Article and method of manufacturing article comprising coating

Abstract

The invention relates to an article and a method of manufacturing an article including a coating. The present disclosure relates to an article comprising a cured coating (32) comprising a cross-linked polymer matrix and optionally a colorant (e.g., pigment particles or dye, or both). The cured coating (32) may include a cross-linked polymer matrix. The cured coating (32) is the product of cross-linking a coating composition comprising an uncross-linked polymer (e.g., a dispersion of the uncross-linked polymer in a carrier to form a cross-linked polymer matrix), where the uncross-linked polymer is cross-linked to form the cross-linked polymer matrix. The cross-linked polymer matrix may be elastic. The present disclosure also relates to articles comprising the bladders (28), methods of forming the bladders (28), and methods of manufacturing articles comprising the bladders (28), wherein the bladders (28) comprise a cured coating (32).

Description

[0001] This application is a continuation of an application entitled “ARTICLES AND METHODS OF MAKING ARTICLES INCLUDING A COATING,” filed October 26, 2018, having application number 202111617559.5, and having a title of “ARTICLES AND METHODS OF MAKING ARTICLES INCLUDING A COATING.”

[0002] The application entitled “ARTICLES AND METHODS OF MAKING ARTICLES INCLUDING A COATING,” filed October 26, 2018, having application number 202111617559.5, is a continuation of an application entitled “ARTICLES AND METHODS OF MAKING ARTICLES INCLUDING A COATING,” filed October 26, 2018, having application number 201880082729.4. Cross Reference to Related Applications

[0003] This application claims the benefit of and priority to U.S. Provisional Application Serial No. 62 / 577,904, filed October 27, 2017, entitled “BLADDERS AND METHODS OF MAKING BLADDERS,” and U.S. Provisional Application Serial No. 62 / 617,665, filed January 16, 2018, entitled “COMPOSITE STRUCTURES AND METHODS OF MAKING COMPOSITE STRUCTURES,” and U.S. Provisional Application Serial No. 62 / 712,683, filed July 31, 2018, entitled “ARTICLES AND METHODS OF MAKING ARTICLES INCLUDING A COATING,” and U.S. Provisional Application Serial No. 62 / 724,260, filed August 29, 2018, entitled “ARTICLES INCLUDING COATED FIBERS AND METHODS OF MAKING COATED FIBERS AND ARTICLES,” the disclosures of which are incorporated by reference herein in their entireties. BACKGROUND

[0004] Footwear, clothing, accessories, or athletic apparel are often a source of expression for the wearer and can include colors associated with a team, coordinated with another item, or provide an attractive or customized item to the user. Footwear can include an upper, a midsole, and an inflated bladder or airbag for cushioning, and each can be colored to be part of the source of expression. SUMMARY

[0005] The present invention relates to the following items: 1. A coated article, comprising: a cushioning element having an outward-facing side comprising a first polymeric material; and a cured coating disposed on the first polymeric material of the outward-facing side, wherein the cured coating comprises a plurality of pigment particles embedded in a crosslinked polyurethane matrix.

[0006] 2. The coated article of item 1, wherein the cured coating is the product of crosslinking a coating composition comprising a dispersion of uncrosslinked polymer in a carrier to form a crosslinked polymeric matrix.

[0007] 3. The coated article of item 1 or 2, wherein the crosslinked polymeric matrix comprises a crosslinked polyester polyurethane.

[0008] 4. The coated article of any of items 1 to 3, wherein the first polymeric material is elastic and the cured coating is elastic.

[0009] 5. The coated article of any of items 1 to 3, wherein the first polymeric material is a foamed polymeric material.

[0010] 6. The coated article of item 5, wherein the foamed polymeric material comprises a vinyl acetate homopolymer or copolymer, an acrylate homopolymer or copolymer, a styrene homopolymer or copolymer, an olefin homopolymer or copolymer, or any combination thereof.

[0011] 7. The coated article of any of items 1 to 4, wherein the cushioning element is an inflated bladder having a bladder wall with an interior-facing side bounding an interior region of the bladder and an exterior-facing side opposite the interior-facing side; wherein the first polymeric material bounds the interior-facing side or the exterior-facing side or both; and wherein the cured coating is disposed on the exterior-facing side or the interior-facing side or both.

[0012] 8. The coated article of item 7, wherein the bladder wall has an average wall thickness of less than 5 millimeters.

[0013] 9. The coated article of item 7 or 8, wherein the bladder wall has a gas permeability to nitrogen of 15 cm3 / m2•atm•day or less for an average wall thickness of 20 mils.

[0014] 10. The coated article of any of items 7-9, wherein the bladder wall includes a thermoplastic polyurethane film on the exterior-facing side of the bladder wall or the interior-facing side of the bladder wall, wherein the cured coating is disposed on the thermoplastic polyurethane film.

[0015] 11. The coated article of any of items 1 to 10, wherein the cured coating reduces a level of ultraviolet light reaching the first polymeric material compared to a substantially identical article without the cured coating.

[0016] 12. The coated article of any of items 1 to 11, wherein the cured coating reduces a level of water reaching the first polymeric material compared to a substantially identical article without the cured coating.

[0017] 13. The coated article of any of items 1 to 12, wherein the article is a sole structure for an article of footwear, and the cushioning element is a midsole component of the sole structure.

[0018] 14. A method of making a coated article, the method comprising: disposing a coating composition comprising pigment particles and uncrosslinked polyurethane onto a first polymeric material of a first side of a cushioning element; and curing the coating composition on the first polymeric material, crosslinking the polyurethane to form a crosslinked polyurethane matrix, forming a cured coating comprising a plurality of pigment particles embedded in the crosslinked polyurethane matrix, and forming the coated article.

[0019] 15. The method of item 14, wherein disposing the coating composition comprises disposing a coating composition onto the first polymeric material, the coating composition comprising a dispersion of the pigment particles and the uncrosslinked polymer in a carrier; and forming the cured coating comprises crosslinking the uncrosslinked polymer of the dispersion to form the crosslinked polymer matrix and embedding the plurality of pigment particles in the crosslinked polymer matrix.

[0020] 16. The method of item 15, wherein the carrier is water or an aqueous solution.

[0021] 17. The method of any of items 14 to 16, wherein the coating composition comprises a thermally initiated crosslinking agent.

[0022] 18. The method of any of items 14 to 17, wherein the first polymeric material is a foamed polymeric material, and the disposing comprises spray coating the coating composition onto the foamed polymeric material.

[0023] 19. The method of any of items 14-17, wherein the cushioning element comprises an inflated bladder having a bladder wall, and the disposing comprises spraying the coating composition onto an exterior-facing side of the bladder wall, or comprises immersing the exterior-facing side of the bladder wall into the coating composition.

[0024] 20. The method of any of items 14-19, wherein the curing comprises raising a temperature of the coating composition to a temperature from about 50 °C to about 90 °C for at least 1 minute. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is a side elevational view of an athletic shoe with a portion of the midsole cut away to expose a cross-sectional view.

[0026] Figure 2 is a bottom elevational view of the athletic shoe of Figure 1 cut away to expose another cross-sectional view.

[0027] Figure 3 is a cross-sectional view taken along line 3-3 of Figure 1 DESCRIPTON

[0028] The present disclosure relates to articles comprising a cured coating, the cured coating comprising a crosslinked polymeric matrix and optionally a colorant (e.g., a pigment particle or a dye or both). The cured coating can comprise a crosslinked polymeric matrix. The cured coating is the product of crosslinking a coating composition comprising an uncrosslinked polymer (e.g., a dispersion of the uncrosslinked polymer in a carrier to form the crosslinked polymeric matrix), where the uncrosslinked polymer is crosslinked to form the crosslinked polymeric matrix. The crosslinked polymeric matrix can be elastic. The cured coating can be formed by disposing (e.g., spraying) the coating composition onto a first polymeric material on a first side of an article, and curing the coating composition on the polymeric material by crosslinking the uncrosslinked polymer of the coating composition to form a crosslinked polymeric matrix from the previously uncrosslinked polymer of the coating composition, and bonding the crosslinked polymeric matrix to the polymeric material on the side of the article. The article can comprise an article of footwear, a component of footwear, a garment, a component of a garment, athletic equipment, or a component of athletic equipment.

[0029] When the cured coating comprises a colorant (e.g., when the coating composition contains a colorant), the cured coating can be used to provide a desired color or appearance to the article. When the colorant is included in the coating composition, the crosslinked polymeric matrix formed by curing the coating composition encases the colorant, and the matrix containing the colorant is bonded to the polymeric material on the side of the article.

[0030] ​It has been discovered that the coating compositions and cured coatings disclosed herein particularly well bond to polymeric materials, including solid polymeric materials and foamed polymeric materials, as well as thermoset materials and thermoplastic materials. The cured coatings well bond to a variety of types of polymers, such as polyesters, polyethers, polyamides, polyolefins, and polyurethanes, including thermoplastic polyurethanes (TPUs). It has also been discovered that these coating compositions and cured coatings well bond to non-polymeric materials such as glass and carbon (e.g., glass fibers and carbon fibers).

[0031] It has also been discovered that when the crosslinked polymeric matrix is elastic (e.g., when the coating composition includes an uncrosslinked, elastic polymer), the coating compositions and cured coatings are particularly well suited for use on articles that can flex or bend during use, such as bladders and foamed materials. For example, these elastic coating compositions and cured coatings are well suited for use on components of articles of footwear, articles of apparel, and articles of sports equipment. When a colorant is included in these coating compositions and cured coatings, the elastic, crosslinked polymeric matrix effectively traps the colorant while remaining bonded to the polymeric material of the article during use.

[0032] The present disclosure also provides a coated article that is a cushioning element, such as an elastic bladder or a component that includes an elastic foam (including an elastic thermoplastic foam material or an elastic thermoset foam material). The cushioning element can have an outward-facing side that includes a first polymeric material; and a cured coating as disclosed herein disposed on the first polymeric material of the outward-facing side. Optionally, the cured coating includes a plurality of pigment particles that are trapped in the crosslinked polymeric matrix. The cured coating can be an elastic material that includes an elastic, crosslinked, elastic polymeric matrix, such that the coating has the ability to flex with the cushioning element without cracking. The cushioning element can be a cushioning element for an article of footwear, such as a midsole component. The cushioning element can be a cushioning element for an article of apparel or for an article of sports equipment.

[0033] In examples in which the article is a bladder (an inflated or deflated bladder), the coating composition can be disposed on a bladder wall formed from a polymeric material. The coating can be on an interior-facing side of the bladder wall, or an exterior-facing side of the bladder wall, or both. When the bladder is an inflated bladder, the interior-facing side bounds at least a portion of an interior region of the inflated bladder. The bladder wall can have an average wall thickness (as measured between the interior-facing side and the exterior-facing side) of less than 5 millimeters. The polymeric material of the bladder wall can be a polyurethane material, such as a thermoplastic polyurethane material that includes a polyester polyurethane copolymer.

[0034] The cured coatings disclosed herein can be used to block UV light and therefore reduce discoloration of the polymeric materials of articles. For example, the coatings disclosed herein can be used to reduce yellowing of polyamide homopolymers and copolymers caused by UV light. Similarly, these cured coatings can restrict or block water contact with the polymeric materials of articles, thus reducing the article's absorption of water. For example, the cured coatings can be used to reduce the water absorption of hydrophilic polymers, including polyamide homopolymers and copolymers. Furthermore, these cured coatings are durable and provide an efficient way to adhere colorants to polymeric materials.

[0035] The coating composition may comprise an uncrosslinked polyurethane homopolymer or copolymer, or both, comprising a dispersion of polyurethane in a carrier, such as a water-borne dispersion of polyurethane in water or an aqueous solution. The cured coating may be a product that crosslinks the uncrosslinked polyurethane homopolymer or copolymer, or both. Optionally, the coating composition may comprise a crosslinking agent, such as an aqueous crosslinking agent. The crosslinked polymer matrix of the cured coating may comprise a crosslinked polyurethane homopolymer or copolymer, or both. In certain examples, the polyurethane may comprise a resilient polyurethane, including resilient polyester polyurethane.

[0036] This disclosure also provides a method of manufacturing an article, the method comprising attaching (e.g., attaching, joining, connecting, etc.) a first article as described above and herein to a second article. For example, the first and second articles may be components of footwear articles, clothing articles, or sports equipment articles, and attaching the first and second articles together may produce a final footwear article, clothing article, or sports equipment article.

[0037] The implementation scheme of this disclosure has now been broadly described, and further discussion of the implementation scheme will follow in more detail.

[0038] This disclosure is not limited to the specific embodiments described, and therefore is subject to change. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be restrictive, as the scope of this disclosure will be limited only by the appended claims.

[0039] When a range of values ​​is provided, every intermediate value between the upper and lower limits of that range (in units of one-tenth of the lower limit, unless the context explicitly indicates otherwise) and any other stated value or intermediate value within that range are included in this disclosure. The upper and lower limits of these smaller ranges may be independently included in the smaller ranges and are also included in this disclosure, subject to any specific excluded limit within the stated range. When a stated range includes one or both limits, the range excluding any one or both of those included limits is also included in this disclosure.

[0040] It will be apparent to those skilled in the art reading this disclosure that each of the various embodiments described and illustrated herein has discrete parts and features that can be easily separated from or combined with features of any of the other several embodiments without departing from the scope or spirit of the disclosure. Any recited method can be conducted in the order of events recited or in any other order that is logically possible.

[0041] Unless otherwise indicated, embodiments of the present disclosure will employ materials science, chemistry, textile, polymer chemistry, and similar techniques within the skill of the art. Such techniques are explained fully in the literature.

[0042] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art of the fields of materials science, chemistry, textile, polymer chemistry, and similar fields. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein.

[0043] As used in the specification and the appended claims, the singular forms "a," "an," and "the" can include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a support" includes more than one support. In this specification and in the claims that follow, reference will be made to a number of terms, which should be defined as having the meanings that follow unless a contrary intent is apparent.

[0044] As briefly described above, an article can include a cured coating, where the cured coating can be on an outer surface of the article. The cured coating has been found to bond well to the surface of the article when the surface is made of a polymeric material. The surface of the article can be made of a polymeric material such as a polyester, a polyether, a polyamide, a polyolefin, or a polyurethane. The cured coating can be physically and / or chemically bonded (e.g., covalently bonded, ionically bonded, hydrogen-bonded, and the like) to the surface of the article. The article can be incorporated into or as part of an article of footwear, and the cured coating can be on a surface of one or more portions (e.g., a bladder, a midsole, an upper, etc.) of the article of footwear that can be observed by a person viewing the article of footwear. When the cured coating includes a colorant, it can impart a decorative or aesthetically pleasing effect to the article.

[0045] The cured coating and coating composition can optionally include one or more colorants such as pigment particles or dyes. The cured coating can be a crosslinked polymer (e.g., a crosslinked polyurethane homopolymer or copolymer, such as a crosslinked polyester polyurethane) matrix in which the colorant is embedded. The pigment particles can be physically embedded in the crosslinked polymer matrix, chemically bound (e.g., covalently bound, ionically bound, hydrogen bond bound, and the like) to the matrix or product, or a combination of physical and chemical binding. The cured coating can have a thickness of about 0.01 pm to 1000 pm.

[0046] The cured coating can be a product of crosslinking a coating composition including an uncrosslinked polymer (or also referred to as a “crosslinking product”). In the coating composition, the uncrosslinked polymer can be dispersed in a carrier such as an organic solvent, water, or an aqueous solution. The uncrosslinked polymer can be a dispersion of uncrosslinked polymer, including an aqueous dispersion of uncrosslinked polymer, such as, for example, an aqueous dispersion of uncrosslinked polyurethane polymer, including an aqueous dispersion of uncrosslinked polyester polyurethane copolymer.

[0047] The term “aqueous” herein means that the carrier of the dispersion includes about 50 weight percent to 100 weight percent water, about 60 weight percent to 100 weight percent water, about 70 weight percent to 100 weight percent water, or about 100 weight percent water. The term “aqueous dispersion” refers to a dispersion of components (e.g., polymers, crosslinking agents, and the like) in water without a cosolvent. A cosolvent can be used in the aqueous dispersion, and the cosolvent can be an organic solvent.

[0048] The first polymeric material of the article can be elastic such that it can flex, expand, contract, bend, or a combination thereof when a force (e.g., pressure from the weight of a person walking in the article of footwear, a gripping force of a hand on the article of sporting equipment, pressure on the straps of a backpack, and the like) is applied (and / or maintained) to the article and then returns to the original shape after the force is removed. The cured coating is similarly elastic as the cured coating can flex, expand, contract, bend, or a combination thereof when a force is applied (and / or maintained) to the article and then returns to the original shape after the force is removed when the article is subjected to the force. One measure of the elastic property is the percent elongation at maximum, which can be determined as appropriate based on the form of the first polymeric material employed in the article using a variety of tensile test methods known in the art. For example, ASTM D638 can be used to test the tensile properties of plastics; ASTM D882 can be used to test the tensile properties of thin plastic sheeting; ASTM D4964-96 (2016) can be used to test textiles, and ISO 37 can be used to test the tensile stress-strain properties of rubbers.

[0049] The article and the cured coating are durable in that both retain their elastic properties after repeated application of force. The article having the cured coating disposed thereon can be a component in an article of footwear, such as a cushioning element. The article of footwear can be subjected to a variety of forces during use, where the use is repeated and of varying intensity, in different environments (e.g., temperature, humidity, exposure, and like conditions significantly varying indoors, outdoors), and the component and cured coating remain elastic over the average life of the article of footwear, such as at least 100 miles or 300 miles of wear. In examples, the article can be a cushioning element or bladder, where the cured coating can be disposed on an exterior surface, an interior surface, or both.

[0050] The cured coating can be incorporated into or disposed on an article, such as a textile. For example, the textile can include an article of footwear or a component thereof, an article of apparel (e.g., a shirt, a sweater, pants, shorts, gloves, eyewear, socks, a visor, a beanie, a jacket, an undergarment) or a component thereof, a container (e.g., a backpack, a bag), and a furnishing for furniture (e.g., a chair, a couch, a vehicle seat), bedding (e.g., a sheet, a blanket), a tablecloth, a towel, a flag, a tent, a sail, and a parachute. Further, the cured coating can be used in the production of or disposed on other articles of manufacture on an article, where the article can be a hitting device (e.g., a bat, a racket, a stick, a cane, a golf club, a paddle, etc.), sports equipment (e.g., a golf bag, baseball and football gloves, soccer constraining structures), protective equipment (e.g., a pad, a helmet, a guard, a visor, a mask, goggles, etc.), motorized equipment (e.g., a bicycle, a motorcycle, a skateboard, an automobile, a truck, a boat, a surfboard, a sled, a snowboard, etc.), a ball or puck for a variety of sports, fishing or hunting equipment, furniture, electronic equipment, building materials, eye protection, a timepiece, jewelry, and the like.

[0051] The article of footwear of the present disclosure can be designed for a variety of uses, such as sporting use, athletic use, military use, work-related use, recreational use, or leisure use. Primarily, the article of footwear is intended for outdoor use on un-paved surfaces (partially or entirely), such as on a ground surface that includes one or more of grass, turf, gravel, sand, dirt, clay, mud, and the like, whether as a sports playing surface or as a general outdoor surface. However, the article of footwear can also be desirable for indoor applications, such as, for example, indoor sports that include a dirt playing surface (e.g., an indoor baseball field with a dirt infield).

[0052] The article of footwear can be designed for outdoor sports activities, such as international football / soccer, golf, American football, rugby, baseball, running, track and field, cycling (e.g., road cycling and mountain biking), etc. The article of footwear can optionally include traction elements (e.g., lugs, cleats, studs, and spikes, and tread patterns) to provide traction on soft and slippery surfaces, where the elastomeric material can be between or among the traction elements, and optionally on the sides of the traction elements, rather than on the surfaces of the traction elements that contact the ground or surface. Cleats, studs, and spikes are typically included in footwear designed for sports such as international football / soccer, golf, American football, rugby, baseball, and similar sports, which are often played on un-paved surfaces. Lugs and / or enhanced tread patterns are typically included in footwear, including boots designed for use in harsh outdoor conditions such as trail running, hiking, and military use.

[0053] In the present disclosure, a cured coating can be disposed on a bladder that can be incorporated into an article such as footwear or a clothing garment. In this regard, one or more portions of the bladder can be exposed (e.g., not covered) so that a person viewing the article can see the cured coating. For example, the bladder can be used in a sole of a shoe, where one or more portions of the bladder are exposed or can otherwise be seen through an opening in the sole or other portion of the shoe. The present disclosure can provide articles in which a cured coating can be included on a bladder, which provides a robust and visually appealing article. The cured coating can provide a decorative feature for footwear.

[0054] The bladder can be incorporated into many different types of articles. For example, the bladder can be used as a cushioning element (e.g., a fluid-filled bladder) when inflated. The bladder can be included in, attached to, incorporated into an article such as an article of footwear, a component of footwear, a garment, a component of a garment, sports equipment, or a component of sports equipment. In particular, the manufactured article can include footwear, skates, a garment, a ball, a bag, a bicycle seat, a saddle, a personal protection article, a furniture article, or a novelty item. When used in footwear or skates, the bladder can be used as a cushioning element that is a component of a sole structure.

[0055] When the bladder is incorporated into footwear, the bladder can be incorporated into a sole that can be attached to an upper and other components to form the footwear. The sole and / or upper can be designed so that one or more portions of the bladder are not covered, include an opening, or otherwise exposed so that the crosslinked coating or crosslinked product on the bladder can be seen.

[0056] Figures 1-3An article of footwear is shown that includes a sole structure and a cushioning device made from the bladder of the present disclosure. The footwear 10 includes an upper 12 to which a sole 14 is attached. The upper 12 can be formed from a variety of conventional materials including, for example, textiles including leathers, vinyls, nylons and other generally woven and non-woven fiber materials. Generally, the upper 12 includes a reinforcement positioned around a toe 16, lacing eyelets 18, a top of the footwear 20 and along a heel region 22. As with most articles of footwear, the sole 14 generally extends the entire length of the footwear 10 from a toe region 16 through a midfoot region 24 and back to a heel portion 22.

[0057] Figure 3 FIG. 1 illustrates the surface of a midfoot bladder 28 with a cured coating 32 (for clarity, Figure 1 and Figure 2 not including the cured coating 32). Further, Figure 1 FIG. 2 illustrates the surface of a sole 14 with a cured coating 32.

[0058] The sole 14 includes one or more bladders 28 disposed in a midsole 26 of the sole structure. The bladder 28 can be formed to have a variety of geometries, such as more than one tubular member positioned in a spaced apart parallel relationship within a heel region 22 of the midsole 26. Many other geometries can be used and the bladder of the present disclosure is not limited to Figures 1-2 the bladder illustrated in FIG. 1. The tubular member is a sealed bladder containing an injected captive gas. Alternatively, the cushioning element can be formed from a foam polymer material.

[0059] The cured coating and coating compositions can include a colorant, such as a pigment (e.g., solid pigment particles) or a dye. The pigment particles can include inorganic pigments such as metals and metal oxides, such as uniform inorganic pigments, core-shell pigments, and the like, as well as carbon pigments (e.g., carbon black), clay pigments, and ultramarine pigments. The pigment particles can be biological or organic pigments. The pigment particles can be of the type known in the art as extender pigments, which include, but are not limited to, calcium carbonate, calcium silicate, mica, clay, silica, barium sulfate, and the like. The amount of pigment particles sufficient to achieve the desired color intensity, depth, and opacity can be in an amount of up to about 5 percent to 25 percent by weight of the cured coating or more. The pigments can include those sold by KP Pigments, such as pearl pigments, colorshift pigments (e.g., CALYPSO, JEDI, VERO, BLACKHOLE, LYNX, ROSE GOLD, and the like), hypershift pigments, interference pigments, and the like.

[0060] The colorant can be a dye, such as an anionic dye, a cationic dye, a direct dye, a metal complex dye, a basic dye, a disperse dye, a solvent dye, a polymeric dye, a polymeric dye colorant, or a nonionic dye, wherein the cured coating can include one or more dyes and / or one or more types of dyes. The dye can be a water-miscible dye. The dye can be a dissolved dye. The anionic dye can be an acid dye. The dye can be applied separately from the cured coating (e.g., before or after applying and / or curing the coating composition).

[0061] Acid dyes are water-soluble anionic dyes. Acid dyes are available in a wide range of shades, from dull tones to brilliant shades. Chemically, acid dyes include azo compounds, anthraquinone compounds, and triarylmethane compounds. The "Colour Index" (C.I.), jointly published by the Society of Dyers and Colourists (UK) and the American Association of Textile Chemists and Colorists (USA), is a comprehensive compilation of dyes and pigments used for large-scale colouring purposes, including 12000 products under 2000 C.I. generic names. In the C.I., each compound is provided with two numbers, which refer to the colour class and the chemical class. The "generic name" refers to the field of application and / or the colouring process, while the other number is the "constitution number".Examples of acid dyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110, 116, 127, 151, 158:1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246, and 250; Acid Red 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183, 184, 186, 194, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278, 283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419, and 447; Acid Violet 3, 5, 7, 17, 54, 90, and 92; Acid Brown 4, 14, 15, 45, 50, 58, 75, 97, 98, 147, 160:1, 161, 165, 191, 235, 239, 248, 282, 283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414, 420, 422, 425, 432, and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61, 67, 74, 80, 86, 94, 139, 142, 144, 154, and 162; Acid Blue 1, 7, 9, 15, 92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green 1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60, 64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, 235, and combinations of these. Acid dyes can be used alone or in any combination in the ink composition.

[0062] Acid dyes and non-ionic disperse dyes are commercially available from many sources, including Dystar L.P., Charlotte, NC, under the trade name TELON; Huntsman Corporation, woodsland, TX, USA, under the trade names ERIONYL and TECTILON; BASF SE, Ludwigshafen, Germany, under the trade name BASACID; and Bezema AG, Montlingen, Switzerland, under the trade name Bemacid.

[0063] The colorant can include a dye and a quaternary ammonium salt (e.g., a quaternary (tetraalkyl)ammonium salt), particularly when the dye is an acid dye. The quaternary ammonium salt can include four groups attached to the N atom, where each group can be independently selected from a hydrocarbon group R (e.g., R can be an alkyl group, such as a Ci to C6 alkyl group) or a non-hydrocarbon chain such as an ether (-C(O)-R1(e.g., R1can be an alkyl group, such as a Ci to C6 alkyl group)), an ester (-C(O)-O-R1(e.g., R1can be an alkyl group, such as a Ci to C6 alkyl group)), and an amide (-C(O)-NR1R2(e.g., R1and R2can each independently be an alkyl group, such as a Ci to C6 alkyl group)). The quaternary (tetraalkyl)ammonium salt can react with the dye (e.g., acid dye) to form a complexed dye that can be used to cure the coating. The “alkyl” group can include a Ci to Cio alkyl group. The quaternary (tetraalkyl)ammonium salt can be selected from a soluble tetrabutylammonium compound and a tetrahexylammonium compound. The counterion of the quaternary ammonium salt should be selected such that the quaternary ammonium salt forms a stable solution with the dye (e.g., anionic dye). The quaternary ammonium compound can be, for example, a halide (such as chloride, bromide, or iodide), a hydroxide, a sulfate, a sulfite, a carbonate, a perchlorate, a chlorate, a bromate, an iodate, a nitrate, a nitrite, a phosphate, a phosphite, a hexafluorophosphite, a borate, a tetrafluoroborate, a cyanide, an isocyanide, an azide, a thiosulfate, a thiocyanate, or a carboxylate (such as acetate or oxalate). The tetraalkylammonium compound can be or can include tetrabutylammonium halide or tetrahexylammonium halide, particularly tetrabutylammonium bromide or tetrabutylammonium chloride or tetrahexylammonium bromide or tetrahexylammonium chloride. The cured coating and coating composition (prior to curing) can include from about 1 to 15 weight percent of the quaternary ammonium salt. The molar ratio of acid dye to quaternary ammonium compound can range from about 4: 1 to 1 :4 or about 1.5: 1 to 1 : 1.5.

[0064] The cured coating and coating composition (e.g., monomers and / or polymers of the crosslinked polymeric matrix, or precursors to the cured coating) can include a crosslinking agent for crosslinking the uncrosslinked polymeric components of the coating composition. The crosslinking agent can be an aqueous crosslinking agent. The crosslinking agent can include one or more of a polycarboxylic acid crosslinking agent, an aldehyde crosslinking agent, a polyisocyanate crosslinking agent, or a combination thereof. The polycarboxylic acid crosslinking agent can be a polycarboxylic acid having from 2 to 9 carbon atoms. For example, the crosslinking agent can include a polyacrylic acid, a polymaleic acid, a copolymer of acids, a copolymer of maleic acid, fumaric acid, or 1,2,3,4-butanetetracarboxylic acid. The concentration of the crosslinking agent can be from about 0.01 to 5 weight percent or from 1 to 3 weight percent of the cured coating.

[0065] The cured coating and coating compositions (e.g., monomers and / or polymers of a crosslinked polymer matrix, or precursors of the cured coating) can include a solvent. The solvent can be an organic solvent. The organic solvent can be a water miscible organic solvent. The cured coating can not include water, or can be substantially free of water. For example, the solvent can be or include acetone, ethanol, 2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethyl ketone, 1-butanol, t-butanol, or any mixture thereof.

[0066] The crosslinking agent can include one or more of a polycarboxylic acid crosslinking agent, an aldehyde crosslinking agent, a polyisocyanate crosslinking agent, or combinations thereof. The polycarboxylic acid crosslinking agent can be a C2-C9 polycarboxylic acid. For example, the crosslinking agent can include polyacrylic acid, polymaleic acid, copolymers of acids, copolymers of maleic acid, fumaric acid, or 1,2,3,4-butanetetracarboxylic acid. The concentration of the crosslinking agent can be about 0.01 wt% to 5 wt%, or 1 wt% to 3 wt%, of the cured coating.

[0067] The coating composition can include a solvent. The solvent can be an organic solvent. The organic solvent can be a water miscible organic solvent. In one example, the organic solvent does not include water. For example, the solvent can be or can include acetone, ethanol, 2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethyl ketone, 1-butanol, t-butanol, or any mixture thereof.

[0068] Having now generally described the aspects of the disclosure, additional details regarding the polymer chemistry of the coating compositions, cured coatings, and the like, are provided. The uncured coating compositions of the present disclosure include uncrosslinked polymers, alone or optionally in combination with unpolymerized monomers and / or oligomers, as described below. The cured coatings of the present disclosure, which include a crosslinked polymer matrix, include crosslinked polymers, optionally in combination with uncrosslinked polymers, as described below. Additionally, the articles or components of articles of the present disclosure can be formed of a polymeric material including a polymer as described below. Additional components of the articles described herein can include a polymeric material including a polymer as described below.

[0069] The polymeric material of the article can be a foamed polymeric material. The polymeric material can be foamed and / or molded using a variety of methods. In one example, the foamed material can be foamed as part of an injection molding process or when the polymeric material is extruded into a mold or sheet. Optionally, the foamed material can be subsequently compression molded. Compression molding of the foamed material can change properties of the foamed material, such as reducing the compression set of the foamed material, which can be beneficial for foamed materials used in footwear-related applications. In one example, the foamed material can include a plurality of foam particles, wherein each individual foam particle of the plurality of foam particles is attached to at least one other individual foam particle of the plurality of foam particles.

[0070] The polymer can be a thermoset polymer or a thermoplastic polymer. The polymer can be an elastomeric polymer, including an elastomeric thermoset polymer or an elastomeric thermoplastic polymer. The polymer can be selected from the group consisting of polyurethanes (including elastomeric polyurethanes, thermoplastic polyurethanes (TPUs), and elastomeric TPU), polyesters, polyethers, polyamides, vinyl polymers (e.g., copolymers of vinyl alcohol, vinyl ester, ethylene, acrylate, methacrylate, styrene, etc.), polyacrylonitrile, polyphenylene ether, polycarbonate, polyurea, polystyrene, copolymers thereof (including polyester-polyurethane, polyether-polyurethane, polycarbonate-polyurethane, polyether block polyamide (PEBA), and styrene block copolymers), and any combination thereof, as described herein. The polymer can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, polyolefin copolymers of each, and combinations thereof.

[0071] The term “polymer” refers to a compound formed from a plurality of repeating structural units, referred to as monomers. Polymers are typically formed by a polymerization reaction in which a plurality of structural units become covalently bonded together. When the monomer units that form the polymer all have the same chemical structure, the polymer is a homopolymer. When the polymer includes two or more monomer units having different chemical structures, the polymer is a copolymer. One example of a copolymer type is a terpolymer, which includes three different types of monomer units. Copolymers can include two or more different monomers randomly distributed in the polymer (e.g., random copolymers). Alternatively, one or more blocks including a plurality of monomers of a first type can be joined to one or more blocks including a plurality of monomers of a second type, forming a block copolymer. Individual monomer units can include one or more different chemical functional groups.

[0072] A polymer having repeat units comprising two or more types of chemical functional groups can be referred to as having two or more segments. For example, a polymer having repeat units of the same chemical structure can be referred to as having repeating segments. Based on the chemical structure of the segments, segments are often described as being relatively hard or soft, and polymers often include relatively hard segments and relatively soft segments that are bound to one another in a single monomeric unit or different monomeric units. When a polymer includes repeating segments, physical interactions or chemical bonds can exist within or between segments, or both. Examples of segments often referred to as hard segments include segments comprising urethane linkages, which can be formed from reacting isocyanates with polyols to form polyurethanes. Examples of segments often referred to as soft segments include segments comprising alkoxy functional groups, such as segments comprising ether functional groups or ester functional groups, and polyester segments. Segments can be referred to based on the name of the functional group present in the segment (e.g., polyether segments, polyester segments), and based on the name of the chemical structure that reacted in order to form the segment (e.g., polyol-derived segments, isocyanate-derived segments). When referring to a segment of a particular functional group or a segment derived from a particular chemical structure, it is understood that the polymer can contain up to 10 mole percent of segments of other functional groups or segments derived from other chemical structures. For example, as used herein, polyether segments are understood to include up to 10 mole percent of non-polyether segments.

[0073] As previously described, the polymer can be a thermoplastic polymer. Generally, a thermoplastic polymer softens or melts when heated, and returns to a solid state when cooled. When the temperature of a thermoplastic polymer is raised to a temperature at or above its softening temperature, the thermoplastic polymer transitions from a solid state to a softened state, and when its temperature is raised to a temperature at or above its melting temperature, the thermoplastic polymer transitions to a liquid state. When sufficiently cooled, the thermoplastic polymer transitions from the softened or liquid state to the solid state. As such, a thermoplastic polymer can be softened or melted, molded, cooled, re-softened or re-melted, re-molded, and re-cooled through multiple cycles. For amorphous thermoplastic polymers, the solid state is understood to be a “rubbery” state above the glass transition temperature of the polymer. The thermoplastic polymer can have a melting temperature from about 90 °C to about 190 °C, and including all subranges therein in 1 degree increments, when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer can have a melting temperature from about 93 °C to about 99 °C when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer can have a melting temperature from about 112 °C to about 118 °C when determined according to ASTM D3418-97 as described herein below.

[0074] The glass transition temperature is the temperature at which an amorphous polymer transitions from a relatively brittle "glassy" state to a relatively more flexible "rubbery" state. The thermoplastic polymer can have a glass transition temperature from about -20 °C to about 30 °C when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer can have a glass transition temperature from about -13 °C to about -7 °C when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer can have a glass transition temperature from about 17 °C to about 23 °C when determined according to ASTM D3418-97 as described herein below.

[0075] The thermoplastic polymer can have a melt flow index from about 10 cubic centimeters per 10 minutes to about 30 cubic centimeters per 10 minutes (cm 3 / 10 min) when tested according to ASTM D1238-13 as described herein below at 160 °C using a weight of 2.16 kilograms (kg). 3 The thermoplastic polymer can have a melt flow index from about 22 cm 3 / 10 min to about 28 cm / 10 min when tested according to ASTM D1238-13 as described herein below at 160 °C using a weight of 2.16 kilograms (kg).

[0076] The thermoplastic polymer can have a cold sole compound flex test result of about 120,000 to about 180,000 cycles without cracking or whitening when tested according to the cold sole compound flex test as described herein below on a thermoformed substrate of the thermoplastic polymer. The thermoplastic polymer can have a cold sole compound flex test result of about 140,000 to about 160,000 cycles without cracking or whitening when tested according to the cold sole compound flex test as described herein below on a thermoformed substrate of the thermoplastic polymer.

[0077] The thermoplastic polymer can have a modulus of about 5 MegaPascals (MPa) to about 100 MPa when determined according to the ASTM D412-98 Standard Test Method for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers - Tension on a thermoformed substrate with the modifications described herein below. The thermoplastic polymer can have a modulus from about 20 MPa to about 80 MPa when determined according to the ASTM D412-98 Standard Test Method for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers - Tension on a thermoformed substrate with the modifications described herein below.

[0078] The polymer can be a thermoset polymer. As used herein, "thermoset polymer" is understood to mean a polymer that cannot be heated and melted because its melting temperature is at or above its decomposition temperature. A "thermoset material" refers to a material that includes at least one thermoset polymer. The thermoset polymer and / or thermoset material can be produced from a precursor (e.g., an uncured or partially cured polymer or material) using thermal energy and / or actinic radiation (e.g., ultraviolet radiation, visible light radiation, high-energy radiation, infrared radiation) to form a partially cured or fully cured polymer or material that no longer retains full thermoplasticity. In some cases, the cured or partially cured polymer or material can retain thermoset properties in that it can be partially softened and molded at elevated temperatures and / or pressures, but it is not possible to melt the polymer or material. For example, curing can be facilitated by using high pressure and / or a catalyst. In many instances, the curing process is irreversible because it results in cross-linking reactions and / or polymerization reactions of the precursor. The uncured or partially cured polymer or material can be malleable or liquid before curing. In some cases, the uncured or partially cured polymer or material can be molded into their final shape, or used as an adhesive. After hardening, the thermoset polymer or material cannot be melted to reshape. The textured surface can be formed by partially or fully curing the uncured precursor material to lock in the texture of the textured structure.

[0079] Polyurethane The polymer can be a polyurethane, such as a thermoplastic polyurethane (also referred to as "TPU"). Alternatively, the polymer can be a thermoset polyurethane. In addition, the polyurethane can be an elastomeric polyurethane, including an elastomeric TPU or an elastomeric thermoset polyurethane. The elastomeric polyurethane can include or consist of hard segments and soft segments. The hard segments can include or consist of urethane segments (e.g., isocyanate-derived segments). The soft segments can include or consist of alkoxy segments (e.g., polyol-derived segments including polyether segments, or polyester segments, or a combination of polyether segments and polyester segments). The polyurethane can include or consist essentially of an elastomeric polyurethane having repeating hard segments and repeating soft segments.

[0080] One or more polyurethanes can be produced by polymerizing one or more isocyanates with one or more polyols to produce a polymer chain having urethane linkages (N(CO)O-), as shown in Formula 1 below, where the isocyanates each preferably include two or more isocyanate (-NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups per molecule (although monofunctional isocyanates can optionally be included, e.g., as chain termination units).

[0081]

[0082] (Formula 1) Each R1group and R2group is independently an aliphatic group or an aromatic group. Optionally, each R2may be a relatively hydrophilic group, including groups having one or more hydroxyl groups.

[0083] Additionally, the isocyanate can also be chain-extended with one or more chain extenders to bridge two or more isocyanates, increasing the length of the hard segment. This can result in a polyurethane polymer chain as shown in Formula 2 below, where R3includes the chain extender. As with each R1and R2, each R3is independently an aliphatic functional group or an aromatic functional group.

[0084]

[0085] (Formula 2) Each R1group in Formula 1 and Formula 2 can independently include a linear or branched group having from 3 to 30 carbon atoms based on the particular isocyanate used, and can be aliphatic, aromatic, or include a combination of aliphatic and aromatic portions. The term “aliphatic” refers to a saturated or unsaturated organic molecule or portion of a molecule that does not include a cyclically conjugated ring system with delocalized p-electrons. In contrast, the term “aromatic” refers to an organic molecule or portion of a molecule that has a cyclically conjugated ring system with delocalized p-electrons that exhibits greater stability than an imaginary ring system with localized p-electrons.

[0086] Each R1group can be present in an amount of from about 5 percent by weight to about 85 percent by weight, from about 5 percent by weight to about 70 percent by weight, or from about 10 percent by weight to about 50 percent by weight, based on the total weight of the polymer-forming reactant compounds or monomers.

[0087] In aliphatic embodiments (from aliphatic isocyanates), each R1group can include a linear aliphatic group, a branched aliphatic group, a cycloaliphatic group, or combinations thereof. For example, each R1group can include a linear or branched alkylene group having from 3 to 20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, or an alkylene having from 6 to 10 carbon atoms), one or more cycloalkylene groups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof. As used herein, the term “olefin” or “alkylene” refers to a divalent hydrocarbon. When used in conjunction with the term C n When used in conjunction, it means that the olefin or alkylene group has “n” carbon atoms. For example, C 1-6Alkylene refers to an alkylene group having, for example, 1, 2, 3, 4, 5, or 6 carbon atoms.

[0088] Examples of suitable aliphatic diisocyanates for producing the polyurethane polymer chains include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), diisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), diisocyanatomethylcyclohexane, diisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), diisocyanatododecane, lysine diisocyanate, and combinations thereof.

[0089] The isocyanate-derived segments can include segments derived from aliphatic diisocyanates. A majority of the isocyanate-derived segments can include segments derived from aliphatic diisocyanates. At least 90 percent of the isocyanate-derived segments are derived from aliphatic diisocyanates. The isocyanate-derived segments can consist essentially of segments derived from aliphatic diisocyanates. The aliphatic diisocyanate-derived segments can be derived substantially (e.g., about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more) from linear aliphatic diisocyanates. At least 80 percent of the aliphatic diisocyanate-derived segments can be derived from aliphatic diisocyanates that do not contain pendant chains. The segments derived from aliphatic diisocyanates can include linear aliphatic diisocyanates having from 2 to 10 carbon atoms.

[0090] When the isocyanate-derived segments are derived from aromatic isocyanates, each R1group can include one or more aromatic groups, such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylenyl, indanyl, indenyl, anthryl, and fluorenyl. Unless otherwise specified, the aromatic groups can be unsubstituted aromatic groups or substituted aromatic groups, and can also include heteroaromatic groups. “Heteroaromatic” refers to monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring systems in which one to four ring atoms are selected from oxygen, nitrogen, or sulfur, and the remaining ring atoms are carbon, and in which the ring system is connected to the remainder of the molecule through any ring atom. Examples of suitable heteroaromatic groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, and benzothiazolyl groups.

[0091] Examples of suitable aromatic diisocyanates for producing polyurethane polymer chains include toluene diisocyanate (TDI), TDI adducts with trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 4,4'-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, and combinations thereof. The polymer chains can be substantially free of aromatic groups.

[0092] The polyurethane polymer chains can be produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof. For example, the polyurethane can include one or more polyurethane polymer chains produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof.

[0093] According to the present disclosure, at least partially crosslinked or crosslinkable polyurethane chains can be used. Crosslinked or crosslinkable polyurethane chains can be produced by reacting polyfunctional isocyanates to form polyurethanes. Examples of suitable triisocyanates for producing polyurethane chains include TDI, HDI, and IPDI adducts with trimethylolpropane (TMP), uretdiones (i.e., dimer isocyanates), polymeric MDI, and combinations thereof.

[0094] The R3groups in Formula 2 can include linear or branched groups having from 2 to 10 carbon atoms based on the particular chain extender polyol used, and can be, for example, aliphatic, aromatic, or ether or polyether. Examples of suitable chain extender polyols for producing polyurethanes include ethylene glycol, lower oligomers of ethylene glycol (e.g., di-, tri-, and tetraethylene glycol), 1,2-propanediol, 1,3-propanediol, lower oligomers of propylene glycol (e.g., dipropylene glycol, tripropylene glycol, and tetrapropylene glycol), 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g., bis(2-hydroxyethyl) ether of hydroquinone and resorcinol, xylene-a,a-diol, bis(2-hydroxyethyl) ether of xylene-a,a-diol), and combinations thereof.

[0095] The R2groups in Formula 1 and Formula 2 can include polyether groups, polyester groups, polycarbonate groups, aliphatic groups, or aromatic groups. Each R2group can be present in an amount of about 5 percent by weight to about 85 percent by weight, from about 5 percent by weight to about 70 percent by weight, or from about 10 percent by weight to about 50 percent by weight, based on the total weight of the reactant monomers.

[0096] The at least one R2group of the polyurethane includes a polyether segment (i.e., a segment having one or more ether groups). Suitable polyether groups include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof. The term “alkyl” as used herein refers to straight chain and branched chain, saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty carbon atoms, or one to ten carbon atoms. When used in conjunction with the term C n When used in conjunction, it means that the alkyl group has “n” number of carbon atoms. For example, C4alkyl refers to an alkyl group having 4 carbon atoms. C 1-7 Alkyl refers to alkyl groups having a number of carbon atoms encompassing the entire range (i.e., 1 to 7 carbon atoms) as well as all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7 carbon atoms). Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise specified, alkyl groups can be unsubstituted alkyl groups or substituted alkyl groups.

[0097] In some examples of the polyurethane, at least one R2group comprises a polyester group. The polyester group can be derived from the polyesterification of one or more dihydric alcohols (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-dihydroxyethane, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid, suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid, and citraconic acid, and combinations thereof). The polyester group can also be derived from polycarbonate prepolymers such as poly(hexamethylene carbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylene carbonate) glycol, and poly(nonanemethylene carbonate) glycol. Suitable polyesters can include, for example, polyethylene adipate (PEA), poly(1,4-butanediol adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly(propylene carbonate), poly(tetramethylene carbonate), poly(nonanemethylene carbonate), and combinations thereof.

[0098] At least one R2group can comprise a polycarbonate group. The polycarbonate group can be derived from the reaction of one or more dihydric alcohols (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-dihydroxyethane, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with ethylene carbonate.

[0099] The aliphatic group can be straight chained and can include, for example, an alkylene chain having from 1 to 20 carbon atoms or an alkenylene chain having from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term “olefin” or “alkylene” refers to a divalent hydrocarbon. The term “alkenylene” refers to a divalent hydrocarbon molecule or moiety having at least one double bond.

[0100] Aliphatic and aromatic groups can be substituted with one or more pendant, relatively hydrophilic and / or charged side groups. Hydrophilic side groups can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) hydroxyl groups. Hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) amino groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) carboxylate groups. For example, aliphatic groups can include one or more polyacrylic acid groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) sulfonate groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) phosphate groups. In some examples, hydrophilic side groups include one or more ammonium groups (e.g., tertiary and / or quaternary ammonium). In other examples, hydrophilic side groups include one or more zwitterionic groups (e.g., betaines such as poly(carboxybetaine) (pCB) and ammonium phosphonate groups such as phosphatidylcholine groups).

[0101] R2groups can include a charged group capable of binding a counterion to ionically crosslink the polymer and form an ionomer. For example, R2is an aliphatic group or an aromatic group having an amino side group, a carboxylate side group, a sulfonate side group, a phosphate side group, an ammonium side group, or a zwitterionic side group, or a combination thereof.

[0102] When present, the hydrophilic side group can be at least one polyether group, such as two polyether groups. In other cases, the hydrophilic side group is at least one polyester. The hydrophilic side group can be a polylactone group (e.g., polyvinylpyrrolidone). Each carbon atom in the hydrophilic side group can be optionally substituted with, for example, an alkyl group having from 1 to 6 carbon atoms. The aliphatic and aromatic groups can be graft polymer groups, where the side group is a homopolymer group (e.g., a polyether group, a polyester group, a polyvinylpyrrolidone group).

[0103] The hydrophilic side group can be a polyether group (e.g., a polyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), a polyvinylpyrrolidone group, a polyacrylic acid group, or a combination thereof.

[0104] The hydrophilic side groups can be bound to the aliphatic group or aromatic group through a linking group. The linking group can be any bifunctional small molecule (e.g., a bifunctional small molecule having from 1 to 20 carbon atoms) capable of linking the hydrophilic side group to the aliphatic group or aromatic group. For example, the linking group can include a diisocyanate group as previously described herein that forms a urethane linkage when linked to the hydrophilic side group and linked to the aliphatic group or aromatic group. The linking group can be 4,4’-diphenylmethane diisocyanate (MDI), as shown below.

[0105]

[0106] (Formula 3) The hydrophilic side group can be a polyethylene oxide group, and the linking group can be MDI, as shown below.

[0107]

[0108] (Formula 4) The hydrophilic side group can be functionalized to enable it to be optionally bound to the aliphatic group or aromatic group through a linking group. For example, when the hydrophilic side group includes an olefin group, the olefin group can undergo Michael addition with a thiol-containing bifunctional molecule (i.e., a molecule having a second reactive group such as a hydroxyl group or an amino group), resulting in a hydrophilic group that can be reacted with the polymer backbone using the second reactive group optionally through a linking group. For example, when the hydrophilic side group is a polyvinylpyrrolidone group, it can be reacted with a thiol group on mercaptoethanol to produce a hydroxyl-functionalized polyvinylpyrrolidone, as shown below.

[0109]

[0110] (Formula 5) At least one R2group in the polyurethane can include a polytetramethylene oxide group. At least one R2group in the polyurethane can include an aliphatic polyol group functionalized with a polyethylene oxide group or a polyvinylpyrrolidone group, such as the polyols described in European Patent No. 2 462 908, which is hereby incorporated by reference. For example, the R2group can be derived from the reaction product of a polyol (e.g., pentaerythritol or 2,2,3-trihydroxypropanol) with MDI-derivatized methoxypolyethylene glycol (to obtain a compound as shown in Formula 6 or Formula 7) or with MDI-derivatized polyvinylpyrrolidone (to obtain a compound as shown in Formula 8 or Formula 9), which have been previously reacted with mercaptoethanol, as shown below.

[0111]

[0112] (Formula 6)

[0113] (Formula 7)

[0114] (Formula 8)

[0115] (Formula 9) At least one R2in the polyurethane can be a polysiloxane. In these cases, the R2group can be derived from a siloxane monomer of Formula 10, such as the siloxane monomers disclosed in U.S. Patent No. 5,969,076, which is hereby incorporated by reference:

[0116] (Formula 10) where: a is 1 to 10 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); each R4is independently hydrogen, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms, an aryl group, or a polyether; and each R5is independently an alkylene group having from 1 to 10 carbon atoms, a polyether, or a polyurethane.

[0117] Each R4group can independently be H, an alkyl group having from 1 to 10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aryl group having from 1 to 6 carbon atoms, a polyethylene group, a polypropylene group, or a polybutylene group. Each R4group can independently be selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, ethenyl, propenyl, phenyl, and a polyethylene group.

[0118] Each R5group can independently include an alkylene group having from 1 to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene group). Each R5group can be a polyether group (e.g., a polyethylene group, a polypropylene group, or a polybutylene group). Each R5group can be a polyurethane group.

[0119] Optionally, the polyurethane can include a polymer network that is at least partially crosslinked, the polymer network including polymer chains that are derivatives of the polyurethane. The level of crosslinking can be such that the polyurethane retains thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane can melt and resolidify under the processing conditions described herein). The crosslinked polyurethane can be a thermoset polymer. As shown in Formula 11 and Formula 12 below, the crosslinked polymer network can be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polysulfhydryl compounds, or combinations thereof:

[0120] (Formula 11)

[0121] (Formula 12) wherein the variables are as described above. Additionally, the isocyanate can also be chain-extended with one or more polyamino or polysulfhydryl chain extenders to bridge two or more isocyanates, such as described previously for the polyurethane of Formula 2.

[0122] The polyurethane chains can be physically crosslinked to another polyurethane chain through, for example, nonpolar interactions or polar interactions between urethane or carbamate groups (hard segments) of the polymers. The R1groups in Formula 1, as well as the R1groups and R3groups in Formula 2, form polymer moieties that are commonly referred to as “hard segments,” and the R2groups form polymer moieties that are commonly referred to as “soft segments.” The soft segments are covalently bound to the hard segments. The polyurethane having physically crosslinked hard segments and soft segments can be a hydrophilic polyurethane (i.e., a polyurethane that includes a thermoplastic polyurethane that includes a hydrophilic group as disclosed herein).

[0123] The polyurethane can be a thermoplastic polyurethane comprising MDI, PTMO, and 1,4-butanediol, as described in U.S. Patent No. 4,523,005. Commercially available polyurethanes suitable for use in accordance with the present application include, but are not limited to, polyurethanes under the trade name “SANCURE” (e.g., the “SANCURE” family of polymers such as “SANCURE” 20025F) or “TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60) (Lubrizol, Countryside, IL, USA), “PELLETHANE” 2355-85ATP and 2355-95AE (Dow Chemical Company of Midland, MI, USA), “ESTANE” (e.g., ALR G 500 or 58213; Lubrizol, Countryside, IL, USA).

[0124] One or more of the polyurethanes (e.g., cured coating, coating composition (e.g., water-dispersible uncrosslinked polyurethane)) can be produced by polymerizing one or more isocyanates with one or more polyols to produce a copolymer chain having urethane linkages (-N(C=0)0-) and one or more water-dispersibility enhancing moieties, where the polymer chain comprises one or more water-dispersibility enhancing moieties (e.g., monomers in the polymer chain). The water-dispersible uncrosslinked polyurethane can also be referred to as a “waterborne uncrosslinked polyurethane polymer dispersion.” The water-dispersibility enhancing moieties can be added to the chain of Formula 1 or Formula 2 (e.g., added within the chain and / or as a side chain to the chain). The inclusion of the water-dispersibility enhancing moieties enables the formation of the waterborne uncrosslinked polyurethane dispersion. The term “waterborne” herein means that the continuous phase of the dispersion or formulation has about 50 weight percent to 100 weight percent water, about 60 weight percent to 100 weight percent water, about 70 weight percent to 100 weight percent water, or about 100 weight percent water. The term “waterborne dispersion” refers to a dispersion of components (e.g., polymers, crosslinkers, and the like) in water without a cosolvent. A cosolvent can be used in the waterborne dispersion, and the cosolvent can be an organic solvent. Additional details regarding the polymers, polyurethanes, isocyanates, and polyols are provided below.

[0125] Polyurethanes (e.g., aqueous, uncrosslinked polyurethane polymer dispersions) can include one or more water-dispersibility enhancing moieties. Water-dispersibility enhancing moieties can have at least one hydrophilic group (e.g., poly(ethylene oxide)), ionic groups, or potentially ionic groups to aid in the dispersion of the polyurethane, thereby enhancing the stability of the dispersion. Water-dispersible, uncrosslinked polyurethanes can be formed by incorporating moieties with at least one hydrophilic group or groups that can be made hydrophilic (e.g., by chemical modification such as neutralization) into the polymer chain. For example, these compounds can be nonionic, anionic, cationic, or zwitterionic or combinations thereof. In one example, anionic groups such as carboxylic acid groups can be incorporated into the chain in an inactive form and subsequently activated by a salt-forming compound such as a tertiary amine. Other water-dispersibility enhancing moieties can also be reacted into the backbone via urethane or urea linkages, including pendant or terminal hydrophilic ethylene oxide units or urea groups.

[0126] Water-dispersibility enhancing moieties can be moieties comprising carboxyl groups. Water-dispersibility enhancing moieties comprising carboxyl groups can be formed from hydroxyl-carboxylic acids having the general formula (HO) x Q(COOH) y where Q can be a divalent hydrocarbon radical containing from 1 to 12 carbon atoms, and x and y can each independently be from 1 to 3. Illustrative examples include dimethylol propanoic acid (DMPA), dimethylol butanoic acid (DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixtures thereof.

[0127] Water-dispersibility enhancing moieties can comprise reactive polymeric polyol components comprising anionic pendant groups that can be polymerized into the backbone to impart water-dispersibility properties to the polyurethane. Anionically functional polymeric polyols can include anionic polyester polyols, anionic polyether polyols, and anionic polycarbonate polyols, with additional details provided in U.S. Patent No. 5,334,690.

[0128] Water-dispersibility enhancing moieties can comprise pendant hydrophilic monomers. For example, water-dispersibility enhancing moieties comprising pendant hydrophilic monomers can include alkylene oxide polymers and copolymers, where the alkylene oxide groups have from 2-10 carbon atoms, as shown in U.S. Patent 6,897,281. Additional types of water-dispersibility enhancing moieties can include mercaptoacetic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol, and the like, and mixtures thereof. Additional details regarding water-dispersibility enhancing moieties can be found in U.S. Patent 7,476,705.

[0129] Polyamides The polymer can include a polyamide such as a thermoplastic polyamide or a thermoset polyamide. The polyamide can be an elastomeric polyamide including an elastomeric thermoplastic polyamide or an elastomeric thermoset polyamide. The polyamide can be a polyamide homopolymer having repeating polyamide segments of the same chemical structure. Alternatively, the polyamide can include a number of polyamide segments having different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments having different chemical structures can be arranged randomly or can be arranged as repeating blocks.

[0130] The polyamide can be a copolyamide (i.e., a copolymer including polyamide segments and non-polyamide segments). The polyamide segments of the copolyamide can include or consist of polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the copolyamide can be arranged randomly or can be arranged as repeating segments. The polyamide segments can include or consist of polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segments and polyamide 12 segments. In examples in which the polyamide segments of the copolyamide include polyamide 6 segments and polyamide 12 segments, the segments can be arranged randomly. The non-polyamide segments of the copolyamide can include or consist of polyether segments, polyester segments, or both polyether segments and polyester segments. The copolyamide can be a block copolyamide or can be a random copolyamide. The copolyamide can be formed from a polyamide oligomer or prepolymer and a second oligomer pre-polymer condensing to form a copolyamide (i.e., a copolymer including polyamide segments). Optionally, the second pre-polymer can be a hydrophilic pre-polymer.

[0131] The polyamide can be a polyamide-containing block copolymer. For example, the block copolymer can have repeating hard segments and repeating soft segments. The hard segments can include polyamide segments and the soft segments can include non-polyamide segments. The polyamide-containing block copolymer can be an elastomeric copolyamide including or consisting of a polyamide-containing block copolymer having repeating hard segments and repeating soft segments. In block copolymers including block copolymers having repeating hard segments and soft segments, physical crosslinks can exist within or between segments, or both within and between segments.

[0132] The polyamide segments of the polyamide itself or the polyamide-containing block copolymer can be derived from the condensation of a polyamide prepolymer such as a lactam, an amino acid, and / or a diamino compound with a dicarboxylic acid or an activated form thereof. The resulting polyamide segments include amide bonds (-(CO)NH-). The term “amino acid” refers to a molecule having at least one amino group and at least one carboxyl group. Each polyamide segment in the polyamide can be the same or different.

[0133] The polyamide or polyamide-containing block copolymer polyamide segment can be derived from the polycondensation of a lactam and / or amino acid, and can comprise an amide segment having the structure shown in Formula 13 below, where the R6group represents a polyamide moiety derived from a lactam or amino acid.

[0134]

[0135] (Formula 13) The R6group can be derived from a lactam. The R6group can be derived from a lactam group having from 3 to 20 carbon atoms, or a lactam group having from 4 to 15 carbon atoms, or a lactam group having from 6 to 12 carbon atoms. The R6group can be derived from capryl lactam or lauryl lactam. The R6group can be derived from one or more amino acids. The R6group can be derived from an amino acid group having from 4 to 25 carbon atoms, or an amino acid group having from 5 to 20 carbon atoms, or an amino acid group having from 8 to 15 carbon atoms. The R6group can be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

[0136] Optionally, to increase the relative degree of hydrophilicity of the polyamide- containing block copolymer, Formula 13 can include a polyamide-polyether block copolymer segment, as shown below:

[0137] (Formula 14) where m is 3-20, and n is 1-8. Optionally, m is 4-15 or 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be 11 or 12, and n can be 1 or 3. The polyamide or polyamide-containing block copolymer polyamide segment can be derived from the condensation of a diamino compound with a dicarboxylic acid or activated form thereof, and can comprise an amide segment having the structure shown in Formula 15 below, where the R7group represents a polyamide moiety derived from a diamino compound, and the R8group represents a moiety derived from a dicarboxylic acid compound:

[0138] (Formula 15) The R7group can be derived from a diamino compound comprising an aliphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbon atoms, or from 6 to 9 carbon atoms. The diamino compound can comprise an aromatic group, such as phenyl, naphthyl, xylyl, and cresyl. Suitable diamino compounds from which the R7group can be derived include, but are not limited to, hexamethylene diamine (HMD), tetramethylene diamine, trimethylhexamethylene diamine (TMD), meta-xylylene diamine (MXD), and 1,5-pentamine diamine. The R8group can be derived from a dicarboxylic acid or activated form thereof, including an aliphatic group having from 4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10 carbon atoms. The dicarboxylic acid or activated form thereof from which R8may be derived includes aromatic groups, such as phenyl, naphthyl, xylyl, and cresyl groups. Suitable carboxylic acids or activated forms thereof from which R8may be derived include adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. The polyamide chain can be substantially free of aromatic groups.

[0139] Each polyamide segment of the polyamide (including the polyamide-containing block copolymer) can independently be derived from a polyamide prepolymer selected from the group consisting of 12-aminolauric acid, caprolactam, hexamethylene diamine, and adipic acid.

[0140] The polyamide can include or consist essentially of a poly(ether-block-amide). The poly(ether-block-amide) can be formed from the polycondensation of a carboxylic acid-terminated polyamide prepolymer with a hydroxyl-terminated polyether prepolymer to form a poly(ether-block-amide), as shown in Formula 16:

[0141] (Formula 16) The poly(ether-block-amide) polymers can be prepared by polycondensation of a polyamide block containing a reactive end with a polyether block containing a reactive end. Examples include: 1) a polyamide block containing a diamine chain end with a polyalkylene oxide block containing a carboxylic acid chain end; 2) a polyamide block containing a dicarboxylic acid chain end with a polyalkylene oxide block containing a diamine chain end obtained by cyanoethylation and hydrogenation of an aliphatic dihydroxylated a-omega polyalkylene oxide known as a polyether diol; 3) a polyamide block containing a dicarboxylic acid chain end with a polyether diol, in this particular case the product obtained is a polyether ester amide. The polyamide segment of the poly(ether-block-amide) can be derived from a lactam, an amino acid, and / or a diamino compound with a dicarboxylic acid, as previously described. The polyether segment can be derived from one or more polyethers selected from the group consisting of polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof.

[0142] Poly(ether block amide) polymers can include those comprising polyamide blocks containing dicarboxylic chain ends derived from the condensation of an α,ω-aminocarboxylic acid, a lactam, or a dicarboxylic acid with a diamine in the presence of a chain-limiting dicarboxylic acid. In this type of poly(ether block amide) polymer, an α,ω-aminocarboxylic acid such as aminoundecanoic acid can be used; a lactam such as caprolactam or lauryl lactam can be used; a dicarboxylic acid such as adipic acid, sebacic acid, or dodecanedioic acid can be used; and a diamine such as hexamethylene diamine can be used; or various combinations of any of the foregoing. The copolymer can comprise polyamide blocks comprising polyamide 12 or polyamide 6.

[0143] Poly(ether block amide) polymers can include those comprising polyamide blocks and are of low mass, i.e. they have a number average molecular weight from 400 to 1000, said polyamide blocks being derived from the condensation of one or more α,ω-aminocarboxylic acids and / or one or more lactams containing from 6 to 12 carbon atoms in the presence of a dicarboxylic acid containing from 4 to 12 carbon atoms. In this type of poly(ether block amide) polymer, an α,ω-aminocarboxylic acid such as aminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylic acid such as adipic acid, sebacic acid, isophthalic acid, succinic acid, 1,4-cyclohexyl dicarboxylic acid, terephthalic acid, the sodium or lithium salt of sulfoisophthalic acid, dimer fatty acids having a dimer content of at least 98 weight percent and which are preferably hydrogenated, and dodecanedioic acid HOOC-(CH2) 10 -COOH; and a lactam such as caprolactam and lauryl lactam can be used; or various combinations of any of the foregoing. The copolymer can comprise polyamide blocks obtained by condensation of lauryl lactam in the presence of adipic acid or dodecanedioic acid and have a number average molecular weight of at least 750, with a melting temperature from about 127°C to about 130°C. The various components of the polyamide blocks and their proportions can be selected so as to obtain a melting point below 150°C or from about 90°C to about 135°C.

[0144] Poly(ether block amide) polymers can include those comprising polyamide blocks derived from the condensation of at least one a, w-amino carboxylic acid (or lactam), at least one diamine, and at least one dicarboxylic acid. In this type of copolymer, the a, w-amino carboxylic acid, lactam, and dicarboxylic acid can be selected from those described above, and diamines such as aliphatic diamines containing from 6 to 12 atoms can be used, and can be acyclic and / or saturated cyclic, such as but not limited to hexamethylene diamine, piperazine, 1-aminoethyl piperazine, diaminopropyl piperazine, tetramethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1,5-diamino hexane, 2,2,4-trimethyl-1,6-diamino hexane, diamine polyols, isophorone diamine (IPD), methyl penta methylene diamine (MPDM), bis(amino cyclohexyl) methane (BACM), and bis(3-methyl-4-aminocyclohexyl) methane (BMACM).

[0145] The polyamide can be a thermoplastic polyamide, and the components of the polyamide block and their proportions can be selected so as to obtain a melting temperature lower than 150°C, such as a melting point from about 90°C to about 135°C. The various components of the thermoplastic polyamide block and their proportions can be selected so as to obtain a melting point lower than 150°C, such as a melting point from about 90°C to about 135°C.

[0146] The number average molar mass of the polyamide block can be from about 300 g / mole to about 15,000 g / mole, from about 500 g / mole to about 10,000 g / mole, from about 500 g / mole to about 6,000 g / mole, from about 500 g / mole to about 5,000 g / mole, or from about 600 g / mole to about 5,000 g / mole. The number average molecular weight of the polyether block can be in the range from about 100 to about 6,000, from about 400 to about 3000, or from about 200 to about 3,000. The poly(ether block amide) polymer can have a polyether (PE) content (x) from about 0.05 to about 0.8 (i.e., from about 5 mole percent to about 80 mole percent). The polyether block can be present in the polyamide in an amount from about 10 weight percent to about 50 weight percent, from about 20 weight percent to about 40 weight percent, or from about 30 weight percent to about 40 weight percent. The polyamide block can be present in the polyamide in an amount from about 50 weight percent to about 90 weight percent, from about 60 weight percent to about 80 weight percent, or from about 70 weight percent to about 90 weight percent.

[0147] The polyether block can comprise units other than ethylene oxide units, such as, for example, propylene oxide or polytetrahydrofuran (which results in polybutylene glycol sequences). It is also possible to use PEG blocks, i.e. blocks consisting of ethylene oxide units, polypropylene glycol (PPG) blocks, i.e. blocks consisting of propylene oxide units, and poly(tetramethylene ether) glycol (PTMG) blocks, i.e. blocks consisting of tetramethylene glycol units, also known as polytetrahydrofuran, simultaneously. Advantageously, PPG blocks or PTMG blocks are used. The amount of polyether block in these copolymers containing polyamide blocks and polyether blocks can be from about 10 to about 50 weight percent, or from about 35 to about 50 weight percent of the copolymer.

[0148] The copolymers containing polyamide blocks and polyether blocks can be prepared by any means for attaching the polyamide blocks and the polyether blocks. In practice, essentially two processes are used, one is a two-step process, and the other is a one-step process.

[0149] In the two-step process, the polyamide blocks with dicarboxylic acid chain ends are first prepared, and then in a second step, these polyamide blocks are linked to the polyether blocks. The polyamide blocks with dicarboxylic acid chain ends are derived from the condensation of polyamide precursors in the presence of a chain terminator dicarboxylic acid. If the polyamide precursors are only lactams or a,ω-aminocarboxylic acids, a dicarboxylic acid is added. If the precursors already contain a dicarboxylic acid, this is used in excess relative to the stoichiometry of the diamines. The reaction typically occurs from about 180 °C to about 300 °C, such as from about 200 °C to about 290 °C, and the pressure in the reactor can be set from about 5 bar to about 30 bar, and maintained for about 2 to 3 hours. The pressure in the reactor is slowly reduced to atmospheric pressure, and then the excess water is distilled off, for example for one or two hours.

[0150] After the polyamide having carboxylic acid end groups has been prepared, the polyether, the polyol and the catalyst are added subsequently. The total amount of polyether can be divided into one or more portions and added in one or more portions, as can the catalyst. The polyether is added first and the reaction of the OH end groups of the polyether and the polyol with the COOH end groups of the polyamide starts, wherein ester bonds are formed and water is eliminated. As much water as possible is removed from the reaction mixture by distillation and then the catalyst is introduced in order to complete the linking of the polyamide blocks with the polyether blocks. This second step is carried out under stirring, preferably under vacuum of at least 50 mbar (5000 Pascal), at a temperature such that the reactants and the obtained copolymer are in the molten state. By way of example, the temperature can be from about 100°C to about 400°C, such as from about 200°C to about 250°C. The reaction is monitored by measuring the torque exerted on the stirrer by the polymer melt or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the torque or of the target power. Catalyst is defined as any product which facilitates the linking of the polyamide blocks with the polyether blocks by esterification. The catalyst can be a derivative of a metal (M) selected from the group formed by titanium, zirconium and hafnium. The derivative can be prepared from a tetraalkoxide salt complying with the general formula M(OR)4, wherein M represents titanium, zirconium or hafnium and R, which can be the same or different, represents a linear or branched alkyl group having from 1 to 24 carbon atoms.

[0151] The catalyst can comprise a salt of a metal (M), in particular a salt of (M) with an organic acid, and a complex salt of an oxide of (M) and / or a hydroxide of (M) with an organic acid. The organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid or crotonic acid. The organic acid can be acetic acid or propionic acid. M can be zirconium and such a salt is called a zirconyl salt, for example a commercially available product sold under the name zirconyl acetate.

[0152] The weight proportion of the catalyst can vary from about 0.01 percent to about 5 percent of the weight of the mixture of dicarboxylic acid polyamide with polyether glycol and polyol. The weight proportion of the catalyst can vary from about 0.05 percent to about 2 percent of the weight of the mixture of dicarboxylic acid polyamide with polyether glycol and polyol.

[0153] In a one-step process, the polyamide precursor, the chain terminator and the polyether are blended together; then what is obtained is a polymer with essentially highly variable lengths of polyether blocks and polyamide blocks, but also a plurality of reactants that have reacted randomly, distributed randomly along the polymer chain. They are the same reactants and the same catalyst as in the two-step process described above. If the polyamide precursor is only a lactam, it is advantageous to add a small amount of water. This copolymer has essentially the same polyether blocks and the same polyamide blocks, but also a small fraction of a plurality of reactants that have reacted randomly, distributed randomly along the polymer chain. As in the first step of the two-step process described above, the reactor is closed and heated under stirring. The determined pressure is from about 5 bar to about 30 bar. When the pressure no longer changes, the reactor is placed under reduced pressure, while still maintaining vigorous stirring of the molten reactants. The reaction is monitored as previously in the case of the two-step process.

[0154] The appropriate ratio of polyamide blocks to polyether blocks can be found in a single poly(ether block amide), or a blend of two or more poly(ether block amide) of different composition can be used with the appropriate average composition. It can be useful to blend a block copolymer with a high level of polyamide groups with a block copolymer with a higher level of polyether blocks to produce a blend with an average polyether block level of about 20 weight percent to about 40 weight percent, or about 30 weight percent to about 35 weight percent of the total blend of poly(amide-block-ether) copolymers. The copolymer can include a blend of two different poly(ether-block-amide) including at least one block copolymer with a polyether block level of less than 35 weight percent and a second poly(ether-block-amide) with at least 45 weight percent of polyether blocks.

[0155] Exemplary commercially available copolymers include, but are not limited to, copolymers available under the following trademarks or also other similar materials produced by other various suppliers: "VESTAMID" (Evonik Industries, Essen, Germany); "PLATAMID" (Arkema, Colombes, France), for example, product code H2694; "PEBAX" (Arkema), for example product codes "PEBAX MH1657" and "PEBAX MV1074"; "PEBAX RNEW" (Arkema); "GRILAMID" (EMS-Chemie AG, Domat-Ems, Switzerland).

[0156] The polyamides can be physically crosslinked by, for example, nonpolar or polar interactions between the polyamide groups of the polymer. In examples where the polyamide is a copolyamide, the copolyamide can be physically crosslinked by interactions between the polyamide groups and, optionally, by interactions between the copolymer groups. When the copolyamide is physically crosslinked by interactions between the polyamide groups, the polyamide segments can form portions of the polymer that are referred to as hard segments, and the copolymer segments can form portions of the polymer that are referred to as soft segments. For example, when the copolyamide is a poly(ether-block-amide), the polyamide segments form the hard segments of the polymer, and the polyether segments form the soft segments of the polymer. Thus, in some examples, the polymer can include a physically crosslinked polymer network having one or more polymer chains with amide bonds.

[0157] The polyamide segments of the copolyamides can include polyamide-11 or polyamide-12, and the polyether segments can be segments selected from the group consisting of polyethylene oxide segments, polypropylene oxide segments, and polytetramethylene oxide segments, and combinations thereof.

[0158] The polyamides can be partially or fully covalently crosslinked, as previously described herein. In some cases, the degree of crosslinking present in the polyamide is such that, when it is thermally processed, for example in the form of a yarn or fiber, to form an article of the present disclosure, the partially covalently crosslinked thermoplastic polyamide retains sufficient thermoplastic character such that the partially covalently crosslinked thermoplastic polyamide melts and resolidifies during processing. In other cases, the crosslinked polyamide is a thermoset polymer.

[0159] Polyesters The polymer can include a polyester. The polyester can include a thermoplastic polyester or a thermoset polyester. Further, the polyester can be an elastomeric polyester, including a thermoplastic polyester; or a thermoset elastomeric polyester. The polyester can be formed by the reaction of one or more carboxylic acids or ester-forming derivatives thereof with one or more di- or polyvalent aliphatic, cycloaliphatic, aromatic, or araliphatic alcohols or bisphenols. The polyester can be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester can include a number of polyester segments having different polyester chemical structures (e.g., polyglycolate segments, polylactate segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments having different chemical structures can be arranged randomly, or can be arranged as repeating blocks.

[0160] Exemplary carboxylic acids that can be used to make polyesters include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acids, alkyl-substituted or halogenated isophthalic acids, nitro-terephthalic acid, 4,4'-oxybenzene dicarboxylic acid, 4,4'-thiobenzene dicarboxylic acid, 4,4'-sulfone-benzene dicarboxylic acid, 4,4'-diphenyl alkylidene dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and cyclohexane-1,3-dicarboxylic acid. Exemplary diols or phenols suitable for making polyesters include, but are not limited to, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and bisphenol A.

[0161] The polyester can be polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyhexamethylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystalline polyester, or a blend or mixture of two or more of the foregoing.

[0162] The polyester can be a copolyester (i.e., a copolymer comprising polyester segments and non-polyester segments). The copolyester can be an aliphatic copolyester (i.e., a copolyester in which both the polyester segments and the non-polyester segments are aliphatic). Alternatively, the copolyester can comprise aromatic segments. The polyester segments of the copolyester can comprise or consist essentially of polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the copolyester can be arranged randomly, or can be arranged as repeating blocks.

[0163] For example, the polyester can be a block copolyester having repeating blocks of relatively hard, identically chemically structured polymeric units (hard segments) and repeating blocks of relatively soft, identically chemically structured (soft segments). In a block copolyester comprising a block copolyester having repeating hard segments and repeating soft segments, physical crosslinks can be present within or between blocks, or both. The polymer can comprise or consist essentially of an elastomeric copolyester having repeating hard segments and repeating soft segments.

[0164] The non-polyester segment of the copolyester can comprise or consist essentially of polyether segments, polyamide segments, or both polyether segments and polyamide segments. The copolyester can be a block copolyester, or can be a random copolyester. The copolyester can be formed from a polyester oligomer or prepolymer and a second oligomer prepolymer condensation to form a block copolyester. Optionally, the second prepolymer can be a hydrophilic prepolymer. For example, the copolyester can be formed from the condensation of terephthalic acid or naphthalene dicarboxylic acid with ethylene glycol, 1,4-butanediol, or 1,3-propanediol. Examples of copolyesters include polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and combinations thereof. The copolyamide can comprise or consist of polyethylene terephthalate.

[0165] The polyester can be a block copolymer comprising segments of one or more of polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyhexamethylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), and liquid crystalline polyester. For example, a suitable polyester as a block copolymer can be a PET / PEI copolymer, a polybutylene terephthalate / tetraethylene glycol copolymer, a polyoxyalkylene imide diacid / polybutylene terephthalate copolymer, or a blend or mixture of any of the foregoing copolymers.

[0166] The polyester can be a biodegradable resin, for example a copolyester in which a poly(alpha-hydroxy acid) such as polyglycolic acid or polylactic acid is included as a primary repeating unit.

[0167] The disclosed polyesters can be prepared by a variety of condensation methods known to the skilled artisan, such as a solvent polymerization process or a melt polymerization process.

[0168] Polyolefins The polymer can include or consist essentially of a polyolefin. The polyolefin can be a thermoplastic polyolefin or a thermoset polyolefin. Further, the polyolefin can be an elastomeric polyolefin, including a thermoplastic elastomeric polyolefin or a thermoset elastomeric polyolefin. Exemplary polyolefins can include polyethylenes, polypropylenes, and olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene with alpha-olefins having 4 to about 8 carbon atoms). The polyolefin can be a polymer including polyethylene, ethylene-alpha-olefin copolymer, ethylene-propylene rubber (EPDM), polybutene, polyisobutylene, poly-4-methyl-pent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymer, and olefin elastomers such as dynamically cross-linked polymers obtained from polypropylene (PP) and ethylene-propylene rubber (EPDM), and blends or mixtures of the foregoing. Additional exemplary polyolefins include polymers of cyclic olefins such as cyclopentene or norbornene.

[0169] It should be understood that the polyethylene that can be optionally cross-linked includes a variety of polyethylenes, including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE), and (ULDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra-high molecular weight polyethylene (HDPE-UHMW), and blends or mixtures of any of the foregoing polyethylenes. The polyethylene can also be a polyethylene copolymer derived from monomers of mono-olefins and di-olefins copolymerized with vinyl, acrylic, methacrylic, ethyl acrylate, vinyl alcohol, and / or vinyl acetate. The polyolefin copolymer containing vinyl acetate derived units can be a high vinyl acetate content copolymer, for example, greater than about 50 weight percent of vinyl acetate derived composition.

[0170] The polyolefins can be formed via free radical polymerization, cationic polymerization, and / or anionic polymerization by methods well known to those skilled in the art (e.g., using peroxide initiators, heat, and / or light). The disclosed polyolefins can be prepared by free radical polymerization at high pressure and at elevated temperatures. Alternatively, the polyolefins can be prepared by catalytic polymerization using a catalyst, which typically contains one or more metals from Group IVb, Group Vb, Group VIb, or Group VIII metals. The catalyst typically has one or more ligands complexed with the Group IVb, Group Vb, Group VIb, or Group VIII metal, typically an oxide, halide, alcoholate, ester, ether, amine, alkyl, alkenyl, and / or aryl that can be either a pi- or ortho-ligand. The metal complex can be in a free form or immobilized on a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina, or silica. The metal catalyst can be soluble or insoluble in the polymerization medium. The catalyst can be used alone for polymerization, or an additional activator can be used, typically a Group la, Group Ila, and / or Group Ilia metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide, or metal alkyloxane. The activator can be conveniently modified with additional ester groups, ether groups, amine groups, or silyl ether groups.

[0171] Suitable polyolefins can be prepared by polymerization of monomers of mono-olefins and di-olefins as described herein. Exemplary monomers that can be used to prepare polyolefins include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof.

[0172] Suitable ethylene-a-olefin copolymers can be obtained by copolymerization of ethylene with a-a-olefins such as propylene, 1-butene, 1-hexene, octene-1, 4-methyl-1-pentene, or the like having a carbon number of 3 to 12.

[0173] Suitable dynamically crosslinked polymers can be obtained by crosslinking a rubber component as a soft segment, while physically dispersing a hard segment such as PP and a soft segment such as EPDM by using a kneader such as a Banbury mixer and a twin-screw extruder.

[0174] The polyolefins can be a mixture of polyolefins, such as a mixture of two or more polyolefins disclosed herein above. For example, suitable polyolefin mixtures can be a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), or a mixture of different types of polyethylene (e.g., LDPE / HDPE).

[0175] The polyolefin can be a copolymer of a suitable mono-olefin monomer or a copolymer of a suitable mono-olefin monomer and a vinyl monomer. Exemplary polyolefin copolymers include ethylene / propylene copolymers, linear low density polyethylene (LLDPE), and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methyl pentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers, and salts thereof (ionomers), as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.

[0176] The polyolefin can be a polypropylene homopolymer, a polypropylene copolymer, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a polyethylene block copolymer, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a medium density polyethylene, a high density polyethylene (HDPE), or a blend or mixture of one or more of the foregoing polymers.

[0177] The polyolefin can be a polypropylene. As used herein, the term "polypropylene" is intended to encompass any polymeric composition comprising propylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes or other monomers such as ethylene, butene and the like. Such term also encompasses any different configuration and arrangement of the constituent monomers, such as atactic, syndiotactic, isotactic, and the like. Thus, this term as applied to fibers is intended to encompass the actual long threads, tapes, sutures and the like of drawn polymers. The polypropylene can have any standard melt flow (by test); however, standard fiber grade polypropylene resins have a melt flow index range between about 1 and 1000.

[0178] The polyolefin can be a polyethylene. As used herein, the term "polyethylene" is intended to encompass any polymeric composition comprising ethylene monomers, either alone or in mixtures or copolymers with other randomly selected and oriented polyolefins, dienes, or other monomers such as propylene, butylene, and the like. Such term also encompasses any different configurations and arrangements of the constituent monomers, such as atactic, syndiotactic, isotactic, and the like. Thus, this term as applied to fibers is intended to encompass the actual long threads, tapes, sutures, and the like of drawn polymer. The polyethylene can have any standard melt flow (by test); however, standard fiber grade polyethylene resins have a melt flow index in the range of between about 1 and 1000.

[0179] The polymeric components of the polymeric material on the surface of the article or forming the article consist of all polymers present in the polymeric material. The polymeric components can consist essentially of one or more polyurethane homopolymers, one or more polyurethane copolymers, or any combination thereof. The polymeric components can consist essentially of one or more polyether homopolymers, one or more polyether copolymers, or any combination thereof.

[0180] The polymeric components can consist essentially of one or more polyester homopolymers, one or more polyester copolymers, or any combination thereof. The polymeric components can consist essentially of one or more polyisoprene homopolymers or copolymers, one or more polybutadiene homopolymers or copolymers, or any combination thereof. The polymeric components can consist essentially of one or more vinyl acetate homopolymers or copolymers, one or more styrene homopolymers or copolymers, or any combination thereof. The polymeric components can consist essentially of one or more olefin homopolymers or copolymers. The polymeric components can consist essentially of one or more olefin homopolymers.

[0181] In reference to "consisting essentially of," the polymeric material does not include a substantial amount (e.g., greater than about 1 wt%) of a polymer type other than those listed, although the material can include non-polymeric ingredients such as fillers, pigments, UV absorbers, and the like.

[0182] The cured coating and coating composition can optionally include additives, fillers, lubricants, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, fungicides, antibacterial agents, combinations thereof, or the like. In addition, the cured coating and coating composition can optionally include monomers, oligomers, thermal initiators, photoinitiators, and catalysts.

[0183] Additives can include, but are not limited to, processing aids, antioxidants, ultraviolet light stabilizers, optical brighteners, extenders, solid and liquid colorants, fillers, coupling agents, plasticizers, rheology modifiers, stabilizers, matting agents, antimicrobials, antistatic agents, and other functional additives, as well as combinations of additives.

[0184] Fillers can be used to increase strength, abrasion resistance, alter thermal properties, reduce cost, and alter the viscosity, thixotropy, or bulk fluid flow properties of the elastomer composition. The amount of filler (e.g., in terms of “phr” or parts by weight based on 100 parts of the elastomer) can vary to achieve the desired effective properties, such as strength, viscosity, and the like.

[0185] Fillers can include, but are not limited to, clay, talc, asbestos, graphite, glass, mica (such as phlogopite, biotite, iron lithia mica, white mica, sodium mica, green mica, and glaukophanite, clintonite, pennantite, nickel chlorite, chlorite, donbasite, clintonite, green mica, mangan mica, antigorite, pennine, amosite, anthophyllite, tremolite, actinolite, hornblende, magnesio hornblende, tephritite, nickel chlorite, pennantite, and the like), calcium metasilicate, alumina, zinc sulfide, aluminum hydroxide, silica (such as amorphous silica, amorphous synthetic silica, and colloidal silica), silicates (such as actinolite, tourmaline, serpentine, aluminosilicates, and the like), silicon carbide, diatomite, carbonates (such as barium carbonate, calcium carbonate, magnesium carbonate, and the like), kaolin (such as delaminated kaolin, calcined kaolin, and the like), metals (such as titanium, tungsten, zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, bronze, cobalt, beryllium, and alloys of these), metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, and the like), suitable organic fillers include, but are not limited to, carbon black, fullerene, and / or carbon nanotubes, melamine colophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters, carbon fibers or mixtures thereof, particulate synthetic plastics (such as high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomeric resin, polyamide, polyester, polyurethane, polyimide, and the like), particulate carbonaceous materials (such as carbon black and the like), sulfates (such as calcium sulfate, magnesium sulfate, barium sulfate, and the like), and cotton flock, cellulose flock, cellulose pulp, leather fibers, and combinations of any of the above. The disclosed fillers can be in spherical, acicular, platelet form, and the like, or irregular forms. The fillers can be high aspect ratio fillers. Such fillers can be organic or inorganic. The high aspect ratio fillers can be inorganic microfibers, such as whiskers (highly crystalline, small single crystal fibers), or slightly less perfect crystalline fibers such as boron fibers, potassium titanate, calcium sulfate, asbestos, and calcium metasilicate. Typical levels of these and other fillers include from about 10 phr to 100 phr or more (where "phr" means parts by weight based on 100 parts of elastomer). The compositions can include about 10-80 phr, 30-70 phr, 40-60 phr, or 50-60 phr of filler. The elastomer compositions include a silica filler. Typical levels of the silica filler include from about 10 phr to 100 phr or more.The composition includes about 10-80 phr, 30-70 phr, 10-60 phr, 40-60 phr, 50-60 phr, or 35-60 phr of the filler.

[0186] The additive can be a softener (also referred to herein as a softening agent). Examples of suitable softeners include, but are not limited to, ethoxylated products of higher fatty acids, fatty alcohols, or fatty acid amides, N-stearyl-urea compounds, and stearylamidomethylpyridinium.

[0187] The additive can be a leveling agent. Examples of leveling agents include, but are not limited to, water-soluble salts of acidic esters obtained from polybasic acids, and ethylene oxide or propylene oxide adducts of relatively long chain base molecules capable of undergoing alkoxylation.

[0188] A cured coating disposed on an article (e.g., a surface comprising a polymeric material) can be effective to reduce the level of UV reaching the polymeric material forming the article compared to the substantially same article without the cured coating. For example, the cured coating can be effective to block at least some UV light (e.g., at least 5 percent, or at least 10 percent, or 20 percent or more) from reaching the underlying polymeric material, thereby protecting the polymeric material and reducing yellowing of the polymeric material. This can be advantageous for polymeric materials including polyamide homopolymers and copolymers, which are more susceptible to UV degradation and yellowing than other polymers.

[0189] A cured coating disposed on an article can reduce the level of water reaching a first polymeric material forming the article compared to the substantially same article without the cured coating. For example, the cured coating can be effective to block at least some water (e.g., at least 5 percent, or at least 10 percent, or 20 percent or more) from reaching the underlying polymeric material, thereby reducing the amount of water that can be absorbed by the polymeric material. This can be advantageous for materials that are relatively hydrophilic and wick enough water to significantly increase the weight of the article.

[0190] Having now described aspects of articles having cured coatings and coating compositions, additional details are provided regarding manufacturing cured coatings and coating compositions. Methods of manufacturing coated articles can include applying a coating composition to a first side of an article. The applying can include spray coating (e.g., using a spray gun), brushing, or dip coating the coating composition or a precursor thereof onto a surface of the article. The article has a first side comprising a first polymeric material, and the applying includes contacting the first polymeric material with the coating composition. Subsequently, the coating composition on the polymeric material can be cured. The curing can include heating the coating composition to about 50 °C to 90 °C or about 60 °C to 80 °C for about 1 minute or about 5 minutes or more.

[0191] The methods can include applying a dye to a side of the article before or after disposing and curing the coating composition. The methods can include printing on the fiber (e.g., three-dimensional printing) using an ink or a polymeric material before or after disposing and curing the coating composition. The methods can include treating the article before applying the coating composition in order to improve the bond of the cured coating to the article. For example, the treating can include applying a primer or tie layer to the article, washing the article to remove dirt or spin finish, applying an oxidation treatment such as a plasma treatment or a corona treatment, and the like.

[0192] The first polymeric material of the article can be a molded resin material. The resin material can be molded before or after applying the coating composition. The molding of the resin material includes injection molding the resin material.

[0193] The first polymeric material of the article can be a foam material. The methods can further include forming the foam material before applying the coating composition. The foaming of the foam material can include injection molding a molten thermoplastic material including a chemical or physical blowing agent and foaming the molten thermoplastic material including the chemical or physical blowing agent. The foaming of the foam material can include extruding a molten thermoplastic material including a chemical or physical blowing agent and foaming the molten thermoplastic material including the chemical or physical blowing agent. The first polymeric material of the article is a foam material, and the foam material can be compression molded before applying the coating composition. The first polymeric material of the article is a film. The film can be thermoformed before applying the coating composition or after applying the coating composition.

[0194] Having now described aspects of the present disclosure, additional details are provided regarding a bladder having a cured coating disposed thereon. The cured coating can be disposed (e.g., the coating composition can be cured) on the inner surface and / or the outer surface. The bladder is a bladder that can include a volume of fluid. An unfilled bladder is a bladder that is fillable with fluid, and a filled bladder is a bladder that has been at least partially inflated with fluid at a pressure equal to or greater than atmospheric pressure. When disposed onto or incorporated into an article of footwear, an article of apparel, or an article of sports equipment, the bladder is typically a fluid-filled bladder at that time. The fluid can be a gas or a liquid. The gas can include air, nitrogen (N2), or other suitable gas.

[0195] The bladder can have a gas permeability to nitrogen, for example, where a given thickness of the bladder wall has a gas permeability to nitrogen that is at least about ten times lower than a gas permeability to nitrogen of a butyl rubber layer having a thickness that is substantially the same as a thickness of the bladder described herein. The bladder can have a first bladder wall having a first bladder wall thickness (e.g., about 0.1 mil to 40 mil). The bladder can have a first bladder wall that can have a gas permeability to nitrogen of less than about 15 cm 3 / m 2 •atm•day, less than about 10 cm 3 / m 2 •atm•day, less than about 5 cm 3 / m 2 •atm•day, less than about 1 cm 3 / m 2 •atm•day (e.g., from about 0.001 cm 3 / m 2 •atm•day to about 1 cm 3 / m 2 •atm•day, about 0.01 cm 3 / m 2 •atm•day to about 1 cm 3 / m 2 •atm•day, or about 0.1 cm 3 / m 2 •atm•day to about 1 cm 3 / m 2 •atm•day). The bladder can have a first bladder wall having a first bladder wall thickness, where the first bladder wall has a gas permeability to nitrogen of 15 cm 3 / m 2 •atm•day or less.

[0196] The bladder has a bladder wall having an interior-facing side and an exterior-facing side, wherein the interior-facing side bounds at least a portion of an interior region of the bladder. The cured coating can be disposed on the exterior-facing side of the bladder, the interior-facing side of the bladder, or both.

[0197] The bladder can include a top wall operatively secured to the upper of the article of footwear, a bottom wall opposite the top wall, and one or more sidewalls extending between the top wall and the bottom wall of the inflated bladder. The top wall, the bottom wall, and the one or more sidewalls collectively bound an interior region of the inflated bladder, and wherein the one or more sidewalls each include an exterior-facing side.

[0198] A recognized method for measuring relative gas transmission, permeation, and diffusion for an inflated bladder is ASTM D-1434-82-V. See, for example, U.S. Patent No. 6,127,026, which is incorporated by reference as if fully set forth herein. According to ASTM D-1434-82-V, the transmission, permeation, and diffusion are measured by the following equations: Transmittance (quantity of gas) / [(area) x (time) x (pressure differential)] = transmission (GTR) / (pressure differential) = cm 3 / m 2 • atm • days (i.e., 24 hours) Permeability (quantity of gas) x (membrane thickness) [(area) x (time) x (pressure differential)] = permeation [(GTR) x (membrane thickness)] / (pressure differential) = [(cm 3 )(mil)] / m 2 • atm • days (i.e., 24 hours) Diffusion at one atmosphere (quantity of gas) / [(area) x (time)] = GTR = cm 3 / m 2 • days (i.e., 24 hours).

[0199] The bladder can include a bladder wall including a membrane including at least one polymeric layer or at least two or more polymeric layers. The thickness of each polymeric layer can be about 0.1 mil to 40 mil. The cured coating can be disposed on the membrane. In embodiments, the cured coating can be disposed between one or more layers of the bladder wall.

[0200] The polymer layer can be formed from a polymer material such as a thermoplastic material as described above and herein. The thermoplastic material can include an elastomeric material such as a thermoplastic elastomeric material. The thermoplastic material can include a thermoplastic polyurethane (TPU) such as those described above and herein. The thermoplastic material can include a polyester-based TPU, a polyether-based TPU, a polycaprolactone-based TPU, a polycarbonate-based TPU, a polysiloxane-based TPU, or combinations thereof. Non-limiting examples of thermoplastic materials that can be used include: “PELLETHANE” 2355-85A TP and 2355-95AE (Dow Chemical Company of Midland, MI., USA), “ELASTOLLAN” (BASF Corporation, Wyandotte, MI, USA), and “ESTANE” (Lubrizol, Brecksville, OH, USA), all of which are either ester-based or ether-based. Additional thermoplastic materials can include those described in U.S. Patent Nos. 5,713,141; 5,952,065; 6,082,025; 6,127,026; 6,013,340; 6,203,868; and 6,321,465, which are incorporated herein by reference.

[0201] The polymer layer can be formed from one or more of the following: ethylene-vinyl alcohol copolymer (EVOH), poly(vinyl chloride), polyvinylidene polymers and copolymers (e.g., polyvinylidene dichloride), polyamide (e.g., amorphous polyamide), acrylonitrile polymers (e.g., acrylonitrile-methyl acrylate copolymer), polyurethane engineering plastics, polymethylpentene resins, ethylene-carbon monoxide copolymers, liquid crystal polymers, polyethylene terephthalate, polyetherimide, polyacrylimide, and other polymer materials known to have a relatively low gas permeability. Also suitable are blends and alloys of these materials and blends and alloys with the TPU described herein, and optionally including combinations of polyimide and crystalline polymers. For example, blends of polyimide and liquid crystal polymers, blends of polyamide and polyethylene terephthalate, and blends of polyamide with styrenics are suitable.

[0202] Specific examples of polymeric materials of the polymeric layers can include acrylonitrile copolymers such as the "BAREX" resins available from Ineos (Rolle, Switzerland); polyurethane engineering plastics such as "ISPLAST" ETPU available from Lubrizol (Brecksville, OH, USA); ethylene-vinyl alcohol copolymers sold under the trade name "EVAL" by Kuraray (Houston, TX, USA), sold under the trade name "SOARNOL" by Nippon Gohsei (Hull, England), and sold under the trade name "SELAR OH" by DuPont (Wilmington, DE, USA); polyvinylidene chloride available from S.C. Johnson (Racine, WI, USA) under the trade name "SARAN" and from Solvay (Brussels, Belgium) under the trade name "IXAN"; liquid crystal polymers such as "VECTRA" from Celanese (Irving, TX, USA) and "XYDAR" from Solvay; "MDX6" nylon, and amorphous nylon such as "NOVAMID" X21 from Koninklijke DSM N.V (Heerlen, Netherlands), "SELAR PA" from DuPont; polyetherimides sold under the trade name "ULTEM" by SABIC (Riyadh, Saudi Arabia); poly(vinyl alcohol)s; and polymethylpentene resins available from Mitsui Chemicals (Tokyo, Japan) under the trade name "TPX".

[0203] Each polymeric layer of the film can be formed from a thermoplastic material, which can include a combination of thermoplastic polymers. In addition to one or more thermoplastic polymers, the thermoplastic material can optionally include colorants, fillers, processing aids, free radical scavengers, ultraviolet light absorbers, and the like. Each polymeric layer of the film can be made from a different thermoplastic material, which includes a different type of thermoplastic polymer.

[0204] Bags can be made by applying heat, pressure, and / or vacuum to a film. Bags (e.g., one or more polymeric layers) can be formed using one or more polymeric materials and using one or more processing techniques including, for example, extrusion, blow molding, injection molding, vacuum molding, rotational molding, transfer molding, compression molding, heat sealing, casting, low pressure casting, spin casting, reaction injection molding, radio frequency (RF) welding, and the like. Bags can be made by co-extrusion, followed by heat sealing or welding to produce an inflatable bag, which can optionally include one or more valves (e.g., one-way valves) that allow the bag to be filled with a fluid (e.g., a gas).

[0205] Item: Item 1. An article comprising: an article having a first side comprising a first polymeric material; and a cured coating disposed on the first polymeric material of the first side, wherein the cured coating comprises a crosslinked polymeric matrix, optionally wherein the first polymeric material is elastic and the cured coating is elastic.

[0206] Item 2. The article of item 1, wherein the cured coating is the product of crosslinking a coating composition comprising a dispersion of uncrosslinked polymer in a carrier to form the crosslinked polymeric matrix.

[0207] Item 3. The article of any preceding item, wherein the cured coating comprises a plurality of pigment particles embedded in the crosslinked polymeric matrix, optionally wherein the pigment particles are selected from the group consisting of metallic and metal oxide pigments, carbon pigments, clay pigments, ultramarine pigments, and combinations thereof.

[0208] Item 4. The article of any preceding item, wherein the cured coating further comprises a dye, optionally wherein the dye is an acid dye.

[0209] Item 5. The article of any preceding item, wherein the cured coating is an elastic cured coating, optionally wherein the elastic cured coating has an elongation of at least 100 percent or at least 200 percent.

[0210] Item 6. The article of any preceding item, wherein the crosslinked polymeric matrix comprises a crosslinked polyurethane homopolymer or copolymer or both, and optionally comprises a crosslinked polyester polyurethane.

[0211] Item 7. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising a dispersion of an uncrosslinked polyurethane polymer in the carrier, and optionally wherein the uncrosslinked polyurethane polymer is an elastomeric polyurethane polymer.

[0212] Item 8. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising a dispersion of an uncrosslinked polyurethane polymer in the carrier, and optionally wherein the uncrosslinked polyurethane polymer is a thermoplastic polyurethane polymer.

[0213] Item 9. The article of any preceding item, wherein the cured coating is the product of crosslinking the coating composition comprising a dispersion of an uncrosslinked polymer in the carrier, and wherein the dispersion of the uncrosslinked polymer is an aqueous dispersion of an uncrosslinked polymer and the carrier is water or an aqueous solution.

[0214] Item 10. The article of any preceding item, wherein the cured coating is the product of crosslinking the coating composition comprising a dispersion of an uncrosslinked polymer and a crosslinking agent in the carrier, optionally wherein the crosslinking agent is an aqueous crosslinking agent and the carrier is water or an aqueous solution.

[0215] Item 11. The article of any preceding item, wherein the cured coating is the product of crosslinking the coating composition comprising an uncrosslinked polymer in the carrier and a dispersion of more than one pigment particle dispersed in the carrier; optionally wherein the pigment particles are selected from the group consisting of metallic and metal oxide pigments, carbon pigments, clay pigments, ultramarine pigments, and combinations thereof.

[0216] Item 12. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising an uncrosslinked polymer in the carrier and a dispersion of a dye dispersed or dissolved in the carrier; optionally wherein the dye is an acid dye.

[0217] Item 13. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising an uncrosslinked polymer in the carrier and a dispersion of an acid dye and a quaternary ammonium compound dispersed or dissolved in the carrier; optionally wherein the quaternary ammonium compound is a tetrabutyl ammonium compound; or optionally wherein the quaternary ammonium compound is a tetrabutyl ammonium halide.

[0218] Item 14. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising an uncrosslinked polymer in the carrier and a dispersion or dissolution of an acid dye and a quaternary ammonium compound in the carrier; optionally wherein the coating composition comprises from about 1 weight percent to about 15 weight percent of the quaternary ammonium compound, or wherein the molar ratio of the acid dye to the quaternary ammonium compound in the coating composition ranges from about 4: 1 to about 1 :4 or from about 1.5: 1 to about 1 : 1.5.

[0219] Item 15. The article of any preceding item, wherein the cured coating is the product of crosslinking a coating composition comprising a dispersion of an uncrosslinked polymer in a solution comprising an organic solvent, optionally wherein the solution is an aqueous solution and the organic solvent is a water-miscible organic solvent.

[0220] Item 16. The article of any preceding item, wherein the first polymeric material is a solid resin material, and optionally the first polymeric material is a molded resin material.

[0221] Item 17. The article of any preceding item, wherein the first polymeric material is a foam material, or optionally the foam material is an injection-molded foam or an extruded foam, or optionally the foam material is a compression-molded foam, or optionally the foam material is a plurality of foam particles, and optionally each individual foam particle of the plurality of foam particles is attached to at least one other individual foam particle of the plurality of foam particles.

[0222] Item 18. The article of any preceding item, wherein the first polymeric material comprises a polyurethane homopolymer or copolymer, a polyamide homopolymer or copolymer, a polyether homopolymer or copolymer, a polyester homopolymer or copolymer, or any combination thereof.

[0223] Item 19. The article of item 18, wherein the polymeric component of the first polymeric material consisting of all polymers present in the first polymeric material consists essentially of one or more polyurethane homopolymers, one or more polyurethane copolymers, or any combination thereof.

[0224] Item 20. The article of item 18 or 19, wherein the polyurethane copolymer comprises a polyester polyurethane copolymer.

[0225] Item 21. The article of item 20, wherein a polymer component of the first polymeric material consisting of all polymers present in the first polymeric material consists essentially of one or more polyether homopolymers, one or more polyether copolymers, or any combination thereof.

[0226] Item 22. The article of item 21, wherein the polyether copolymer comprises a polyether block amide (PEBA) copolymer.

[0227] Item 23. The article of item 18, wherein a polymer component of the first polymeric material comprising all polymers present in the first polymeric material consists essentially of one or more polyester homopolymers, one or more polyester copolymers, or any combination thereof.

[0228] Item 24. The article of item 23, wherein the polyester homopolymer comprises a poly(ethylene terephthalate) homopolymer or copolymer.

[0229] Item 25. The article of item 18, wherein the first polymeric material comprises a polyamide homopolymer or copolymer.

[0230] Item 26. The article of item 25, wherein a polymer component of the first polymeric material comprising all polymers present in the first polymeric material consists essentially of one or more polyamide homopolymers, one or more polyamide copolymers, or any combination thereof.

[0231] Item 27. The article of any preceding item, wherein the first polymeric material comprises a polyisoprene homopolymer or copolymer, a polybutadiene homopolymer or copolymer, or any combination thereof.

[0232] Item 28. The article of item 27, wherein a polymer component of the first polymeric material consisting of all polymers present in the first polymeric material consists essentially of one or more polyisoprene homopolymers or copolymers, one or more polybutadiene homopolymers or copolymers, or any combination thereof.

[0233] Item 29. The article of any preceding item, wherein the first polymeric material comprises a vinyl acetate homopolymer or copolymer, an acrylic ester homopolymer or copolymer, a styrene homopolymer or copolymer, an olefin homopolymer or copolymer, or any combination thereof.

[0234] Item 30. The article of item 29, wherein a polymer component of the first polymeric material consisting of all polymers present in the first polymeric material consists essentially of one or more vinyl acetate homopolymers or copolymers, one or more styrene homopolymers or copolymers, or any combination thereof.

[0235] Item 31. The article of any of items 29 or 30, wherein the ethylene vinyl acetate copolymer is an ethylene-vinyl acetate copolymer.

[0236] Item 32. The article of any of items 29 or 30, wherein the styrene copolymer is a styrene-ethylene-butadiene copolymer.

[0237] Item 33. The article of any of items 29 or 30, wherein the olefin homopolymer or copolymer comprises a polyethylene homopolymer or copolymer, a polypropylene homopolymer or copolymer, or any combination thereof.

[0238] Item 34. The article of item 33, wherein the polymer component consisting of all polymers present in the first polymeric material of the first polymeric material consists essentially of one or more olefin homopolymers or copolymers.

[0239] Item 35. The article of item 34, wherein the polymer component consists essentially of one or more olefin homopolymers.

[0240] Item 36. The article of any of items 20 to 35, wherein the olefin homopolymer comprises a polyethylene homopolymer, a polypropylene homopolymer, or both.

[0241] Item 37. The article of any preceding item, wherein the cured coating layer reduces the level of ultraviolet light reaching the first polymeric material compared to a substantially identical article without the cured coating layer.

[0242] Item 38. The article of any preceding item, wherein the cured coating layer reduces the level of water reaching the first polymeric material compared to a substantially identical article without the cured coating layer.

[0243] Item 39. The article of any preceding item, wherein the first side of the article is an outward-facing side of the article, wherein the article comprises a film present on the first side of the article, wherein the film comprises the first polymeric material, and optionally the cured coating layer is on an inner surface of the film, or the cured coating layer is on an outer surface of the film.

[0244] Item 40. The article of any preceding item, wherein the article is a bladder wall having an interior-facing side and an exterior-facing side, wherein the interior-facing side bounds at least a portion of an interior region of an inflated bladder, wherein the bladder wall has an average wall thickness of less than 5 millimeters between the interior-facing side and the exterior-facing side, wherein the first side of the article comprises the exterior-facing side of the bladder wall or the interior-facing side of the bladder wall, wherein the bladder wall comprises the first polymeric material on the exterior-facing side of the bladder wall or the interior-facing side of the bladder wall, wherein the cured coating is disposed on the exterior-facing side of the bladder wall or the interior-facing side of the bladder wall.

[0245] Item 41. The article of any preceding item, wherein the bladder is a filled bladder comprising a volume of a fluid, optionally the fluid is a gas, optionally the gas comprises nitrogen, optionally the filled bladder comprises a volume of the fluid at a pressure higher than atmospheric pressure.

[0246] Item 42. The article of any preceding item, wherein a first bladder wall has a gas permeability of 15 cm 3 / m 2 • atm • day or less for an average wall thickness of 20 mils for nitrogen.

[0247] Item 43. The article of any preceding item, wherein the bladder wall comprises a film on the exterior-facing side of the bladder wall or the interior-facing side of the bladder wall, wherein the cured coating is on the film.

[0248] Item 44. The article of any preceding item, wherein the article is an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of sports equipment, or a component of an article of sports equipment; optionally wherein the article is a cushioning component or a decorative component.

[0249] Item 45. The article of any preceding item, wherein the article is a component of an upper of an article of footwear or a component of a sole structure of an article of footwear; optionally wherein the article is a component of a sole structure of an article of footwear; and optionally wherein the article is a plate for an article of footwear and the cured coating is visible on or through an exterior surface of the plate, the exterior surface of the plate being configured as a surface facing the ground.

[0250] Item 46. An article of footwear, an article of apparel, or an article of sports equipment, wherein the article comprises a component formed from the article of any of the preceding items.

[0251] Item 47. A method of making a coated article, the method comprising: disposing a coating composition onto a first side of an article, wherein the first side comprises a first polymeric material; and curing the coating composition on the first polymeric material to form a cured coating comprising a crosslinked polymeric matrix, thereby forming the coated article.

[0252] Item 48. The method of item 47, wherein disposing the coating composition comprises disposing a coating composition onto the first polymeric material, the coating composition comprising a dispersion of uncrosslinked polymer in a carrier; and forming the cured coating comprises crosslinking the uncrosslinked polymer of the dispersion to form the crosslinked polymeric matrix.

[0253] Item 49. The method of any preceding item, wherein the cured coating is the cured coating of any of items 1 to 46.

[0254] Item 50. The method of any preceding item, wherein the coating composition is the coating composition of any of items 1 to 46.

[0255] Item 51. The method of any preceding item, wherein the applying comprises spray coating the coating composition onto a side of the article, brush coating the coating composition onto a side of the article, or dipping a side of the article into the coating composition.

[0256] Item 52. The method of any preceding item, wherein the curing comprises increasing a temperature of the coating composition to a temperature from about 50 °C to about 90 °C for at least 1 minute; or optionally increasing a temperature of the coating composition to a temperature from about 60 °C to about 80 °C for at least 1 minute.

[0257] Item 53. The method of any preceding item, wherein the method further comprises applying a dye solution to the first side of the article before or after applying the coating composition.

[0258] Item 54. The method of any preceding item, wherein the method further comprises printing on a side of the article before or after applying the coating composition.

[0259] Item 55. The method of any preceding item, wherein the article is a pouch, and the method further comprises forming the pouch from a film, wherein the film is the film of any preceding item.

[0260] Item 56. The method according to any of the preceding items, wherein the process of forming the capsule includes applying the coating composition to the membrane before or after forming the capsule, and applying heat, pressure and / or vacuum to the membrane to form the capsule.

[0261] Item 57. A method of manufacturing an article, the method comprising: attaching a first article of an article according to any one of items 1-46 to a second article to form the article.

[0262] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. It should be understood that such range format is used for convenience and brevity, and therefore should be interpreted flexibly to include not only the numerical values ​​explicitly stated as range limits, but also all individual numerical values ​​or subranges contained within that range, as each numerical value and subrange is explicitly stated. For example, the concentration range “about 0.1 percent to about 5 percent” should be interpreted to include not only the explicitly stated concentrations of about 0.1 wt percent to about 5 wt percent, but also individual concentrations (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and subranges (e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4 percent) within the indicated range. In one aspect, the term “about” may include conventional rounding based on the significant figures of the numerical value. Additionally, the phrase “about 'x' to 'y'” includes “about 'x' to about 'y'”.

[0263] Various changes and modifications may be made to the aspects described above. All such modifications and changes are intended to be included within the scope of this disclosure and are protected by the appended claims.

Claims

1. A component of the upper (12) of a footwear article (10) or a component of the sole structure (14) of a footwear article (10), comprising: An article having a first side comprising an elastic polymer material, the elastic polymer material being a molded thermoplastic or thermosetting resin material, and an elastic, cured coating (32) disposed on the polymer material on the first side, characterized in that the cured coating comprises a crosslinking agent and more than one pigment particle embedded in a crosslinked polymer matrix.

2. The component according to any of the preceding claims, wherein the polymer material is a foam material.

3. The component according to any of the preceding claims, wherein the polymer material comprises polyurethane homopolymer or copolymer, polyamide homopolymer or copolymer, polyether homopolymer or copolymer, polyester homopolymer or copolymer, or any combination thereof.

4. The component according to any of the preceding claims, wherein the pigment particles are selected from the group consisting of: metal and metal oxide pigments, carbon pigments, clay pigments, ultramarine pigments, and combinations thereof.

5. The component according to any of the preceding claims, wherein the polymer material comprises polyisoprene homopolymer or copolymer, polybutadiene homopolymer or copolymer, or any combination thereof.

6. The component according to any of the preceding claims, wherein the polymer material comprises vinyl acetate homopolymer or copolymer, acrylate homopolymer or copolymer, styrene homopolymer or copolymer, olefin homopolymer or copolymer, or any combination thereof.

7. The component according to any of the preceding claims, wherein the article is a plate for footwear (10), and the cured coating is visible on or through the outer surface of the plate, the outer surface of the plate being configured to face the ground.

8. The component according to any of the preceding claims, wherein the cured coating (32) is a product of crosslinking the coating composition, the coating composition comprising a dispersion of an uncrosslinked polymer in a carrier to form the crosslinked polymer matrix.

9. The component according to any of the preceding claims, wherein the crosslinked polymer matrix comprises a crosslinked polyurethane homopolymer or copolymer or both.

10. The component according to any of the preceding claims, wherein the crosslinked polymer matrix comprises crosslinked polyester polyurethane.

11. The component according to any of the preceding claims, wherein the cured coating (32) reduces the level of ultraviolet light reaching the polymer material compared to an article substantially the same as one without the cured coating (32), or the cured coating (32) reduces the level of water reaching the polymer material compared to an article substantially the same as one without the cured coating (32), or both.

12. A footwear article comprising the component according to any of the preceding claims.

13. A method of manufacturing a covered article, wherein the covered article is a component of the upper (12) of a footwear article (10) or a component of the sole structure (14) of a footwear article (10), the method comprising: A coating composition is disposed on a first side of an article, wherein the first side comprises a first elastic material, the first elastic material being a molded thermoplastic or thermosetting resin material; characterized in that the coating composition comprises an uncrosslinked polymer, a crosslinking agent, and more than one pigment particle; and the coating composition on the first elastic material is cured to form a cured coating (32), the cured coating (32) comprising a crosslinked polymer matrix, including the more than one pigment particle embedded in the crosslinked polymer matrix, thereby forming the coated article.

14. The method of claim 12, wherein disposing of the coating composition comprises disposing the coating composition onto the first elastic material, the coating composition comprising a dispersion of an uncrosslinked polymer in a carrier; and forming the cured coating comprises crosslinking the uncrosslinked polymer of the dispersion to form the crosslinked polymer matrix.

15. A method for manufacturing footwear, the method comprising: The component according to any one of claims 1-10 is attached to a second article to form the footwear article, the component comprising a cured coating comprising a crosslinking agent and more than one pigment particle embedded in a crosslinked polymer matrix.

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