyurethane dispersion comprises a prepolymer containing a glycol, an isocyanate, and a diol compound.
With water, neutralizers, surfactants, defoamers, antioxidants, or thickeners,
The method according to claim 1, wherein the method comprises. The method of claim 2, wherein the prepolymer further comprises 1-hexanol. The method according to claim 2, wherein the isocyanate is a dicyclohexylmethane diisocyanate. The method of claim 2, wherein the prepolymer comprises at least 70% glycol, at least 20% isocyanate, and at least 2% diol. The method of claim 3, wherein the prepolymer comprises less than 1% 1-hexanol. The aqueous polyurethane dispersion is
With the prepolymer
Water, neutralizers, surfactants, defoamers, antioxidants, and thickeners with water,
2. The method according to claim 2. The method of claim 2, wherein the aqueous polyurethane dispersion comprises at least 30% glycol, at least 10% isocyanate, and at least 1% diol. The aqueous polyurethane dispersion further comprises at least 50% water, at least 1% surfactant and / or thickener, and / or less than 1% neutralizer, antioxidant or defoamer. Item 8. The method according to Item 8. A fabric product that exhibits improved local correction and / or support, shape retention, comfort and / or misalignment, manufactured according to the method according to any one of claims 1-9.