Methods of manufacturing items using foam particles

Abstract

This application relates to a method for manufacturing articles using foam particles. A method for manufacturing articles, including footwear, clothing, and sports equipment, is provided. The method includes decorating more than one foam particle. Decoration may include applying a coating to the foam particle, or embossing or debossing the foam particle, or both. Decoration may include applying a coating to the foam particle by printing, coating, dyeing, applying a film, or any combination thereof. Aspects of using more than one foam particle with additive manufacturing methods are attached. This abstract is intended as a browsing tool for searching in a particular field and is not intended to limit the scope of this disclosure.

Description

[0001] This application is a divisional application of the application filed on November 19, 2019, with application number 201980031583.5 and invention title "Method for Manufacturing Articles Using Foam Particles".

[0002] Cross-references to related applications

[0003] This application claims the benefit of U.S. Provisional Applications Nos. 62 / 776,124 and 62 / 776,129, each filed on December 6, 2018, which are incorporated herein by reference in their entirety. Technical Field

[0004] This disclosure generally relates to methods for manufacturing and decorating articles using foam particles in additive manufacturing processes. background

[0005] The design of sports equipment, apparel, and footwear involves a wide range of factors, from aesthetics and comfort to performance and durability. While designs and fashions can change rapidly, the market demand for enhanced performance remains constant. To balance these needs, designers utilize a variety of materials and designs for the various components that make up sports equipment, apparel, and footwear. Attached Figure Description

[0006] Other aspects of this disclosure will be readily understood when viewed in conjunction with the accompanying drawings and after reviewing the detailed description described below.

[0007] Figure 1 This is a front view of a footwear article having a sole component, in accordance with this disclosure.

[0008] Figure 2 yes Figure 1 An exploded view of the sole component of footwear.

[0009] Figure 3 yes Figure 1 A plan view of the bottom of the sole component of footwear.

[0010] Figure 4 This is a bottom view of the insert for the sole component of footwear.

[0011] Figure 5 It is inserted into the first part to form the sole component. Figure 4 Top view of the insert.

[0012] Figure 6 This is an outside view of footwear, showing the upper and sole components of the shoe.

[0013] Figure 7 This is a plan view of the bottom of the shoe sole component.

[0014] Figure 8 yes Figure 7 The bottom cross-sectional view of the sole component shown depicts the sub-regions where different foam particles are fused together.

[0015] Figure 9 yes Figure 8 The transverse cross-sectional view along line AA of the sole component shown in the figure depicts the sub-regions where different foam particles are fused together.

[0016] Figure 10 yes Figure 7 The bottom cross-sectional view of the sole component shown depicts the sub-regions where different foam particles are fused together.

[0017] Figure 11 Representative differential scanning calorimetry (DSC) data for a representative disclosed thermoplastic elastomer foam particle are shown. The foam particle (referred to herein as "thermoplastic COPE foam particle") was prepared using a thermoplastic block copolyester comprising crystalline (or hard) segments containing polybutylene terephthalate and amorphous (or soft) segments containing polyether.

[0018] Figure 12 Representative particle size distribution data of a representative publicly disclosed thermoplastic elastomer foam particle (sample size = 2,000 foam particles) are shown, including the roundness or circularity distribution data of the thermoplastic elastomer foam particle. Figure 13 As shown in the image.

[0019] Figure 13 Representative roundness or sphericity distribution data of a representative publicly disclosed thermoplastic elastomer foam particle (sample size = 2,000 foam particles) are shown. The particle size distribution data of this thermoplastic elastomer foam particle is... Figure 12 As shown in the image.

[0020] Figure 14 Images of representative articles prepared using the disclosed method are shown.

[0021] Figure 15 An image of a representative sole interlayer on a production platform is shown, in which unattached particles surround the sole interlayer.

[0022] Figure 16 It shows Figure 15 The image shown is of a representative shoe sole interlayer after cleaning and removal of unattached particles.

[0023] Figure 17Images of representative shoe sole interlayers prepared using the disclosed method are shown. The representative shoe sole interlayers were dyed after fusing foam particles by immersing them in an aqueous dye solution heated to 60 degrees Celsius. The aqueous dye solution contained one or more acidic dyes and / or reactive dyes in isopropanol.

[0024] Figure 18 Shown at a high magnification Figure 17 The image shows a representative section of the midsole.

[0025] Figure 19 Images of representative shoe sole interlayers prepared using the disclosed method are shown. The representative shoe sole interlayers were dyed after fusing foam particles by immersing them in an aqueous dye solution heated to 60 degrees Celsius. The aqueous dye solution contained one or more acidic dyes and / or reactive dyes in isopropanol.

[0026] Figure 20 Images of a representative shoe sole interlayer prepared using the disclosed method are shown. In short, white foam particles are arranged and then bonded together by depositing black energy-absorbing ink, followed by heating the foam particles to melt their surfaces, thereby fusing them together.

[0027] Figure 21 It shows the use of and Figure 20 Images of representative articles prepared by methods similar to those described are shown. These articles include areas where energy-absorbing ink deposition has not occurred (distinct circular white areas on the inner surface of the article), and in these areas, the foam particles are generally unattached (see the diagram highlighting the unattached foam article with dashed lines and two areas indicated by appropriate arrows). Other areas of the article undergo energy-absorbing ink deposition and are then heated. In this way, the foam particles in these areas adhere to each other.

[0028] Figure 22 It shows Figure 21 The image depicts a representative article. However, in areas containing unattached foam particles, the foam particles have been removed, creating void areas (see the diagram highlighted with dashed lines showing two void areas where the unattached foam particles have been removed and indicated by appropriate arrows). Other areas of the article undergo deposition of energy-absorbing ink, followed by heating. In this way, the foam particles in these areas remain attached to each other.

[0029] Figure 23 It shows the use of and Figure 20Images of representative articles prepared using methods similar to those described in the disclosed method are shown. However, for the articles shown, a larger concentration of binder material is applied to the left side of the box compared to the right side, resulting in a greater bulk density and stiffness on the left side than on the right.

[0030] Figure 24 Shown at a high magnification Figure 23 The image shows a segment along the left edge of a representative midsole layer.

[0031] Figure 25 Shown at a high magnification Figure 23 The image shows a segment along the right edge of a representative midsole layer. The image reveals individual spots formed by droplets of binder material on the foam particles. Detailed description

[0032] This disclosure relates to methods for decorating components formed from more than one attached foam particle. This disclosure also relates to articles comprising decorated components formed from more than one foam particle, including articles manufactured according to the manufacturing methods described herein, which include aspects of additive manufacturing methods. These novel manufacturing methods, including aspects of additive manufacturing methods, provide new approaches to integrating decoration steps into the manufacturing process, and to unique and aesthetically attractive decorated components.

[0033] Due to their speed, customizability, and flexibility, these manufacturing methods, incorporating aspects of additive manufacturing, are highly desirable for manufacturing many types of articles. In particular, these methods are useful alternatives for manufacturing parts that are currently produced at great expense or with great difficulty using conventional molding, casting, or machining methods. In some cases, the desired part may not even be suitable for manufacture using conventional molding, casting, or machining methods.

[0034] Certain aspects of additive manufacturing methods have been found to be applicable to foam particles comprising thermoplastic elastomers. The ability to use foam particles in additive manufacturing methods allows the methods to produce parts with properties, such as bulk density, that are not possible using polymer powders. The disclosed methods may include attaching more than one foam particle to each other to form a structure, and attaching more than one foam particle to the surface of a part such as a textile element or a solid resin element. The resulting structures also have a unique physical appearance. The disclosed methods also include using a variety of techniques to decorate such structures, such as by coating the foam particles or structure, embossing or debossing the structure, or both.

[0035] Furthermore, it has been found that the disclosed method allows for the decoration of articles that combine the useful properties and material characteristics of foamed polymer materials discovered in the process with the flexibility, customizability, and rapid throughput of additive manufacturing methods. In particular, it has been found that the disclosed method of decoration using foam particles can be used to decorate components used in the manufacture of footwear, such as preforms, insole midsoles, outsoles, insoles, and heel cushioning pads. It has been found that the disclosed method reduces article decoration and build time by at least one-third while allowing the manufacture of components with more than one sub-region containing distinctly attached foam particles. The more than one sub-region can be discrete regions including desired geometries and / or shapes. Alternatively, the article can include a gradient of distinctly attached foam particles. It has been found that the method can provide decorated articles with regions of highly attached foam particles, such as outer or inner edges of articles demarcating sub-regions in which are entirely unattached foam particles.

[0036] This disclosure relates to a method of forming an article, the method comprising decorating a portion of more than one foam particle. Optionally, the method may further comprise arranging more than one foam particle, wherein the arranged more than one foam particle comprises a first thermoplastic elastomer material, and wherein the arranged more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and attaching at least a portion of the more than one foam particle together, wherein the arrangement and the attachment are iterated two or more times to form a part. When the method further comprises the arrangement and the attachment, the decoration may occur before, during, or after the arrangement and the attachment. Decoration may occur during the attachment. Decoration may occur after the attachment. Decoration may include applying a coating to the portion, or embossing or debossing the portion, or both. Decoration may include applying a coating to the portion, wherein applying a coating further comprises printing on the portion, coating the portion, dyeing the portion, applying a film on the portion, or any combination thereof.

[0037] This disclosure also relates to a method of forming an article, the method comprising: arranging more than one foam particle, wherein the arranged more than one foam particle comprises a first thermoplastic elastomer material, and wherein the arranged more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and attaching at least a portion of the more than one foam particle to a first bonding material, wherein the arrangement and the attachment are iterated two or more times to form a component, wherein attaching at least a portion of the more than one foam particle includes: depositing the first bonding material in a bonding material target region, wherein the bonding material target region includes at least a portion of the arranged more than one foam particle, and wherein the first bonding material is deposited to cover at least a portion of the defining surface of the arranged more than one foam particle; and curing the deposited first bonding material in at least the first bonding material target region and covering at least a portion of the defining surface of the arranged more than one foam particle, wherein curing includes attaching at least a portion of the arranged more than one foam particle in the target region. The method may also include using a second bonding material to attach a second portion of more than one foam particle, or attaching a second or more foam particles in a manner other than using a second bonding material as described above. The first bonding material may impart a first color to the foam particles, and the second bonding material may impart a second color to the foam particles, the second color being different from the first color in at least one of hue, lightness, and chroma.

[0038] This disclosure also relates to an article comprising: a decorated component formed of more than one attached foam particle, wherein each individual foam particle in the more than one attached foam particle is formed of a thermoplastic elastomer material and includes one or more bonding regions on the outer surface of the individual foam particle, the bonding regions attaching the individual foam particle to one or more adjacent foam particles, the one or more adjacent foam particles comprising a thermoplastic elastomer material; the component formed of the more than one attached foam particle includes more than one gap between the foam particles; wherein prior to attachment, the more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and wherein a portion of the more than one attached foam particle of the component includes a coating, or the surface of the component including a portion of the foam particle is embossed or debossed, or both.

[0039] In a first aspect, this disclosure relates to a method of forming an article, the method comprising: decorating a portion of more than one foam particle, wherein the method optionally further comprises: arranging more than one foam particle, wherein the arranged more than one foam particle comprises a first thermoplastic elastomer material, and wherein the arranged more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and attaching at least a portion of the more than one foam particle together, wherein the arrangement and the attachment are iterated two or more times to form a component.

[0040] In the second aspect, this disclosure relates to articles manufactured by the disclosed methods.

[0041] In a third aspect, this disclosure relates to an article comprising: a component formed of more than one attached foam particle, wherein each individual foam particle in the more than one attached foam particle is formed of a thermoplastic elastomer material and includes one or more bonding regions on the outer surface of the individual foam particle, the bonding regions attaching the individual foam particle to one or more adjacent foam particles, the one or more adjacent foam particles comprising a thermoplastic elastomer material; the component formed of the more than one attached foam particle includes more than one gap between the foam particles; wherein prior to attachment, the more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and wherein a portion of the more than one attached foam particle of the component includes a coating, or the surface of the component including a portion of the foam particle is embossed or debossed, or both.

[0042] This disclosure will be better understood after reading the following numbered aspects, which should not be confused with the claims. In some cases, any aspect numbered below may be combined with aspects described elsewhere in this disclosure, and such combinations are intended to be part of this disclosure.

[0043] Aspect 1. A method of forming an article, the method comprising: decorating a portion of more than one foam particle, wherein the method optionally further comprises: arranging more than one foam particle, wherein the arranged more than one foam particle comprises a first thermoplastic elastomer material, and wherein the arranged more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and attaching at least a portion of the more than one foam particle together, wherein the arrangement and the attachment are iterated two or more times to form a component.

[0044] Aspect 2. The method according to aspect 1, wherein the decoration comprises: applying a coating to the portion; or embossing or debossing the portion; or both.

[0045] Aspect 3. The method according to any one of Aspects 1 to 2, wherein applying the coating to the portion of the more than one foam particle comprises printing on the portion, coating the portion, dyeing the portion, applying a film or any combination thereof to the portion.

[0046] Aspect 4. The method according to any one of Aspects 1 to 3, wherein the portion of the more than one foam particle has a first color, and the coating has a second color different from the first color.

[0047] Aspect 5. The method according to any one of Aspects 1 to 4, wherein when measured according to the CIE 1976 color space under given illumination conditions at an observation angle between -15 degrees and +60 degrees, the first color has a first color measurement value having coordinates L1* and a1* and b1*, and the second color has a second color measurement value having coordinates L2* and a2* and b2*, wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the a1* coordinate value is at least 10 percent larger or smaller than the a2* coordinate value; the b1* coordinate value is at least 10 percent larger or smaller than the b2* coordinate value; or a combination thereof.

[0048] Aspect 6. The method according to any one of Aspects 1 to 5, wherein when measured according to the CIE 1976 color space under given illumination conditions at an observation angle between -15 degrees and +60 degrees, the first color has a first color measurement value having coordinates L1* and a1* and b1*, and the second color has a second color measurement value having coordinates L2* and a2* and b2*, wherein the L1* and L2* values ​​may be the same or different, wherein the a1* and a2* coordinate values ​​may be the same or different, wherein the b1* and b2* coordinate values ​​may be the same or different, and wherein ΔE*ab between the first color measurement value and the second color measurement value is greater than or equal to about 60, wherein ΔE*ab = [(L1* - L2*)] 2 +(a1*–a2*) 2 +(b1*-b2*) 2 ] 1 / 2 , optionally greater than or equal to about 80, or optionally greater than or equal to about 100.

[0049] Aspect 7. The method according to any one of Aspects 1 to 6, wherein when measured at an observation angle between -15 degrees and +60 degrees under given illumination conditions according to the CIELCH color space, the first color has a first color measurement value having coordinates L1* and C1* and h1°, and the second color has a second color measurement value having coordinates L2* and C2* and h2°, wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the C1* coordinate value is at least 10 percent larger or smaller than the C2* coordinate value; the h1° coordinate value is at least 10 percent larger or smaller than the h2° coordinate value; or a combination thereof.

[0050] Aspect 8. The method according to any one of Aspects 1 to 7, wherein the arrangement of more than one foam particle comprises depositing a substantially planar layer comprising the more than one foam particle.

[0051] Aspect 9. The method according to any one of Aspects 1 to 8, wherein the arrangement of more than one foam particle comprises arranging more than one first foam particle comprising a first thermoplastic elastomer material and more than one second foam particle comprising a second thermoplastic elastomer material.

[0052] Aspect 10. The method according to any one of Aspects 1 to 9, wherein the method comprises mixing the more than one first foam particle with the more than one second foam particle prior to the arrangement.

[0053] Aspect 11. The method according to any one of Aspects 1 to 10, wherein the arrangement and the attachment are iterated three or more times.

[0054] Aspect 12. The method according to any one of Aspects 1 to 11, wherein the arrangement and the attachment are iterated three times to 500 times.

[0055] Aspect 13. The method according to any one of Aspects 1 to 12, wherein the decoration is performed during an iteration, after an iteration, between two or more iterations, or a combination thereof.

[0056] Aspect 14. The method according to any one of Aspects 1 to 13, wherein the decoration is performed on the component after the last iteration.

[0057] Aspect 15. The method according to any one of aspects 1 to 14, wherein the decoration is performed between the arrangement and the attachment.

[0058] Aspect 16. The method according to any one of Aspects 1 to 15, wherein attaching at least a portion of the more than one foam particle together comprises: depositing a bonding material in a bonding material target region, wherein the bonding material target region includes at least a portion of the arranged more than one foam particle, and wherein the deposition covers at least a portion of the defining surface of the arranged more than one foam particle with the bonding material; and curing the deposited bonding material covering at least a portion of the defining surface of the arranged more than one foam particle in at least the bonding material target region, wherein curing comprises attaching at least a portion of the arranged more than one foam particle in the target region.

[0059] Aspect 17. The method according to any one of Aspects 1 to 16, wherein the curing comprises solidifying the deposited bonding material and bonding the deposited bonding material to at least a portion of the defined surface of the arranged more than one foam particle.

[0060] Aspect 18. The method according to any one of Aspects 1 to 17, wherein the curing comprises: applying energy to the deposited bonding material and the arranged more than one foam particle in an amount sufficient to soften at least a portion of the first thermoplastic elastomer material covering the defining surface of the arranged more than one foam particle for a duration sufficient to soften at least a portion of the first thermoplastic elastomer material covering the defining surface of the arranged more than one foam particle; and reducing the temperature of the region of the arranged more than one foam particle to or below the temperature at which the softened thermoplastic elastomer material re-solidifies; thereby attaching at least a portion of the at least a portion of the defined surface of the arranged more than one foam particle in the target region of the bonding material.

[0061] Aspect 19. The method according to any one of Aspects 1 to 18, wherein the application of energy comprises applying energy to more than one foam particle substantially all of the arrangement.

[0062] Aspect 20. The method according to any one of aspects 1 to 19, wherein the applied energy comprises applied energy within the infrared spectrum.

[0063] Aspect 21. The method according to any one of Aspects 1 to 20, wherein the bonding material comprises one or more monomers, one or more polymers or combinations thereof; and wherein curing comprises: forming at least one chemical bond between one or more monomers, one or more polymers or combinations thereof of the bonding material; and / or forming at least one chemical bond between at least a portion of the covered surface of the more than one foam particle arranged in the target region of the bonding material and one or more monomers, one or more polymers or combinations thereof of the bonding material; thereby attaching at least a portion of the covered foam particle arranged in the target region of the bonding material to each other or to an uncovered foam particle.

[0064] Aspect 22. The method according to any one of Aspects 1 to 21, wherein depositing the bonding material comprises depositing the bonding material by spraying, atomizing, or a combination thereof; wherein the bonding material comprises a solvent; wherein the method further comprises: after the deposition, dissolving at least a portion of the defining surface of the arranged more than one foam particle with the solvent to form a dissolved defining surface of the arranged foam particles; and wherein the curing comprises, after the dissolution, removing at least a portion of the solvent of the bonding material and solidifying at least a portion of the dissolved defining surface of the arranged foam particles; thereby attaching at least a portion of the arranged more than one foam particle in the target region of the bonding material to each other or to an uncoated foam particle.

[0065] Aspect 23. The method according to any one of Aspects 1 to 22, wherein the deposition comprises depositing a first bonding material and a second bonding material; wherein the first bonding material comprises a solvent; wherein the second bonding material comprises a bonding thermoplastic elastomer material soluble in the solvent; and wherein the curing comprises removing the solvent and solidifying the bonding thermoplastic elastomer material onto at least a portion of the defining surface of the arranged foam particles; thereby attaching at least a portion of the arranged more than one foam particle in the target region of the bonding material to each other or to an uncoated foam particle.

[0066] Aspect 24. The method according to any one of Aspects 1 to 23, wherein the more than one foam particle comprises a foam particle having a density of about 0.1 g per cubic centimeter to about 0.8 g per cubic centimeter.

[0067] Aspect 25. The method according to any one of Aspects 1 to 24, wherein the more than one foam particle has a bulk density of about 80 g / L to about 200 g / L.

[0068] Aspect 26. The method according to any one of aspects 1 to 25, wherein attaching at least a portion of the more than one foam particle together comprises: raising the temperature of at least a portion of the more than one foam particle by photochemical radiation under conditions effective for melting or softening a portion of the first thermoplastic elastomer material at a first surface of at least one of the more than one foam particle; and lowering the temperature of the melted or softened portion of the first thermoplastic elastomer material, thereby causing the melted or softened portion of the first thermoplastic elastomer material to solidify and form more than one fused foam particle; wherein raising the temperature is performed at least once.

[0069] Aspect 27. The method according to any one of Aspects 1 to 26, wherein raising the temperature of at least a portion of the more than one foam particle by photochemical radiation, under conditions effective for melting or softening a portion of the first thermoplastic elastomer material at a first surface of at least one of the more than one foam particle, further comprises mixing the molten first thermoplastic elastomer material from the first surface of the foam particle with molten first thermoplastic elastomer material at a second surface of an adjacent foam particle; and wherein lowering the temperature of the molten or softened portion of the first thermoplastic elastomer material comprises lowering the temperature of the mixed thermoplastic elastomer material, thereby causing the molten portion of the thermoplastic elastomer to solidify and form more than one fused foam particle.

[0070] Aspect 28. The method according to any one of Aspects 1 to 27, wherein the more than one foam particle has a bulk density of about 80 g / L to about 200 g / L.

[0071] Aspect 29. The method according to any one of Aspects 1 to 28, wherein raising the temperature of at least a portion of the more than one foam particle includes raising the temperature of a target region of the more than one foam particle.

[0072] Aspect 30. The method according to any one of aspects 1 to 29, wherein raising the temperature of the target region of the more than one foam particle comprises raising the temperature of the target region of the more than one foam particle using a directional energy beam of photochemical radiation.

[0073] Aspect 31. The method according to any one of Aspects 1 to 30, wherein the directional energy beam of the photochemical radiation is a laser beam.

[0074] Aspect 32. The method according to any one of aspects 1 to 31, wherein the laser beam has a beam width of about 0.1 mm to about 0.7 mm.

[0075] Aspect 33. The method according to any one of Aspects 1 to 32, wherein the directed energy beam of the photochemical radiation has a scanning mode such that the directed energy beam of the photochemical radiation is directed in the xy plane; and wherein the directed energy beam of the photochemical radiation is configured to change the amount of energy over a certain amount of time at each point in the xy plane.

[0076] Aspect 34. The method according to any one of Aspects 1 to 33, wherein the first thermoplastic elastomer material or the second thermoplastic elastomer material or both comprise thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, thermoplastic polyether elastomers, thermoplastic copolyether ester elastomers, thermoplastic polyamide elastomers, thermoplastic polystyrene elastomers, thermoplastic polyolefin elastomers, thermoplastic copolyether amide elastomers, thermoplastic styrene diene copolymer elastomers, thermoplastic styrene block copolymer elastomers, thermoplastic polyamide elastomers, thermoplastic polyimide elastomers, any copolymers thereof, or any blends thereof.

[0077] Aspect 35. The method according to any one of Aspects 1 to 34, wherein the first thermoplastic elastomer material or the second thermoplastic elastomer material or both comprise a thermoplastic polyether block amide copolymer.

[0078] Aspect 36. The method according to any one of Aspects 1 to 35, wherein the first thermoplastic elastomer material or the second thermoplastic elastomer material or both are characterized by a range of at least 10°C, in which the first thermoplastic elastomer material or the second thermoplastic elastomer material exhibits softening and melting behavior as determined by differential scanning calorimetry.

[0079] Aspect 37. The method according to any one of Aspects 1 to 36, wherein the printing includes screen printing, pad printing, inkjet printing, 3D printing, flexographic printing, thermal transfer printing, or any combination thereof.

[0080] Aspect 38. The method according to any one of aspects 1 to 37, wherein printing comprises printing a marker onto one or more foam particles.

[0081] Aspect 39. The method according to any one of Aspects 1 to 38, wherein printing includes printing a marker onto at least a portion of the outer surface of the component after the component has been formed.

[0082] Aspect 40. The method according to any one of aspects 1 to 39, wherein printing includes depositing at least one ink onto a target printing area of ​​the component.

[0083] Aspect 41. The method according to any one of aspects 1 to 40, wherein printing includes depositing more than one type of ink onto a target printing area of ​​the component.

[0084] Aspect 42. The method according to any one of Aspects 1 to 41, wherein at least one ink comprises a CMYK formulation or an RGB formulation.

[0085] Aspect 43. The method according to any one of Aspects 1 to 42, wherein at least one ink comprises a sublimation ink formulation.

[0086] Aspect 44. The method according to any one of Aspects 1 to 43, wherein printing comprises depositing sublimation ink on the outer surface of the component, and then raising the temperature of the component to above the sublimation temperature of the sublimation ink.

[0087] Aspect 45. The method according to any one of Aspects 1 to 44, wherein depositing sublimation ink on the outer surface of the component comprises providing release paper printed with sublimation ink and transferring the sublimation ink from the release paper to the surface of the component.

[0088] Aspect 46. The method according to any one of Aspects 1 to 45, wherein at least one ink comprises a formulation containing an infrared radiation absorber, and printing comprises depositing the ink on a target location to be exposed to infrared radiation.

[0089] Aspect 47. The method according to any one of aspects 1 to 46 further includes adding a primer layer to the surface of the component and printing on the primer layer.

[0090] Aspect 48. The method according to any one of Aspects 1 to 47, wherein the primer layer comprises pigment, dye, or both.

[0091] Aspect 49. The method according to any one of Aspects 1 to 48, wherein the primer layer comprises a coating, an ink, or both.

[0092] Aspect 50. The method according to any one of Aspects 1 to 49, wherein the primer layer comprises a re-ground and at least partially degraded polymer.

[0093] Aspect 51. The method according to any one of Aspects 1 to 50, wherein the primer layer comprises a polymer coating composition.

[0094] Aspect 52. The method according to any one of Aspects 1 to 51, wherein the coating is a cross-linked coating comprising a cross-linked polymer matrix, and optionally comprises more than one solid pigment particle embedded in the cross-linked polymer matrix.

[0095] Aspect 53. The method according to any one of Aspects 1 to 52, wherein the crosslinked polymer matrix comprises a crosslinked elastomer polymer, optionally the crosslinked elastomer polymer comprises a crosslinked polyurethane homopolymer or a crosslinked polyurethane copolymer or both, and optionally the crosslinked polyurethane copolymer comprises a crosslinked polyester polyurethane.

[0096] Aspect 54. The method according to any one of Aspects 1 to 53, wherein the coating is a product of crosslinking a polymer coating composition, the polymer coating composition comprising a dispersion of a polymer and optionally comprising at least one of a crosslinking agent, more than one solid pigment particle, a dye, and an organic solvent.

[0097] Aspect 55. The method according to any one of Aspects 1 to 54, wherein the primer layer has a transmittance of about 40 percent or less.

[0098] Aspect 56. The method according to any one of aspects 1 to 55, wherein printing includes providing a printing film and attaching the printing film to at least a portion of the outer surface of the component.

[0099] Aspect 57. The method according to any one of Aspects 1 to 56, wherein the printing includes an additive manufacturing process that deposits a polymer material onto the outer surface of the component, thereby creating a topology on the outer surface of the component with a larger surface area compared to the topology on the outer surface of the component prior to printing.

[0100] Aspect 58. The method according to any one of Aspects 1 to 57, wherein the printing comprises printing a three-dimensional structure onto the outer surface of the component.

[0101] Aspect 59. The method according to any one of Aspects 1 to 58, wherein the printing comprises: receiving a set of predetermined information of the three-dimensional structure; wherein the set of predetermined information includes a first thickness of a region of the three-dimensional structure and the thickness of a structural layer; calculating the number of structural layers to be printed in the region to achieve the first thickness of the region of the three-dimensional structure; instructing a printing apparatus to use the set of predetermined information to print one or more structural layers onto the component, wherein the number of structural layers is equal to the calculated number of structural layers; and printing the one or more structural layers onto the component to provide the three-dimensional structure having the first thickness.

[0102] Aspect 60. The method according to any one of aspects 1 to 59, wherein the printing further comprises printing one or more color layers.

[0103] Aspect 61. The method according to any one of Aspects 1 to 60, wherein applying the coating comprises applying the coating to dye foam particles, attached foam particles, bonding materials, the component or a portion thereof, or a combination thereof.

[0104] Aspect 62. The method according to any one of Aspects 1 to 61, wherein the dyeing comprises spraying a dye composition onto a target dye area.

[0105] Aspect 63. The method according to any one of Aspects 1 to 62, wherein the dyeing comprises spraying the dye composition onto at least a portion of the outer surface region of the component.

[0106] Aspect 64. The method according to any one of Aspects 1 to 63, wherein dyeing comprises adding a dye composition to the binding material.

[0107] Aspect 65. The method according to any one of Aspects 1 to 64, wherein the dyeing comprises immersing at least a portion of the component in a dye composition.

[0108] Aspect 66. The method according to any one of aspects 1 to 65, wherein the dye composition comprises a dye solution containing at least one dye.

[0109] Aspect 67. The method according to any one of Aspects 1 to 66, wherein the dye solution is an aqueous dye solution.

[0110] Aspect 68. The method according to any one of Aspects 1 to 67, wherein the dye solution comprises a water-soluble organic solvent from about 1 percent to about 50 percent by volume.

[0111] Aspect 69. The method according to any one of Aspects 1 to 68, wherein the water-soluble organic solvent is a solvent selected from the group consisting of methanol, ethanol, n-propanol, acetone, methyl ethyl ketone, butyl acetate, and combinations thereof.

[0112] Aspect 70. The method according to any one of aspects 1 to 69, wherein the at least one dye is an acid dye.

[0113] Aspect 71. The method according to any one of Aspects 1 to 70, wherein the acid dye is an anionic acid dye.

[0114] Aspect 72. The method according to any one of aspects 1 to 71, wherein the at least one dye is a disperse dye.

[0115] Aspect 73. The method according to any one of Aspects 1 to 72, wherein the dye solution comprises a quaternary ammonium compound.

[0116] Aspect 74. The method according to any one of Aspects 1 to 73, wherein the quaternary ammonium compound is a soluble tetrabutylammonium compound.

[0117] Aspect 75. The method according to any one of Aspects 1 to 74, wherein the soluble tetrabutylammonium compound comprises tetrabutylammonium bromide or tetrabutylammonium chloride or both.

[0118] Aspect 76. The method according to any one of aspects 1 to 75, wherein the dye solution comprises from about 0.1 equivalents to about 5 equivalents of a quaternary ammonium compound per amount of the at least one dye.

[0119] Aspect 77. The method according to any one of aspects 1 to 76, wherein the dye solution comprises the at least one dye from about 0.001 g / L to about 5.0 g / L.

[0120] Aspect 78. The method according to any one of aspects 1 to 77, wherein the dye solution comprises the anionic dye from about 0.01 g / L to about 2.0 g / L.

[0121] Aspect 79. The method according to any one of Aspects 1 to 78, wherein the dye composition comprises an infrared absorbing dye.

[0122] Aspect 80. The method according to any one of Aspects 1 to 79, wherein the infrared absorbing dye is anthraquinone dye, cyanine dye, polymethyl dye, azo dye, azo dye, polyazo dye, diamine dye, ammonium dye, phthalocyanine dye, naphthyl phthalocyanine dye, indocyanine dye, naphthoquinone dye, indophenol dye, triallylmethane dye, metal complex dye, nickel dithiol complex dye, cobalt azo complex dye, squaric acid cyanine dye, or a combination thereof.

[0123] Aspect 81. The method according to any one of Aspects 1 to 80, wherein the infrared absorbing dye is added to the binding material at a weight percentage from about 0.001 to about 0.08% based on the total weight of the binding material.

[0124] Aspect 82. The method according to any one of Aspects 1 to 81, wherein the infrared absorbing dye is added to the binding material at a weight percentage from about 0.005 to about 0.06% based on the total weight of the binding material.

[0125] Aspect 83. The method according to any one of Aspects 1 to 82, wherein applying the coating comprises applying the coating to foam particles, attached foam particles, bonding materials, the component or a portion thereof, or a combination thereof.

[0126] Aspect 84. The method according to any one of Aspects 1 to 83, wherein applying the coating comprises depositing a colorant composition onto a target colorant region.

[0127] Aspect 85. The method according to any one of Aspects 1 to 84, wherein the deposition comprises brushing, spraying or coating a colorant composition onto a target colorant area.

[0128] Aspect 86. The method according to any one of Aspects 1 to 85, wherein applying the coating comprises immersing at least a portion of the component in a colorant composition.

[0129] Aspect 87. The method according to any one of Aspects 1 to 86, wherein applying the coating comprises adding a colorant composition to the bonding material.

[0130] Aspect 88. The method according to any one of Aspects 1 to 87, wherein the colorant composition comprises pigment, ink, dye, coating or combination thereof.

[0131] Aspect 89. The method according to any one of Aspects 1 to 88, wherein embossing or debossing the component or a portion thereof comprises: contacting a first surface of the component with a second surface of a relief device; and after the contact, removing the second surface of the relief device from the first surface of the component while retaining the embossed or debossed texture on the first surface of the component.

[0132] Aspect 90. The method according to any one of Aspects 1 to 89 further comprises: raising the temperature of the first surface of the component to a temperature above one of the following before or during the contact: the creep relaxation temperature, heat distortion temperature, Vicat softening temperature, or melting temperature of the thermoplastic material of the first surface, so as to at least partially melt or soften the first surface.

[0133] Aspect 91. The method according to any one of Aspects 1 to 90, further comprising: during or after the contact, reducing the temperature of the first surface of the component to below a temperature of: the creep relaxation temperature, heat distortion temperature, Vicat softening temperature, or melting temperature of the thermoplastic material of the first surface, so as to at least partially resolidify the first surface.

[0134] Aspect 92. The method according to any one of Aspects 1 to 91, wherein the embossing device comprises a cylinder, plate, roller, mold, or release paper.

[0135] Aspect 93. The method according to any one of Aspects 1 to 92, wherein the second surface of the embossing device comprises a relief pattern, and the method results in the formation of an imprint of the relief pattern on the first surface of the component.

[0136] Aspect 94. The method according to any one of Aspects 1 to 93, wherein the embossing device is a mold having a mold surface; and the step of contacting the second surface of the embossing device with the first surface of the component comprises inserting the component into the mold such that the first surface of the component contacts the mold surface of the mold.

[0137] Aspect 95. The method according to any one of aspects 1 to 94 further includes applying pressure between the second surface of the relief device and the first surface of the component.

[0138] Aspect 96. An article comprising an article manufactured by the method according to any one of the preceding aspects.

[0139] Aspect 97. The article according to aspect 96, wherein the article is a component for manufacturing footwear, clothing, or sports equipment.

[0140] Aspect 98. The article according to any one of Aspects 96 to 97, wherein the component used in the manufacture of footwear, clothing, or sports equipment articles is a cushioning element or shock-absorbing element for footwear.

[0141] Aspect 99. The article according to any one of Aspects 96 to 98, wherein the cushioning element for footwear articles is a midsole, an outsole, a combined midsole-outsole unit, an insole, an ankle collar, or a heel cushioning pad.

[0142] Aspect 100. The article according to any one of Aspects 96 to 99, wherein the component for manufacturing footwear, clothing or sports equipment is a preform.

[0143] Aspect 101. The article according to any one of Aspects 96 to 100, wherein the article is a padding component for manufacturing sports helmets, backpacks, clothing, sports uniform padding, or combat gear.

[0144] Aspect 102. The article according to any one of aspects 96 to 101, wherein the article is a component for manufacturing tactical equipment articles.

[0145] Aspect 103. The article according to any one of Aspects 96 to 102, wherein the tactical equipment article is a bag, backpack, equipment bag, chest bag, rifle sling, belt, pistol holster, vest or jacket.

[0146] Aspect 104. The article according to any one of Aspects 96 to 103, wherein the component used for manufacturing tactical equipment articles is a padding component.

[0147] Aspect 105. The article according to any one of Aspects 96 to 104, wherein the article is a component for manufacturing work safety equipment articles.

[0148] Aspect 106. The article according to any one of Aspects 96 to 105, wherein the work safety equipment article is a safety garment, a work helmet, work boots, or work gloves.

[0149] Aspect 107. The article according to any one of aspects 96 to 106, wherein the component used in manufacturing the work safety equipment article is a padding component.

[0150] Aspect 108. An article comprising: a component formed of more than one attached foam particle, wherein each individual foam particle of the more than one attached foam particle is formed of a thermoplastic elastomer material and includes one or more bonding regions on the outer surface of the individual foam particle, the bonding regions attaching the individual foam particle to one or more adjacent foam particles, the one or more adjacent foam particles comprising a thermoplastic elastomer material, the component formed of the more than one attached foam particle including more than one gap between the foam particles; wherein prior to attachment, the more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and wherein a portion of the more than one attached foam particle of the component includes a coating, or the surface of the component including a portion of the foam particle is embossed or debossed, or both.

[0151] Aspect 109. The article according to any one of Aspects 96 to 108, wherein the gaps between the foam particles occupy at least 10 percent of the total volume of the component.

[0152] Aspect 110. An article according to any one of aspects 96 to 109, wherein, prior to attachment, at least 20 percent of the more than one foam particle is spherical or ellipsoidal in shape, and at least 20 percent of the spherical or ellipsoidal foam particles in the component retain a generally spherical or ellipsoidal shape.

[0153] Aspect 111. The article according to any one of aspects 96 to 110, wherein the more than one attached foam particle comprises layers of attached foam particles, and the average number of layers per millimeter in the component is from about 0.1 layers per millimeter to about 2.5 layers per millimeter.

[0154] Aspect 112. The article according to any one of aspects 96 to 111, wherein the average number of layers per millimeter in said component is from about 0.3 layers per millimeter to 2 layers per millimeter.

[0155] Aspect 113. The article according to any one of aspects 96 to 112, wherein the component comprises from 3 to 100 layers.

[0156] Aspect 114. The article according to any one of aspects 96 to 113, wherein the component comprises from 3 to 50 layers.

[0157] Aspect 115. The article according to any one of Aspects 96 to 114, wherein the coating comprises ink, paint, dye, film or any combination thereof.

[0158] Aspect 116. The article according to any one of aspects 96 to 115, wherein the individual foam particles of the more than one attached foam particles of the component have a first color, and the coating has a second color different from the first color.

[0159] Aspect 117. The article according to any one of aspects 96 to 116, wherein each individual foam particle of the more than one attached foam particle of the component has a first color, and the coating has a second color different from the first color.

[0160] Aspect 118. An article according to any one of Aspects 96 to 117, wherein, when measured at an angle between -15 degrees and +60 degrees under given illumination conditions according to the CIE 1976 color space, the first color has a first color measurement value having coordinates L1* and a1* and b1*, and the second color has a second color measurement value having coordinates L2* and a2* and b2*, wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the a1* coordinate value is at least 10 percent larger or smaller than the a2* coordinate value; the b1* coordinate value is at least 10 percent larger or smaller than the b2* coordinate value; or a combination thereof.

[0161] Aspect 119. An article according to any one of Aspects 96 to 118, wherein when measured at an angle between -15 degrees and +60 degrees under given illumination conditions according to the CIE 1976 color space, the first color has a first color measurement having coordinates L1* and a1* and b1*, and the second color has a second color measurement having coordinates L2* and a2* and b2*, wherein the L1* and L2* values ​​may be the same or different, wherein the a1* and a2* coordinate values ​​may be the same or different, wherein the b1* and b2* coordinate values ​​may be the same or different, and wherein ΔE*ab between the first color measurement and the second color measurement is greater than or equal to about 60, wherein ΔE*ab = [(L1*-L2*)² + (a1*–a2*)² + (b1*-b2*)²]¹ / ², optionally greater than or equal to about 80, or optionally greater than or equal to about 100.

[0162] Aspect 120. An article according to any one of Aspects 96 to 119, wherein, when measured at an angle between -15 degrees and +60 degrees under given illumination conditions according to the CIELCH color space, the first color has a first color measurement value having coordinates L1* and C1* and h1°, and the second color has a second color measurement value having coordinates L2* and C2* and h2°, wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the C1* coordinate value is at least 10 percent larger or smaller than the C2* coordinate value; the h1° coordinate value is at least 10 percent larger or smaller than the h2° coordinate value; or a combination thereof.

[0163] Aspect 121. The article according to any one of aspects 96 to 120, wherein the bonding region comprises a portion of the thermoplastic elastomer material from the surface of the individual foam particles mixed with a portion of the thermoplastic elastomer material from the surface of one or more adjacent foam particles.

[0164] Aspect 122. The article according to any one of aspects 96 to 121, wherein the bonding region comprises a bonding material, a portion of the thermoplastic elastomer material from the foam particle or at least one of the one or more adjacent foam particles, a portion of the thermoplastic elastomer material from the individual foam particle mixed with a portion of the thermoplastic elastomer material from at least one of the one or more adjacent foam particles, or any combination thereof.

[0165] Aspect 123. The article according to any one of aspects 96 to 122, wherein the bonding region comprises a dissolved and resolidified thermoplastic elastomer material from the individual foam particles, from at least one of the one or more adjacent foam particles, or both.

[0166] Aspect 124. The article according to any one of Aspects 96 to 123, wherein the bonded region comprises a dissolved and re-solidified binder material from the individual foam particles, from at least one of the one or more adjacent foam particles, or both.

[0167] Aspect 125. The article according to any one of Aspects 96 to 124, wherein the coating of the foam particle portion comprises printed markings on the outer surface of the article.

[0168] Aspect 126. The article according to any one of aspects 96 to 125, wherein the printed markings comprise at least one ink.

[0169] Aspect 127. The article according to any one of aspects 96 to 126, wherein the printed markings comprise more than one type of ink.

[0170] Aspect 128. The article according to any one of Aspects 96 to 127, wherein at least one of the inks comprises a CMYK formulation or an RGB formulation.

[0171] Aspect 129. The article according to any one of aspects 96 to 128, wherein at least one of the inks comprises a sublimation ink formulation.

[0172] Aspect 130. The article according to any one of aspects 96 to 129, wherein at least one of the inks comprises a formulation containing an infrared radiation absorber.

[0173] Aspect 131. The article according to any one of aspects 96 to 130, comprising a primer layer disposed between the outer surface of the article and the printed markings.

[0174] Aspect 132. The article according to any one of aspects 96 to 131, wherein the primer layer comprises pigment, dye or both.

[0175] Aspect 133. The article according to any one of Aspects 96 to 132, wherein the primer layer comprises a coating, an ink, or both.

[0176] Aspect 134. The article according to any one of Aspects 96 to 133, wherein the primer layer comprises a re-ground and at least partially degraded polymer.

[0177] Aspect 135. The article according to any one of Aspects 96 to 134, wherein the primer layer is a coating, wherein the coating comprises a polymer coating composition.

[0178] Aspect 136. The article according to any one of Aspects 96 to 135, wherein the coating is a cross-linked coating comprising a cross-linked polymer matrix and optionally comprises more than one solid pigment particle embedded in the cross-linked polymer matrix.

[0179] Aspect 137. The article according to any one of Aspects 96 to 136, wherein the crosslinked polymer matrix comprises a crosslinked elastomer polymer, optionally the crosslinked elastomer polymer comprises a crosslinked polyurethane homopolymer or a crosslinked polyurethane copolymer or both, and optionally the crosslinked polyurethane copolymer comprises a crosslinked polyester polyurethane.

[0180] Aspect 138. The article according to any one of Aspects 96 to 137, wherein the coating is a product of crosslinking a polymer coating composition comprising a dispersion of a polymer and optionally comprising at least one of a crosslinking agent, more than one solid pigment particle, a dye, and an organic solvent.

[0181] Aspect 139. The article according to any one of aspects 96 to 138, wherein the primer layer has a transmittance of about 40 percent or less.

[0182] Aspect 140. An article according to any one of aspects 96 to 139, comprising a three-dimensional structure on the outer surface of the article.

[0183] Aspect 141. The article according to any one of Aspects 96 to 140, wherein one or more of the foam particles, the bonding material, the component or combination thereof include colorants, inks, dyes, coatings or pigments.

[0184] Aspect 142. The article according to any one of aspects 96 to 141, wherein at least a portion of the outer surface of the article has an embossed or recessed texture.

[0185] Aspect 143. An article according to any one of Aspects 96 to 142, wherein the article is characterized by more than one sub-region, the more than one sub-region comprising a first sub-region characterized by a first property and a second sub-region characterized by a second property, wherein the first property is not equal to the second property, and wherein the first property and the second property are flexural modulus, stiffness, bulk density or elasticity.

[0186] Aspect 144. The article according to any one of Aspects 96 to 143, wherein the first property is at least 10 percent greater than the second property.

[0187] Aspect 145. An article according to any one of aspects 96 to 144, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first flexural modulus and a second sub-region characterized by a second flexural modulus, wherein the first flexural modulus is not equal to the second flexural modulus.

[0188] Aspect 146. An article according to any one of Aspects 96 to 145, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first packing density and a second sub-region characterized by a second packing density, wherein the first packing density is not equal to the second packing density.

[0189] Aspect 147. An article according to any one of Aspects 96 to 146, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first stiffness and a second sub-region characterized by a second stiffness, wherein the first stiffness is not equal to the second stiffness.

[0190] Aspect 148. An article according to any one of Aspects 96 to 147, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first elasticity and a second sub-region characterized by a second elasticity, wherein the first elasticity is not equal to the second elasticity.

[0191] Aspect 149. A footwear article comprising: an upper operatively coupled to a sole structure, wherein the sole structure includes a cushioning element comprising an article according to any one of aspects 96 to 148.

[0192] Items manufactured using the disclosed methods.

[0193] Footwear 10 is an exemplary article of athletic footwear, comprising one or more component articles manufactured using the methods of this disclosure. Although illustrated as a running shoe, footwear 10 can be optionally configured for any suitable athletic performance, such as baseball shoes, basketball shoes, soccer / international soccer shoes, American soccer shoes, running shoes, cross-training shoes, cheerleading shoes, golf shoes, etc. While athletic footwear... Figure 1The examples are illustrated herein, but it will be readily understood that some of the terminology used will also apply to other footwear articles or to other styles of shoes. Footwear 10 includes an upper 12 and a sole component 14 attached to the upper 12. The sole component 14 may be attached to the upper 12 by adhesive or any other suitable means. As used herein, the sole component 14 may be a monolithic component formed entirely of an article manufactured using the methods disclosed herein, or a multi-component assembly formed of more than one monolithic component, wherein at least one of the monolithic components is formed entirely of an article manufactured using the methods disclosed herein.

[0194] Footwear 10 has an inner or medial side 16 and an outer or lateral side 18. For ease of discussion, footwear 10 can be divided into three parts: a forefoot portion 20, a midfoot portion 22, and a heel portion 24. Parts 20, 22, and 24 are not intended to precisely delineate the areas of footwear 10. Rather, parts 20, 22, and 24 are intended to represent the various areas of footwear 10, which provides a frame of reference during the discussion below. Unless otherwise indicated, directional terms used herein, such as backward, forward, top, bottom, inward, downward, upward, etc., refer to directions relative to footwear 10 itself. Footwear 10 in Figure 1 The orientation is generally horizontal, as if it would be positioned on a horizontal surface when worn by the wearer. However, it should be understood that footwear 10 is not required to be limited to such an orientation. Therefore, in Figure 1 In the middle, towards the back is the part facing the heel 24 (e.g.) Figure 1 (As seen in the image, to the right), forward is towards the front part of the shoe (e.g., 20). Figure 1 (As seen in the image, to the left), and downwards is towards... Figure 1 The bottom of the page as seen in the image. The top refers to the area facing upwards. Figure 1 The element at the top of the view, while the bottom refers to the element facing the top. Figure 1 The element at the bottom of the view. Inward is towards the center of footwear 10, and outward is towards the outer edge of footwear 10.

[0195] The component can be a shoe sole component, such as in Figures 1-5 The shoe sole component 14 depicted includes an article manufactured using the methods disclosed herein. The component may be an insert, such as... Figures 4-5The insert 36 or 60 depicted herein includes articles manufactured using the methods disclosed herein. The sole component and the insert for the sole component may be manufactured partially or entirely from articles manufactured using the methods disclosed herein. Any portion of the sole component or the insert for the sole component may be manufactured from articles manufactured using the methods disclosed herein. For example, a first portion 26 of the sole component (optionally including a lower surface 44 engaging the ground, such as more than one protrusion 46 and / or a groove 48 surrounding the protrusion), the entire insert 36, portions 62 or 64 of the insert 60, a separate outsole component, or any combination thereof, may include articles manufactured using the methods disclosed herein.

[0196] The sole component 14, typically positioned between the wearer's foot and the ground, provides attenuation of ground reaction forces (i.e., cushioning), adhesive friction, and can control foot movements such as pronation. Like conventional footwear, the sole component 14 may include an insole (not shown) located within the upper 12. The sole component may be an insole or insole, or a multi-part assembly including an insole or insole, and may also include an insole or insole located within the upper, wherein the insole or insole is formed wholly or partially from an article manufactured using the methods disclosed herein. The footwear articles described herein may include insoles or insoles formed wholly or partially from articles manufactured using the methods disclosed herein.

[0197] like Figure 2 As can be seen, the sole component 14 consists of a first portion 26 having an upper surface 27 with recesses 28 formed therein. The upper surface 27 is secured to the upper 12 using an adhesive or other suitable fastening means. More than one generally horizontal rib 30 is formed on the exterior of the first portion 26. The rib 30 extends rearward from the central portion of the forefoot portion 20 on the inner side 16 along the first portion 26, around the heel portion 24, and forward on the outer side 18 of the first portion 26 to the central portion of the forefoot portion 20.

[0198] The first part 26 provides an external attachment friction surface for the sole component 14. It should be understood that a separate outsole component can be attached to the lower surface of the first part 26. When a separate outsole component is attached to the lower surface of the first part 26, the first part 26 is a sole interlayer component. The article can be a sole interlayer component for footwear articles.

[0199] The item can be an insert, such as an insert 36 that can be received in the recess 28, such as... Figure 2As illustrated in the diagram. Insert 36 can provide cushioning or elasticity in the sole component. First portion 26 can provide structure and support for insert 36. First portion 26 can be formed of a material with higher density and / or higher hardness compared to insert 36, such as non-foamed materials including, for example, rubber and thermoplastic polyurethane, as well as foamed materials. Insert 36 can be formed of an article manufactured using the methods disclosed herein.

[0200] The insert 36 has a curved rear surface 38 to mate with the curved rear surface 32 of the recess 28, and a transverse front surface 40 to mate with the transverse front surface 34 of the recess 28. The upper surface 42 of the insert 36 contacts the upper 12 and is secured to the upper 12 by adhesive or other suitable fastening means. For example, when the insert 36 is present, the recess 28 can extend from the heel portion 24 to the forefoot portion 20. The rear surface 32 of the recess 28 can be bent to generally follow the contour of the rear of the heel portion 24, and the front surface 34 of the recess 28 extends transversely across the first portion 26.

[0201] like Figure 3 As best viewed from the center, the lower surface 44 of the mating surface of the first portion 26 includes more than one protrusion 46. Each protrusion 46 is surrounded by a groove 48. More than one lateral slot 50 is formed in the lower surface 44, extending between adjacent protrusions 46. A longitudinal slot 52 extends along the lower surface 44 from the heel portion 26 to the forefoot portion 20.

[0202] Figure 4 and Figure 5 The diagram shows a bottom view and a top view of an insert 60, which can be used in a shoe sole component as described herein. Insert 60 is similar to insert 36, but... Figure 4 and Figure 5 As illustrated in the figure, the insert 60 is formed of two types of materials 62 and 64, wherein at least one of the materials is an article manufactured using the methods disclosed herein. Figure 4 A bottom view of the insert 60 is shown, while Figure 5 A top view of an insert 60, formed of two types of materials 62 and 64, is shown, wherein the insert is placed inside a first portion 66 to form a sole component 14. Inserts having more than two types of materials can also be used, at least one of which is an article manufactured using the methods disclosed herein. Figure 4 and Figure 5In the example illustrated, a portion of the first material 62 can be used in the heel region of the insert, and a portion of the second material 64 can be used in the toe region of the insert. A higher-density material can be used to support the heel region, while a lower-density material can be used to support the toe region. For example, the density of the first material can be at least 0.02 g / cm³ greater than the density of the second material. The shapes of the portions of the two materials 62 and 64 of the insert can be any suitable shape. For example, the heel region can be wedge-shaped. Inserts formed from these two types of materials are useful in running shoes as well as in basketball shoes.

[0203] Figure 6 An external view of a footwear article 100, such as an athletic shoe article, is shown. The footwear article 100 has an upper 110 and a sole component 120. The footwear article 100 may also include other components typical of footwear or athletic shoes, such as a sole midsole, insole, padded collar, etc. However, for ease of discussion herein, only the upper 110 and sole component 120 are specifically shown in the figures. The disclosed article may be the sole component 120, which has, for example... Figure 6 The outer shape shown or other outer shapes as determined by the specific requirements of footwear items. Figure 7 A corresponding plan view of the sole component 120 is shown, and a corresponding outer view of the sole component 120 is shown in... Figure 6 As shown in the diagram. The disclosed item may be a sole component 120, which has, for example... Figure 7 The plan view shape shown or other plan view shapes as determined by the specific needs of footwear items.

[0204] Figure 8 A plan view of a sole component 120 is shown, comprising three sub-regions with different properties prepared using the disclosed method described herein. The sole component 120 may include two or more sub-regions with different properties, such as density, flexural modulus, elasticity, etc., which may be associated with different types of foam particles, different binders, or different heating levels experienced by each sub-region in the method. For example, sub-regions 121a, 121b, and 121c have defined planar geometry generally located within the heel portion of the sole component. Although these sub-regions 121a, 121b, and 121c are shown as having rectangular geometry, those skilled in the art will understand that any number of geometries are possible and contemplated herein. Furthermore, the arrangement of these sub-regions 121a, 121b, and 121c may vary based on the geometry, size, and location of desired sub-regions with desired densities to provide desired performance characteristics for the sole component.

[0205] The foam particles within these subregions 121a, 121b, and 121c can be completely unattached. For example, as the energy beam passes through the xy coordinates within 121a, 121b, and 121c, the energy beam can pause energy beam emission within these subregions; or the binding material can be deposited in a manner such that no binding material is deposited within subregions 121a, 121b, and 121c. Therefore, the density of these subregions 121a, 121b, and 121c can be less than that of other subregions exposed to the energy beam for one or more iterations or receiving binding material, as appropriate. Alternatively, the foam particles within these subregions 121a, 121b, and 121c can undergo only a single iteration of energy beam exposure. The foam particles within these subregions 121a, 121b, and 121c can undergo 2–7 iterations of energy beam exposure, but fewer iterations than subregions 122 or 123. Alternatively, the foam particles within these sub-regions 121a, 121b, and 121c may receive a portion of the binding material deposited in other regions such as sub-regions 122 or 123.

[0206] In comparison, Figure 8 Subregion 122 comprises attached foam particles having substantially the same properties, such as density. For example, in some embodiments, the foam particles in subregion 122 are exposed to an energy beam of the same intensity and duration. In other embodiments, subregion 122 comprises a homogeneous composition of an adhesive composition and foam particles. In the illustrated plan view, subregion 123 is essentially the edge of the sole component 120. The foam particles in this subregion are characterized as highly fused or highly bonded. The densities of subregions 122 and 123 may be greater than the densities of subregions 121a, 121b, and 121c. The density of subregion 123 may be greater than the density of subregion 122.

[0207] Figure 9 It shows Figure 8 The figure shows a cross-sectional view of the sole component 120 along line AA. This cross-sectional view shows that the sub-regions 121a, 121b, and 121c can not only have defined planar geometry, but can also extend along different portions of the depth (or z-axis) of the sole component 120.

[0208] Figure 10A planar view of the sole component 120 is shown, which includes a gradient variation in the fusion of the foam particles contained therein. For example, variables such as energy beam output and exposure time can be changed in very small xy-dimensional steps, such that the fusion level of the foam particles has a gradient characteristic from sub-region 124a to sub-region 124b to sub-region 124c. Alternatively, the deposition of the bonding material on the foam particles may also have a gradient characteristic from sub-region 124a to sub-region 124b to sub-region 124c. Therefore, properties associated with the fusion level, such as the density of the sub-regions, can vary gradient from one sub-region to another. Figure 10 In the diagram, the fusion level of the foam particles is represented by the grayscale values ​​shown, where brighter areas have lower fusion levels and darker areas have higher fusion levels. For example... Figure 10 As shown, the sole component 120 includes another sub-region 123 that defines the highly fused or joined outer edge of the sole component 120.

[0209] While the methods disclosed herein can be used to manufacture any of a variety of components, including those for footwear articles, components may include pre-formed sole interlayers, outsoles, insoles, heel cushioning pads, insoles, or inserts. Other articles may include tongue pads, collar pads, and combinations thereof. As described above and in more detail below, articles manufactured using the methods disclosed herein may exhibit sub-regions with different properties, such as, but not limited to, bulk density, elasticity, or flexural modulus. Sub-regions may be discrete regions having properties that are more or less uniformly distributed within the sub-regions. Articles manufactured by the disclosed methods can be characterized by a gradient distribution of properties along the x-axis, y-axis, and / or z-axis of the article.

[0210] The item can be a padding component in shin guards, shoulder pads, chest protectors, covers, helmets or other headgear, knee protectors and other protective equipment; a component placed between textile layers in clothing items; or it can be used in other known padding applications for protection or comfort, especially applications where the weight of the padding is a concern.

[0211] This disclosure relates to articles manufactured using the methods disclosed herein. These articles can be used to manufacture footwear. Articles used in the manufacture of footwear can be sole interlayers, outsoles, insoles, or heel cushioning pads, or can be preforms that are compression molded to form sole interlayers, outsoles, insoles, or heel cushioning pads. Articles can be padding components for sports helmets, backpacks, clothing, sports uniform padding, or combat gear.

[0212] In several instances, an article is characterized by more than one sub-region, which includes a first sub-region characterized by a first property and a second sub-region characterized by a second property, wherein the first property is not equal to the second property, and wherein the first property and the second property are flexural modulus, stiffness, bulk density or elasticity.

[0213] In several instances, an article is characterized by more than one cross-sectional sub-region, which includes a first sub-region characterized by a first flexural modulus and a second sub-region characterized by a second flexural modulus, wherein the first flexural modulus is not equal to the second flexural modulus.

[0214] In several instances, an article is characterized by more than one cross-sectional sub-region, which includes a first sub-region characterized by a first packing density and a second sub-region characterized by a second packing density, wherein the first packing density is not equal to the second packing density.

[0215] In several instances, an object is characterized by more than one cross-sectional sub-region, which includes a first sub-region characterized by a first stiffness and a second sub-region characterized by a second stiffness, wherein the first stiffness is not equal to the second stiffness.

[0216] In several instances, an item is characterized by more than one cross-sectional sub-region, which includes a first sub-region characterized by a first elasticity and a second sub-region characterized by a second elasticity, wherein the first elasticity is not equal to the second elasticity.

[0217] A method of manufacturing parts using foam particles.

[0218] This disclosure relates to a method for forming an article, the method comprising: arranging more than one foam particle, wherein the arranged more than one foam particle comprises a thermoplastic material, and wherein the arranged more than one foam particle has a number-average particle size of about 0.04 mm to about 10 mm in its longest dimension; and attaching at least a portion of the more than one foam particle together, wherein the arrangement and the attachment are iterated two or more times to form a part; and decorating a portion of the more than one foam particle. As described in more detail below, the decoration may include applying a coating to a portion of the more than one foam particle, embossing or debossing a portion of the more than one foam particle, or both.

[0219] The methods described herein include multiple disclosed steps, each of which may be repeated, and as used herein, "iteration" is understood to refer to the repetition of a step or set of steps. For example, the disclosed methods may include steps such as arranging more than one foam particle and attaching at least one or more foam particles together, as described above. Therefore, it should be understood that this disclosure covers one or more iterations of each step independent of the other steps. For example, the arrangement step may be repeated one or more times independently of the other steps or iterations of steps. In a similar manner, attachment may be repeated one or more times independently of iterations of the arrangement step. In other cases, iteration may include one or more repetitions of all steps or a set of steps. For example, the method may include one or more iterations involving a combination of arrangement steps and attachment steps or a series of arrangement steps and attachment steps. It should be understood that iteration may include one or more other steps, either commonly or independently, or portions of steps as described herein. Therefore, a loop comprising a series of steps may be repeated one or more times. The number of iterations can be from 1 to approximately 500 iterations, from 1 to approximately 400 iterations, from 1 to approximately 300 iterations, from 1 to approximately 250 iterations, from 1 to approximately 200 iterations, from 1 to approximately 150 iterations, from 1 to approximately 100 iterations, from 1 to approximately 90 iterations, from 1 to approximately 80 iterations, from 1 to approximately 70 iterations, from 1 to approximately 60 iterations, from 1 to approximately 50 iterations, from 1 to approximately 40 iterations, from 1 to approximately 30 iterations, from 1 to approximately 20 iterations, from 1 to approximately 10 iterations, from 1 to approximately 9 iterations, from 1 to approximately 8 iterations, from 1 to approximately 7 iterations, from 1 to approximately 6 iterations, from 1 to approximately 5 iterations, from 1 to approximately 4 iterations, from 1 to approximately 3 iterations, from 1 to approximately 2 iterations, any subrange of the aforementioned range, or any set of values ​​within the aforementioned range.

[0220] Depositing more than one foam particle may include depositing a layer containing more than one foam particle. This layer may be substantially planar. The component formed by the disclosed method may be formed from a single layer. Alternatively, the component formed by the disclosed method may be formed from at least two layers. The component may be formed from 2 to 50 layers; 2 to 40 layers; 2 to 30 layers; 2 to 25 layers; 2 to 20 layers; 2 to 15 layers; 2 to 10 layers; or 2 to 5 layers. The component may be formed layer by layer from more than one layer.

[0221] The step of arranging more than one foam particle in the disclosed method includes arranging it using a roller mechanism, a wiping mechanism, a blower mechanism, or a combination thereof. An exemplary roller mechanism may include a smooth roller surface, or alternatively, a textured roller surface. Arranging more than one foam particle may include arranging it using a wiping mechanism. It should be understood that arranging more than one foam particle can be arranging more than one layer of foam particles.

[0222] Attaching multiple foam particles together can include attaching arranged foam particles to a target area. As discussed further below, attachment can include depositing a bonding material into the target area and then curing the bonding material to attach multiple foam particles to the target area. As discussed further below, attachment can include applying photochemical radiation to the target area to fuse multiple foam particles to the target area. A target area is understood to include any area containing more than one foam particle to which bonding material or photochemical radiation is directed. A target area can include the outer surface of a region or sub-region, and the portion below it that is adjacent to or communicates with the outer surface of the region or sub-region. A target area can include not only the outer surface of more than one foam particle, but also those portions of the bonding material accessible to more than one foam particle. A target area can include not only the outer surface of more than one foam particle, but also those portions of the photochemical radiation accessible to more than one foam particle for softening or melting the foam particle. For example, a target area can be part of a layer of more than one foam particle. In some cases, the bonding material can be provided via a nozzle such as a piezoelectric printhead, which is used to spray or coat the bonding material onto a subset of more than one foam particle in certain portions of a layer of more than one foam particle. Alternatively, if the desired target area includes all foam particles, the bonding material can be provided to all or substantially all of the more than one foam particle. In some cases, photochemical radiation can be provided via a directed energy beam, which is used to raise the temperature of a subset of more than one foam particle in certain portions of a layer of more than one foam particle. Alternatively, if the desired target area includes all foam particles, the photochemical radiation can be provided to all or substantially all of the more than one foam particle. In some embodiments, the component may include more than one target area, each of which independently receives the desired application of photochemical radiation or bonding material. For example, the method may include depositing a first bonding material onto a first target area and depositing a second bonding material onto a second target area. Similarly, the method may include applying photochemical radiation to a first target area under a first set of conditions and applying a second set of conditions to a second target area. The method may include depositing a bonding material onto a first target region and depositing photochemical radiation onto a second target region. In this way, components having sub-regions with different properties can be manufactured.

[0223] Use bonding materials for attachment.

[0224] Attaching at least a portion of more than one foam particle together may include attaching the foam particles using one or more bonding materials. The bonding materials may include any of the bonding materials described herein.

[0225] Therefore, attachment may include depositing a binder material in a target region of the binder material, wherein the target region of the binder material includes at least a portion of more than one foam particle disposed therefrom. The binder material may be liquid or solid. The binder material may include one or more binder materials. The deposited binder material coats at least a portion of the defining surface of more than one foam particle disposed therefrom. After deposition, the deposited binder material solidifies or cures in at least the target region of the binder material, wherein solidification or curing results in the attachment of at least a portion of more than one foam particle disposed therefrom to the target region.

[0226] Solidification or curing of the bonding material may include lowering the temperature of the bonding material to a temperature below its creep relaxation temperature, heat distortion temperature, Vicat softening temperature, or melting temperature, so as to at least partially solidify the bonding material. Attachment may include: applying an amount of energy to the deposited bonding material and more than one arranged foam particle for a duration sufficient to soften the bonding material; and lowering the temperature of the region containing more than one arranged foam particle to or below the temperature at which the softened bonding material re-solidifies; thereby attaching at least a portion of at least a portion of the encapsulated portion of more than one foam particle in the target region of the bonding material. Applying energy may include applying energy in the infrared spectrum.

[0227] The bonding material may comprise one or more monomers, one or more polymers, or combinations thereof; and solidification or curing includes: forming at least one chemical bond between one or more monomers, one or more polymers, or combinations thereof in the bonding material; and / or forming at least one chemical bond between at least a portion of the covered surface of more than one foam particle arranged in the target region of the bonding material and one or more monomers, one or more polymers, or combinations thereof in the bonding material; thereby attaching at least a portion of the covered foam particle arranged in the target region of the bonding material to each other or to an uncovered foam particle.

[0228] The bonding material may include a solvent for the foam particles, and after the bonding material is deposited, at least a portion of the defining surface of more than one foam particle is dissolved in the solvent to form a dissolved defining surface of the arranged foam particles. After dissolution, solidification and curing include: removing at least a portion of the solvent from the bonding material, and solidifying at least a portion of the dissolved defining surface of the arranged foam particles, thereby attaching at least a portion of the more than one foam particle in the target region of the bonding material to each other or to uncoated foam particles.

[0229] The method may include depositing a first bonding material and a second bonding material, the first bonding material comprising a solvent, and the second bonding material being a solvent-soluble bonded thermoplastic elastomer. Solidification or curing may include removing the solvent and solidifying the bonded thermoplastic elastomer material on at least a portion of the defining surface of the arranged foam particles, thereby attaching at least a portion of more than one foam particle arranged in the bonding material target region to each other or to an uncoated foam particle.

[0230] Depositing a bonding material can include spraying or atomizing the bonding material onto a target area of ​​an arrangement of more than one foam particle. For example, the bonding material can be dispensed using one or more nozzles, such as piezoelectric nozzles. A device including multiple nozzles can be configured such that each nozzle can be individually controlled to vary the fluid dispensing rate, droplet size, and / or other properties that alter the area of ​​the target region onto which the bonding material is deposited in each deposition iteration and / or the amount of bonding material deposited onto the target region in each deposition iteration. The bonding material can be deposited via one or more nozzles at frequencies of approximately 0.1 kHz, 0.5 kHz, 1 kHz, 2 kHz, 3 kHz, 4 kHz, 5 kHz, 6 kHz, 7 kHz, 8 kHz, 9 kHz, 10 kHz, 15 kHz, 20 kHz, a range covered by one of the aforementioned values, or a set of values ​​within a range covered by one of the aforementioned values. The bonding material can be deposited via one or more nozzles, such that the droplets dispensed from each nozzle have a longest dimension of approximately 1 micrometer, 2 micrometer, 3 micrometer, 4 micrometer, 5 micrometer, 10 micrometer, 15 micrometer, 20 micrometer, 25 micrometer, 30 micrometer, 35 micrometer, 40 micrometer, 45 micrometer, 50 micrometer, 55 micrometer, 60 micrometer, 70 micrometer, 80 micrometer, 90 micrometer, 100 micrometer, 150 micrometer, 200 micrometer, a range covered by one of the aforementioned values, or a set of values ​​within a range covered by one of the aforementioned values. In some cases, the droplets dispensed from one or more nozzles are spherical or ellipsoidal.

[0231] Adhesion using photochemical radiation

[0232] Attaching more than one foam particle together can include using photochemical radiation to fuse portions of the foam particles together.

[0233] Therefore, the disclosed method may include heating a target region containing more than one foam particle with a directed energy beam, under conditions effective for fusing a portion of more than one foam particle containing one or more thermoplastic elastomers. Heating of the target region may be performed one or more iterations. Heating the target region with a directed energy beam may include selective laser sintering of the foam particles.

[0234] The attachment may include: raising the temperature of at least a portion of more than one foam particle by photochemical radiation, under conditions that are effective for melting or softening a portion of a first thermoplastic elastomer material at at least one of the first surfaces of more than one foam particle; and lowering the temperature of the melted or softened portion of the first thermoplastic elastomer material, thereby causing the melted or softened portion of the first thermoplastic elastomer material to solidify and form more than one fused foam particle; wherein the temperature raising is performed at least once.

[0235] In some embodiments, raising the temperature of at least a portion of the first thermoplastic elastomer material at at least one first surface of more than one foam particle by photochemical radiation, while effectively used to melt or soften a portion of the first thermoplastic elastomer material at at least one first surface of the foam particle, further includes mixing the molten first thermoplastic elastomer material from the first surface of the foam particle with the molten first thermoplastic elastomer material at the second surface of an adjacent foam particle. In some embodiments, lowering the temperature of the molten or softened portion of the first thermoplastic elastomer material includes lowering the temperature of the mixed thermoplastic elastomer material, thereby causing the molten portion of the thermoplastic elastomer to solidify and form more than one fused foam particle.

[0236] It should be understood that the arrangement and heating steps can be repeated for a given layer in order to achieve the desired properties for that layer or for a sub-region within that layer.

[0237] A directed energy beam can be a laser beam. The laser beam can be emitted by a gas dynamic laser, a diode laser, or a lead salt laser. The laser beam can also be emitted by a carbon dioxide laser. The laser beam can be within the infrared spectrum. It can broadly encompass all or most of the infrared spectrum, or alternatively, it can include sub-regions of the infrared spectrum, such as the far-infrared, near-infrared, or mid-infrared spectra.

[0238] A laser beam may include two or more laser beams, each of which is directed at a target region. Each of the two or more laser beams may include a different portion of the electromagnetic spectrum. For example, a laser beam may include one laser beam emitted in the near-infrared spectrum and a second laser beam emitted in the far-infrared spectrum.

[0239] Laser beams can emit beams with wavelengths of about 700 nanometers to about 1 millimeter; about 1 micrometer to about 20 micrometers; about 3 micrometers to about 15 micrometers; about 3 micrometers to about 8 micrometers; about 8 micrometers to about 15 micrometers; or about 9 micrometers to about 11 micrometers.

[0240] The laser beam may have a beam width of about 0.1 mm to about 0.7 mm; about 0.2 mm to about 0.6 mm; about 0.3 mm to about 0.5 mm; or about 0.3 mm to about 0.4 mm. The laser beam may be defocused.

[0241] The laser beam can have a scan pattern such that each passing laser beam overlaps with the adjacent passing laser beam by approximately 0.1 to 0.5 fractional amounts. Alternatively, the laser beam can have a scan pattern such that each passing laser beam overlaps with the adjacent passing laser beam by approximately 0.3 fractional amounts.

[0242] Directional energy beams can have a power output of approximately 25 watts to approximately 75 watts; approximately 35 watts to approximately 55 watts; approximately 45 watts to approximately 65 watts; or approximately 50 watts to approximately 60 watts. A directional energy beam can have a power output of approximately 55 watts.

[0243] Processing conditions may include guiding the directed energy beam at a scan rate across the target area of ​​about 7,500 mm / s to about 25,000 mm / s, or optionally at a scan rate across the target area of ​​about 10,000 mm / s to about 15,000 mm / s. Processing conditions may include guiding the directed energy beam at a scan rate across the target area of ​​about 12,500 mm / s.

[0244] Heating a given target region comprising more than one foam particle can be performed with varying numbers of iterations, such as 1 to 500 iterations; 1 to 10 iterations; 1 to 8 iterations; 1 to 7 iterations; 2 to 10 iterations; 2 to 8 iterations; or 2 to 7 iterations. Heating a target region comprising more than one foam particle can be performed with at least 2 iterations. Heating the target region can be performed with 1, 2, 3, 4, 5, 6, or 7 iterations.

[0245] Heating the target area can fuse the first foam particle in the target area to the second foam particle, wherein the first foam particle is melted to a depth of about 10 micrometers to about 500 micrometers measured from the surface of the first foam particle, and wherein the second foam particle is melted to a depth of about 10 micrometers to about 500 micrometers measured from the surface of the second foam particle. Heating the target area can also fuse the first foam particle in the target area to the second foam particle, wherein the first foam particle is melted to a depth of about 25 micrometers to about 200 micrometers measured from the surface of the first foam particle, and wherein the second foam particle is melted to a depth of about 25 micrometers to about 200 micrometers measured from the surface of the second foam particle.

[0246] After the energy beam is directed to the target area, the target area of ​​more than one foam particle can have a density of about 0.100 g / cm³ to about 0.700 g / cm³, or optionally about 0.300 g / cm³ to about 0.500 g / cm³.

[0247] The disclosed method of forming an article may further include heating more than one target region on more than one particle. The article may have boundary regions defined by subsets of more than one target region. The article may include a first cross-sectional region comprising a subset of more than one target region, and wherein the first cross-sectional region is heated. Alternatively, the article may include a first cross-sectional region comprising a subset of more than one target region, and wherein the first cross-sectional region is not heated. Heating of more than one target region can be performed by directing a directed energy beam to each target region using a vector scanning method. Alternatively, heating of more than one target region can be performed by directing a directed energy beam to each target region using a raster scanning method. More than one target region may include a first more than one target region and a second more than one target region.

[0248] The disclosed method may further include: distributing selectively laser-sintered powder on the surface of an article such that the selectively laser-sintered powder contains a second thermoplastic elastomer; and heating a target region of the laser-sintered powder with a directional energy beam under conditions effective for fusing the laser-sintered powder, wherein the heating of the target region of the laser-sintered powder is performed at least once.

[0249] Selective laser sintering (SLS) powders can be conventional SLS powders containing thermoplastic elastomers. The thermoplastic elastomer referred to herein as a second thermoplastic elastomer can independently include any thermoplastic elastomer or combination of thermoplastic elastomers as disclosed herein, including but not limited to thermoplastic polyurea elastomers, thermoplastic polyether elastomers, thermoplastic copolyether ester elastomers, thermoplastic polyamide elastomers, thermoplastic polystyrene elastomers, thermoplastic polyolefin elastomers, thermoplastic copolyether amide elastomers, thermoplastic styrene-diene copolymer elastomers, thermoplastic styrene block copolymer elastomers, thermoplastic polyamide elastomers, thermoplastic polyimide elastomers, any copolymers thereof, and any blends thereof. The SLS powders used can have a particle size of about 0.020 mm to about 0.100 mm. The SLS powders used can be substantially unfoamed materials.

[0250] The selective laser sintering (SLS) powder can be arranged on the surface of an article and the target area of ​​the SLS powder heated can be repeated iteratively multiple times. In some cases, the arrangement iterations include depositing a layer containing the SLS powder. Multiple iterations of arranging and heating the SLS powder can be used to form a skin on an article manufactured using foam particles using the disclosed method. Therefore, the thickness of the skin can be adjusted by the number of iterations of arranging and heating the SLS powder placed on the surface of the foam article. Heating can be sustained at a temperature sufficient to melt the SLS powder for a certain period of time. In some cases, heating can be sustained at a temperature sufficient to melt the SLS powder, allowing it to flow in a molten state for a certain period of time. That is, heating can be sufficient to melt the SLS powder for a sufficient time to form molten SLS powder; and a portion of the molten SLS powder is flowable. The SLS powder can be selected based on the viscosity it would have in its molten state. For example, if it is desired that the selectively laser-sintered powder does not significantly penetrate into the article (i.e., a foamed article prepared using foam particles using the disclosed method), a more viscous selectively laser-sintered powder may be selected. Alternatively, a selectively laser-sintered powder with low viscosity in the molten state may be desirable when the selectively laser-sintered powder can penetrate deeper into the foamed article.

[0251] Depositing selective laser sintering powder can include depositing the selective laser sintering powder onto the surface of an article. Alternatively, depositing selective laser sintering powder can include spraying a suspension of the selective laser sintering powder in a solvent onto the surface of the article. The solvent can be water or an aqueous solution, or alternatively, an organic solvent.

[0252] The disclosed method of forming an article may further include providing an additive to the layers. The additive may be provided during the formation of layers containing more than one foam particle. Alternatively, the additive may be provided after the formation of layers containing more than one foam particle and before the guiding energy beam. The additive may be provided simultaneously with or approximately simultaneously with the guiding energy beam. The additive may be provided after the guiding energy beam. It should be understood that providing the additive may include spraying, sublimation, brushing, dipping, or other means suitable for contacting the additive with at least one surface of the article.

[0253] Additives can be polyurea coatings or polyurethane coatings. Polyurea coatings or polyurethane coatings can be sprayed onto more than one foam particle. Additives can include binders, adhesives, lubricants, antioxidants, colorants, fillers, laser sensitizers, and any combination thereof. Additives can be adhesives. Adhesives can include photocurable elastomer resins, thermally activated resins, and combinations thereof.

[0254] Additives may include laser sensitizers, such as infrared absorbers. Infrared absorbers may be infrared absorbing dyes or infrared absorbing pigments. Infrared absorbing pigments may be carbon black.

[0255] The disclosed methods may also include spraying or coating one or more layers of polyurea, polyurethane, or combinations thereof onto articles manufactured using the methods described herein. For example, articles, such as sole components manufactured using the disclosed methods, or shoes comprising such sole components, may be sprayed with one or more layers of polyurea, polyurethane, or combinations thereof. Suitable sprayable polyurea or polyurethane are commercially available, such as STS 300 polyurethane, HIGHLINE 200 polyurethane, SUREGRIP polyurea, HIGHLINE 310 polyurea, or HIGHLINE 510 polyurea manufactured by ArmorThane USA, Inc. (Springfield, Missouri, USA). At least the ground-facing surface of the sole component may be coated with polyurea, polyurethane, or combinations thereof. At least the ground-facing surface and side surfaces of the sole component may be coated with polyurea, polyurethane, or combinations thereof.

[0256] Foam particles.

[0257] Various methods for arranging and attaching foam particles have been described, and we further describe the foam particles themselves. The foam particles used in the disclosed methods can be prepared via a suspension process or an extrusion process. The term "foam particle" is used herein to refer to a foamed polymer in granular form, meaning a granular foamed polymer in granular form such that the particles have gas-filled pores within at least a portion of the internal volume of the foam particle, the gas-filled pores including open-cell structures, closed-cell structures, or combinations thereof. In some cases, more than about 50%, about 60%, about 70%, about 80%, about 90%, or more of the internal volume of the foam particle may be formed by gas-filled pores. In some cases, it is desirable that substantially all of the internal volume is formed by gas-filled pores. The foam particle may optionally have a surface layer covering more than about 50%, about 60%, about 70%, about 80%, about 90%, or more of the outer surface area of ​​the foam particle. In some cases, the optional surface layer may cover substantially all of the outer surface area of ​​the foam particle. Foam particles can have a variety of shapes, or include mixtures of shapes, such as regularly shaped particles, for example, rod-shaped, spherical, ellipsoidal, or oval shapes; or irregularly shaped particles. Foam particles may optionally include a non-foam surface layer.

[0258] In suspension processes, thermoplastic elastomers in the form of microspheres can be heated in a closed reactor to above their softening point, in the presence of water, a suspending agent, or a foaming agent. The microspheres are then impregnated with a foaming agent. It is then possible to cool the hot suspension, causing the particles to solidify in the presence of the foaming agent, and to depressurize the reactor. Microspheres containing the foaming agent and obtained in this way are then foamed by heating to produce foam particles. Alternatively, it is possible to abruptly depressurize the hot suspension without cooling (an explosive expansion process), causing the softened beads containing the foaming agent to immediately foam to produce foam particles.

[0259] In extrusion processes, thermoplastic elastomers can be mixed in an extruder while molten with a foaming agent introduced into the extruder. The mixture containing the foaming agent can be extruded and granulated under pressure and temperature conditions so that the thermoplastic elastomer does not foam. For example, a method used for this purpose is underwater granulation, which is operated with a water pressure greater than 2 bar to provide expandable beads containing the foaming agent, and then the expandable beads are foamed by subsequent heating to give foam particles. Alternatively, the mixture can also be extruded and granulated at atmospheric pressure. In this process, the melt extrudate is foamed and the product obtained by granulation includes foam particles.

[0260] Thermoplastic elastomers can be used in commercially available pellets, powders, granules, or any other form. The use of pellets is advantageous. An example of a suitable form is known as minipellets, with a preferred average diameter from 0.2 mm to 10 mm, particularly from 0.5 mm to 5 mm. These mostly cylindrical or spherical minipellets are produced by extrusion of the thermoplastic elastomer and, where appropriate, extrusion of other additives discharged from the extruder, followed by cooling and granulation, where appropriate. In the case of cylindrical minipellets, the length can be from 0.2 mm to 10 mm, or alternatively, from 0.5 mm to 5 mm. The pellets can also have a lamellar shape. The average diameter of the thermoplastic elastomer containing the foaming agent is preferably from 0.2 mm to 10 mm.

[0261] The blowing agent can be selected, at least in part, depending on the specific process used. In the case of a suspension process, the blowing agent used can include organic liquids or inorganic gases or mixtures thereof. Liquids that can be used include halogenated hydrocarbons, but saturated aliphatic hydrocarbons are preferred, particularly those having 3 to 8 carbon atoms. Suitable inorganic gases are nitrogen, air, ammonia, or carbon dioxide.

[0262] The blowing agent can be a supercritical fluid. Non-limiting examples of suitable supercritical fluids include carbon dioxide (critical temperature 31.1°C, critical pressure 7.38 MPa), nitrous oxide (critical temperature 36.5°C, critical pressure 7.24 MPa), ethane (critical temperature 32.3°C, critical pressure 4.88 MPa), ethylene (critical temperature 9.3°C, critical pressure 5.12 MPa), nitrogen (critical temperature -147°C, critical pressure 3.39 MPa), and oxygen (critical temperature -118.6°C, critical pressure 5.08 MPa). The blowing agent can be a supercritical fluid selected from supercritical nitrogen, supercritical carbon dioxide, or mixtures thereof. The blowing agent may include supercritical carbon dioxide or be substantially composed of supercritical carbon dioxide.

[0263] Supercritical carbon dioxide fluid can be made more compatible with polar thermoplastic elastomers (especially thermoplastic polyurethanes, polyurea, and polyamide elastomers) by mixing it with polar fluids such as methanol, ethanol, propanol, or isopropanol. The polar fluid used should have a strength equal to or greater than 9 MPa. -1 / 2The Hildebrand solubility parameter. Increasing the weight fraction of the polar fluid increases the amount of carbon dioxide absorbed, but the polar fluid is also absorbed, and at some point, there is a transition from the maximum absorption of supercritical carbon dioxide to the increase in the amount of non-foaming polar fluid being absorbed by the thermoplastic elastomer article. When used for injection into polyurethane elastomers, polyurea elastomers, or polyamide elastomers, the supercritical fluid may include a polar fluid from about 0.1 mol percent to about 7 mol percent based on the total fluid.

[0264] Supercritical fluids can be used in combination. For example, in some cases, supercritical nitrogen can be used as a nucleating agent in a small weight percentage together with supercritical carbon dioxide or another supercritical fluid that acts as a foaming agent. Nanoscale particles such as nanoclay, carbon black, crystals, immiscible polymers, and inorganic crystals such as salts can be included as nucleating agents.

[0265] In the production of foamed particles via extrusion processes, the blowing agent may comprise volatile organic compounds (VOCs) with boiling points ranging from -25°C to 150°C at approximately 10¹³ mbar atm. These VOCs may also have boiling points ranging from -10°C to 125°C at approximately 10¹³ mbar atm. Halogen-free hydrocarbons are well-suited, particularly alkanes with 4 to 10 carbon atoms, such as isomers of butane, pentane, hexane, heptane, and octane, including secondary pentane. Other suitable blowing agents are larger compounds, examples of which are alcohols, ketones, esters, ethers, and organic carbonates.

[0266] It is also possible to use halogenated hydrocarbons, but the blowing agent may be halogen-free. However, the possibility of a very small proportion of halogenated blowing agent in the blowing agent mixture cannot be ruled out. Of course, it is also possible to use a mixture of the mentioned blowing agents.

[0267] The amount of foaming agent, based on 100 parts by weight of the thermoplastic elastomer used, is preferably from 0.1 to 40 parts by weight, particularly from 0.5 to 35 parts by weight, and especially preferably from 1 to 30 parts by weight.

[0268] In suspension processes, operations are typically carried out in batches in an impregnator, such as a stirred tank reactor. Thermoplastic elastomers are fed into the reactor, for example, in the form of mini-spheres, along with water or another suspending medium and a foaming agent, and optionally a suspending agent. Exemplary suspending agents include water-insoluble inorganic stabilizers such as tricalcium phosphate, magnesium pyrophosphate, and metal carbonates; as well as polyvinyl alcohol and surfactants such as sodium dodecyl aryl sulfonate. Based on the thermoplastic elastomer, these substances are typically used in amounts ranging from 0.05% to 10% by weight.

[0269] The reactor is then sealed, and the reactor contents are heated to the impregnation temperature, typically at least 100 degrees Celsius. The foaming agent can be added before, during, or after heating the reactor contents. The impregnation temperature should be close to the softening point of the thermoplastic elastomer. For example, an impregnation temperature from about 100 degrees Celsius to about 150 degrees Celsius, or optionally from about 110 degrees Celsius to about 145 degrees Celsius, can be used.

[0270] After sealing the reactor, the pressure inside the reactor can be adjusted to a target pressure (e.g., impregnation pressure). The target pressure of the reactor can be selected to vary, for example, with the amount and properties of the foaming agent, as well as the temperature. The target pressure (i.e., impregnation pressure) is typically from 2 bar to 100 bar (absolute value). If necessary, the pressure can be adjusted via a pressure control valve or by introducing additional foaming agent under pressure. Under the elevated temperature and atmospheric pressure provided by the impregnation conditions, the foaming agent diffuses into the polymer microspheres. The impregnation time can typically be from 0.5 hours to 10 hours.

[0271] In one example of a suspension process, cooling of the heated suspension occurs after the impregnation process. The suspension is typically cooled to below a suitable temperature, such as about 100 degrees Celsius, resulting in the re-solidification of the thermoplastic material and the inclusion of the foaming agent. The material is then depressurized. The product is foam particles, which are routinely separated from the suspension. Adhering water is typically removed by drying, for example, in a pneumatic dryer. Subsequently or previously, if desired, the adhered suspension can be removed by treating the beads with a suitable solvent or reagent. By way of example, treatment with acids such as nitric acid, hydrochloric acid, or sulfuric acid can be used to remove acid-soluble suspensions, such as metal carbonates or tricalcium phosphate.

[0272] In extrusion processes, it is desirable to introduce the thermoplastic elastomer, foaming agent, and optional additives together (e.g., in the form of a mixture) or separately into one or more locations within the extruder. It is possible, but not required, to prepare the mixture from the solid components beforehand. By way of example, it is possible to begin by mixing the thermoplastic elastomer and, where appropriate, the additives, and introduce the mixture into the extruder, and then introduce the foaming agent into the extruder, such that the extruder incorporates the foaming agent into the polymer melt. It is also possible to introduce a mixture of the foaming agent and the additives into the extruder, i.e., to premix the additives with the foaming agent.

[0273] In an extruder, the aforementioned starting materials are mixed, at least partially melting the thermoplastic elastomer simultaneously. Any conventional screw-based machine can be used as an extruder, particularly single-screw and twin-screw extruders (e.g., Werner & Pfleiderer ZSK machines), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders, and shear roll extruders as known to those skilled in the art. The extruder can operate at temperatures where the thermoplastic elastomer is in melt form, for example from about 150 degrees Celsius to about 250 degrees Celsius or from about 180 degrees Celsius to about 210 degrees Celsius. However, the desired temperature will depend on the melting temperature characteristics of the given thermoplastic elastomer.

[0274] The rotation, length, diameter and design of the extruder screw, the amount introduced and the extruder productivity are selected in a known manner in order to give a uniform distribution of the additive in the extruded thermoplastic elastomer.

[0275] In one example of an extrusion process, foamed granules are produced. To prevent premature foaming of the melt containing the foaming agent upon discharge from the extruder, the melt extrudate is discharged from the extruder and granulated under temperature and pressure conditions that result in virtually no foaming. These conditions can be determined as a function of the type and amount of the polymer, additives, and especially the foaming agent. Ideal conditions can be readily determined through preliminary experiments.

[0276] The method for preparing the foam particles used in the disclosed methods and articles described herein is underwater granulation in a water bath at a temperature below 100 degrees Celsius and under a pressure of at least 2 bar (absolute value). Excessively low temperatures should be avoided, as the melt will otherwise harden on the die plate, and excessively high temperatures should also be avoided, as the melt will otherwise expand. As the boiling point of the blowing agent increases and the amount of blowing agent decreases, the permissible water temperature becomes higher and the permissible water pressure becomes lower. In the case of the particularly preferred blowing agent, sec-pentane, the ideal water bath temperature is from about 30 degrees Celsius to about 60 degrees Celsius, and the ideal water pressure is from 8 bar to 12 bar (absolute value). It is also possible to use other suitable coolants instead of water. Water-cooled die-face pelletization is also possible. In this process, the cutting chamber is enclosed to allow the granulation equipment to operate under pressure. The foam particles can then be separated from the water and dried, where appropriate.

[0277] The foam particles used in the disclosed methods and articles can be prepared using a continuous process, wherein a thermoplastic elastomer is melted in a twin-screw extruder in a first stage, and then the polymer melt is conveyed in a second stage through one or more static and / or dynamic mixing elements and impregnated with a foaming agent. The foam-impregnated melt can then be extruded and cut through a suitable die to give foam particle material, for example using an underwater granulation system (UWPS). UWPS can also be used to cut melt directly from the die to give foam particle material or to give foam particle material with a controlled initial degree of foaming. Controlled production of foam bead material is possible by controlling the back pressure and temperature in the water bath of the UWPS.

[0278] Underwater granulation is typically carried out at pressures ranging from 1.5 bar to 10 bar to produce expandable polymer bead materials. The template usually has more than one cavity system with more than one pore. Typically, pore diameters ranging from 0.2 mm to 1 mm can provide expandable polymer bead materials with a preferred average bead diameter ranging from 0.5 mm to 1.5 mm. Expandable polymer bead materials with a narrow particle size distribution and an average particle diameter ranging from 0.6 mm to 0.8 mm result in better filling of automated molding systems, where the molded parts are designed with a relatively fine structure. This also provides a better surface finish on the molded parts, with smaller volumetric voids.

[0279] The foam particles used in the disclosed methods and articles can have a wide range of shapes, generally including spherical, cylindrical, ellipsoidal, cubic, rectangular, and other generally polygonal shapes, as well as irregular or other shapes, including shapes with a circular, ellipsoidal, square, rectangular, or other polygonal cross-sectional perimeter or irregular cross-sectional shapes with or without uniform width or diameter along an axis. As used herein, the term "generally" to describe a shape is intended to indicate an overall shape that may have defects and irregularities such as protrusions, depressions, misaligned edges, corners, or sides, etc.

[0280] The foam particles used in the disclosed methods and articles may be generally spherical or elliptical. At least a portion of the foam particles may be ellipsoidal or generally ellipsoidal in shape. For example, at least about 20 percent, or at least about 25 percent, or at least about 30 percent of the foam particles are elliptical in shape. At least a portion of the foam particles may be spherical or generally spherical in shape. For example, at least about 20 percent, or at least about 25 percent, or at least about 30 percent of the foam particles are spherical in shape.

[0281] At least a portion of the foam particles may be irregularly shaped. Alternatively, at least a portion of the foam particles may be regularly shaped or polygonal. In the case of non-spherical particles, the foam particles may have an aspect ratio, which is the ratio of the largest principal diameter of the cross-section perpendicular to the principal (longest) axis of the particle. Non-spherical foam particles may have an aspect ratio of about 0.1 to about 1.0; about 0.60 to about 0.99; about 0.89 to about 0.99; or about 0.92 to about 0.99. Foam particles may have a number-average roundness value of about 0.60 to about 0.99, or from about 0.89 to about 0.99, or from about 0.92 to about 0.99.

[0282] The foam particles used in the disclosed methods and articles may have a number-average particle size of about 0.4 mm to about 10 mm in their longest dimension. The foam particles may have the following dimensions: about 0.04 mm to about 7 mm in their longest dimension; about 0.04 mm to about 5 mm in their longest dimension; about 0.04 mm to about 4 mm in their longest dimension; about 0.04 mm to about 3 mm in their longest dimension; about 0.04 mm to about 2 mm in their longest dimension; about 0.04 mm to about 1.5 mm in their longest dimension; about 0.04 mm to about 1 mm in their longest dimension; about 0.04 mm to about 0.9 mm in their longest dimension; and so on. The particle size is approximately 0.04 mm to approximately 0.8 mm; approximately 0.04 mm to approximately 0.7 mm in the longest dimension; approximately 0.04 mm to approximately 0.6 mm in the longest dimension; approximately 0.04 mm to approximately 0.5 mm in the longest dimension; approximately 0.04 mm to approximately 0.4 mm in the longest dimension; approximately 0.04 mm to approximately 0.3 mm in the longest dimension; approximately 0.04 mm to approximately 0.2 mm in the longest dimension; or a number-average particle size of approximately 0.04 mm to approximately 0.1 mm in the longest dimension. The foam particles can have dimensions of approximately 0.04 mm; approximately 0.05 mm; approximately 0.06 mm; approximately 0.07 mm; approximately 0.08 mm; approximately 0.09 mm; approximately 0.10 mm; approximately 0.15 mm; approximately 0.20 mm; approximately 0.25 mm; approximately 0.30 mm; approximately 0.35 mm; approximately 0.40 mm; approximately 0.45 mm; approximately 0.50 mm; approximately 0.55 mm; approximately 0.60 mm; approximately 0.65 mm; approximately 0.70 mm; approximately 0.75 mm; approximately 0.80 mm; approximately 0.85 mm; approximately 0.90 mm; approximately 0.95 mm; approximately 1.0 mm; approximately 1.1 mm; approximately 1.2 mm; approximately 1.3 mm; approximately 1.4 mm. mm; about 1.5 mm; about 1.6 mm; about 1.7 mm; about 1.8 mm; about 1.9 mm; about 2.0 mm; about 2.1 mm; about 2.2 mm; about 2.3 mm; about 2.4 mm; about 2.5 mm; about 2.6 mm; about 2.7 mm; about 2.8 mm; about 2.9 mm; about 3.0 mm; about 3.5 mm; about 4.0 mm; about 4.5 mm; about 5.0 mm; about 5.5 mm; about 6.0 mm; about 6.5 mm; about 7.0 mm; about 7.5 mm; about 8.0 mm; about 8.5 mm; about 9.0 mm; about 9.5 mm; about 10 mm; or any range or combination of the foregoing values ​​for number-average particle size.

[0283] The foam particles used in the disclosed methods and articles may have a number-average particle size of about 1 mm to about 10 mm in the longest dimension. The foam particles may have a number-average particle size of about 0.3 mm to about 7 mm in the longest dimension; about 0.5 mm to about 5 mm in the longest dimension; about 1 mm to about 5 mm in the longest dimension; about 1 mm to about 4 mm in the longest dimension; about 1 mm to about 3 mm in the longest dimension; about 1 mm to about 2 mm in the longest dimension; about 1.5 mm to about 5 mm in the longest dimension; about 1.5 mm to about 4 mm in the longest dimension; about 1.5 mm to about 3 mm in the longest dimension; or about 1.5 mm to about 2.5 mm in the longest dimension. The foam particles can have dimensions of approximately 0.10 mm; approximately 0.15 mm; approximately 0.20 mm; approximately 0.25 mm; approximately 0.30 mm; approximately 0.35 mm; approximately 0.40 mm; approximately 0.45 mm; approximately 0.50 mm; approximately 0.55 mm; approximately 0.60 mm; approximately 0.65 mm; approximately 0.70 mm; approximately 0.75 mm; approximately 0.80 mm; approximately 0.85 mm; approximately 0.90 mm; approximately 0.95 mm; approximately 1.0 mm; approximately 1.1 mm; approximately 1.2 mm; approximately 1.3 mm; approximately 1.4 mm; approximately 1.5 mm; approximately 1.6 mm; approximately 1.7 mm; Approximately 1.8 mm; approximately 1.9 mm; approximately 2.0 mm; approximately 2.1 mm; approximately 2.2 mm; approximately 2.3 mm; approximately 2.4 mm; approximately 2.5 mm; approximately 2.6 mm; approximately 2.7 mm; approximately 2.8 mm; approximately 2.9 mm; approximately 3.0 mm; approximately 3.5 mm; approximately 4.0 mm; approximately 4.5 mm; approximately 5.0 mm; approximately 5.5 mm; approximately 6.0 mm; approximately 6.5 mm; approximately 7.0 mm; approximately 7.5 mm; approximately 8.0 mm; approximately 8.5 mm; approximately 9.0 mm; approximately 9.5 mm; approximately 10 mm; or any range or combination of the foregoing values ​​for the number-average particle size.

[0284] Foam particles can have a density of about 0.1 g / cm³ to about 0.8 g / cm³. Foam particles can have a density of about 0.30 g / cm³ to about 0.50 g / cm³; or about 0.32 g / cm³ to about 0.48 g / cm³. Optionally or additionally, foam particles can be characterized by their bulk density. Thus, foam particles can have a bulk density of about 80 g / L to about 200 g / L. The foam particles can have a density of approximately 90 g / L to approximately 200 g / L; approximately 90 g / L to approximately 190 g / L; approximately 90 g / L to approximately 180 g / L; approximately 90 g / L to approximately 170 g / L; approximately 90 g / L to approximately 160 g / L; approximately 90 g / L to approximately 150 g / L; approximately 90 g / L to approximately 140 g / L; approximately 90 g / L to approximately 130 g / L; approximately 100 g / L to approximately 200 g / L; approximately 100 g / L to approximately 190 g / L; approximately 100 g / L to approximately 180 g / L; approximately 100 g / L to approximately 170 g / L; approximately 10 Bulk density of about 0 g / L to about 160 g / L; about 100 g / L to about 150 g / L; about 100 g / L to about 140 g / L; about 100 g / L to about 130 g / L; about 110 g / L to about 200 g / L; about 110 g / L to about 190 g / L; about 110 g / L to about 180 g / L; about 110 g / L to about 170 g / L; about 110 g / L to about 160 g / L; about 110 g / L to about 150 g / L; about 110 g / L to about 140 g / L; or about 110 g / L to about 130 g / L. The foam particles may have a bulk density of approximately 80 g / L; approximately 85 g / L; approximately 90 g / L; approximately 95 g / L; approximately 100 g / L; approximately 105 g / L; approximately 110 g / L; approximately 115 g / L; approximately 120 g / L; approximately 125 g / L; approximately 130 g / L; approximately 135 g / L; approximately 140 g / L; approximately 145 g / L; approximately 150 g / L; approximately 155 g / L; approximately 160 g / L; approximately 165 g / L; approximately 170 g / L; approximately 175 g / L; approximately 180 g / L; approximately 185 g / L; approximately 190 g / L; approximately 195 g / L; approximately 200 g / L; or any range or combination of the foregoing values.

[0285] Each individual foam particle can have a weight ranging from about 2.5 mg to about 50 mg.

[0286] Foam particles can have a dense outer surface. As used herein, "dense surface" means that the foam pores in the outer region of the foam particle are smaller than those in the inner region. Optionally, the outer region of the foam particle may be poreless.

[0287] Foam particles can be closed-cell foam particles.

[0288] Foam particles may also include one or more colorants, such as any colorants disclosed herein, or may be coated with colorants to provide a desired appearance. More than one foam particle may include two or more different colorants.

[0289] Combine materials.

[0290] According to some of the disclosed methods, the binding material can be used to attach more than one foam particle. The binding material can be a heat absorber, such as a microwave heat absorber or an infrared heat absorber; an adhesive material, such as an adhesive comprising one or more monomers, one or more polymers, or combinations thereof; one or more solvents capable of softening or partially dissolving a portion of the foam particle or capable of softening or partially dissolving a coating applied to the foam particle; or a combination thereof.

[0291] The binding material may include a heat absorber. The binding material containing the heat absorber may be a liquid or a flowable gel. The heat absorber may be present in the binding material as a dispersion. Alternatively or additionally, the heat absorber may be present in the binding material as an emulsion. The binding material containing the heat absorber can be provided via a printhead, such as an inkjet printhead. Therefore, the binding material containing the heat absorber may have a viscosity that allows the dispersion to pass through the printhead. The heat absorber may be present in the binding material and provided via spray using a nozzle with one or more orifices of suitable diameter. In such a case, the binding material containing the heat absorber has a viscosity that allows it to be applied via the printhead. The heat absorber may include carbon in the form of graphite, carbon fibers, carbon nanotubes, carbon black, or combinations thereof. Carbon black may be in the form of nanoparticles.

[0292] Thermal energy absorbers can be microwave energy absorbers. Microwave energy absorbers can include metals, metal salts, metal oxides, metal nitrides, metal carbides, metal sulfides, hydrated salts, carbon, clay, silicates, ceramics, zeolites, silica, alumina, titanium dioxide gel, vermiculate clay, attapulgite, molecular sieves, or combinations thereof. Microwave energy absorbers can also be metal salts such as CuX. nThe microwave energy absorber can be a hydrated salt, such as NiCl2●6H2O, Al2(SO4)3●18H2O, or a combination thereof. The microwave energy absorber can be a metal oxide, such as CuO, NiO, Fe3O4, Co2O3, BaTiO3, or a combination thereof. The microwave energy absorber can be a metal sulfide, such as Ag2S, CuS, MoS3, PbS, ZnS, FeS, FeS2, or a combination thereof. The microwave energy absorber can be a metal carbide, such as SiC, W2C, B4C, or a combination thereof. A variety of different metal nitrides are suitable for use as microwave energy absorbers, including but not limited to TiN. The microwave energy absorber can be carbon, such as carbon in the form of graphite, carbon fiber, carbon nanotubes, carbon black, or a combination thereof. Carbon black can be any suitable form for use as a microwave energy absorber, such as nanoparticles or microparticles. Various types of clay are suitable for use as microwave energy absorbers, including but not limited to sepiolite clay. The microwave energy absorber may be water or may also include water. The microwave energy absorber may have an average particle size from about 0.1 nanometers to about 50 micrometers. The microwave energy absorber may be present in the binding material at a weight percentage from about 0.1% to about 25% based on the total weight of the binding material.

[0293] The thermal energy absorber can be an infrared energy absorber. A variety of suitable infrared energy absorbers exist that can be used in the disclosed bonding materials. Infrared energy absorbers can include metal oxides, metal complexes, infrared absorbing dyes, or combinations thereof. Infrared energy absorbers can be metal oxides, such as tin oxide, zinc oxide, copper oxide; antimony-doped tin oxide, indium-doped tin oxide, or combinations thereof. Infrared energy absorbers can be metal complexes, such as zinc oxides containing at least one element selected from the group consisting of In, Ga, Al, and Sb, or combinations thereof. Infrared energy absorbers can be infrared absorbing dyes, such as anthraquinone dyes, cyanine dyes, polymethyl dyes, azomethine dyes, azo dyes, polyazo dyes, diimonium dyes, aminium dyes, phthalocyanine dyes, naphthylphthalocyanine dyes, indocyanine dyes, naphthoquinone dyes, indophenol dyes, triallylmethane dyes, metal complex dyes, nickel dithiol complex dyes, cobalt azo complex dyes, squarylium dyes, or combinations thereof. The binding material may contain an infrared energy absorber at a weight percentage of about 0.001 to about 0.08% based on the total weight of the binding material. The binding material may contain an infrared energy absorber at a weight percentage of about 0.005 to about 0.06% based on the total weight of the binding material.

[0294] The binding material may include an adhesive material. The adhesive material in the binding material may include one or more monomers, one or more polymers, or combinations thereof. The binding material containing the adhesive material may be a liquid or a flowable gel. The adhesive material may be present in the binding material as a dispersion. Alternatively, the adhesive material may be present in the binding material as an emulsion. The binding material containing the adhesive material can be deposited via a printhead such as an inkjet printhead. Therefore, the binding material containing the adhesive material has a viscosity that allows the dispersion to flow through the printhead. The adhesive material can be provided via spray using a printhead with one or more orifices of suitable diameter. In such a case, the binding material containing the adhesive material has a viscosity that allows it to be applied via the printhead.

[0295] The binding material may include one or more monomers, one or more polymers, or combinations thereof. One or more monomers may include one or more epoxy groups, one or more acrylic groups, one or more methacrylic acids, one or more methyl methacrylate groups, or combinations thereof. One or more polymers may include photocurable elastomer resins, thermally activated resins, and combinations thereof. One or more polymers may include polyacrylates; polyepoxides; copolymers derived from one or more monomers, said monomers including one or more epoxy groups, one or more acrylic groups, one or more methacrylic acids, one or more methyl methacrylate groups; or combinations thereof. Useful copolymers include block copolymers comprising at least one polyacrylate block, a polymethacrylate block, a polymethyl methacrylate block, or combinations thereof. The binding material may also include ultraviolet (UV) photoactivated free radical polymerization initiators, thermally activated polymerization initiators, or combinations thereof.

[0296] The binding material may include one or more solvents capable of softening or partially dissolving a portion of the foam particles or a coating applied to the foam particles. One or more solvents capable of softening or partially dissolving a portion of the foam particles or a coating applied to the foam particles are referred to herein as "binding solvents". In some cases, a binding solvent may be applied to more than one foam particle, for example, by applying binding solvent droplets, such that the solvent dissolves and softens a portion of the outer layer of the foam particles, wherein at least some of the beads include an outer layer in direct contact with the outer layers of other beads. A binding solvent may be applied to more than one foam particle including a coating, for example, by applying binding solvent droplets, such that the solvent dissolves and softens a portion of the coating, wherein at least some of the beads include an outer layer on the outer layer in direct contact with the coating on the outer layers of other beads.

[0297] The binder can have a viscosity suitable for applications in which the binder is deposited in the target region of the binder. For example, the viscosity can be between about 1 centipoise and about 50 centipoise, about 1 centipoise and about 40 centipoise, about 1 centipoise and about 30 centipoise, about 1 centipoise and about 20 centipoise, about 1 centipoise and about 10 centipoise, about 1 centipoise and about 5 centipoise, about 5 centipoise and about 50 centipoise, about 5 centipoise and about 40 centipoise, about 5 centipoise and about 30 centipoise, about 5 centipoise and about 20 centipoise, about 5 centipoise and about 10 centipoise, about 10 centipoise and about 50 centipoise, about 20 centipoise and about 50 centipoise, about 30 centipoise and about 50 centipoise, about 40 centipoise and about 50 centipoise, a subrange of any of the aforementioned ranges, or a set of values ​​within any of the aforementioned ranges.

[0298] The bonding material can have a surface tension suitable for applications in which the bonding material is deposited in the target region of the bonding material. For example, the surface tension can be from about 1 millinewtons per meter to about 50 millinewtons per meter, from about 1 millinewtons per meter to about 40 millinewtons per meter, from about 1 millinewtons per meter to about 30 millinewtons per meter, from about 1 millinewtons per meter to about 20 millinewtons per meter, from about 1 millinewtons per meter to about 10 millinewtons per meter, from about 5 millinewtons per meter to about 50 millinewtons per meter, from about 5 millinewtons per meter to about 40 millinewtons per meter, from about 5 millinewtons per meter to about 30 millinewtons per meter, from about 5 millinewtons per meter to about 20 millinewtons per meter, and from about 5 millinewtons per meter to about 20 millinewtons per meter. The range of Newtons per meter to about 10 millinewtons per meter, about 10 millinewtons per meter to about 50 millinewtons per meter, about 10 millinewtons per meter to about 40 millinewtons per meter, about 10 millinewtons per meter to about 30 millinewtons per meter, about 10 millinewtons per meter to about 20 millinewtons per meter, about 20 millinewtons per meter to about 50 millinewtons per meter, about 30 millinewtons per meter to about 50 millinewtons per meter, about 40 millinewtons per meter to about 50 millinewtons per meter, is a subrange of any of the aforementioned ranges, or a set of values ​​within any of the aforementioned ranges.

[0299] The bonding material can have a vapor pressure suitable for applications in which the bonding material is deposited in the target region of the bonding material. For example, the vapor pressure can be less than about 60 hectopascals, about 55 hectopascals, about 50 hectopascals, about 45 hectopascals, about 40 hectopascals, about 35 hectopascals, or about 30 hectopascals.

[0300] The binding material may include additives such as initiators and catalysts, and a delayer may be added to the particulate material, for example, to enhance the binding reaction. For example, the binding material may include a monomer binding system based on urethane, acrylate, methacrylate, styrene, or crosslinked or non-crosslinked polymerization triggered by UV light, radiation, heat, or reactive activators. For example, the binding material may include monomers forming polyurethane and one or more isocyanates. Such a binding material can be cured by depositing water or water mist onto the binding material to initiate the reaction.

[0301] The bonding material may include a multi-component adhesive system, such as a polyurethane resin or an epoxy resin, which crosslinks through the reaction of two components. It should be understood that the bonding material comprises a multi-component system, such as the adhesive system mentioned above, where each component of the multi-component system can be dispensed via a separate nozzle and mixed during deposition, for example, by spraying such that the stream dispensed from each nozzle is mixed before being deposited on the surface of more than one foam particle. Alternatively, each component of the multi-component system may be delivered from a separate feed supply and mixed in a mixing chamber immediately before being dispensed from the nozzle.

[0302] The binding material may include substances such as organic solvents or aqueous solutions that dissolve all or part of the foam particles and bind them together in this way.

[0303] The binder material may also include mixtures of different solvents and / or monomers, chemicals that induce crosslinking, and / or reaction aids such as retarders, catalysts, and fillers as disclosed herein or known to those skilled in the art. For example, to improve the properties of the binder material used for deposition, the binder material may include additional additives, such as additives for changing viscosity. That is, the binder material may include additives to increase or decrease viscosity, surface tension, and / or change the manner in which the binder material is deposited on the foam particles, such as flow, spraying, dispensing from a nozzle, or other combinations thereof. In this way, the deposition of the binder material can be improved.

[0304] The bonding of foam particles can be achieved through a bonding material, which includes one or more solvents, a mixed solvent system, and optionally water or an aqueous solution. The mixed solvent system includes a mixed solvent system containing one or more organic solvents. Non-limiting examples of solvents include alcohols, ketones, acetates, or mixtures thereof. It can also be a mixture of different solvents. The bonding function of the solvent is based on the foam particles being at least partially dissolved in the region where the bonding material containing the solvent is deposited. When the solvent escapes, the contact surfaces of the foam particles are bonded, and a solid region is established. In some cases, a reduction in material may be observed.

[0305] The selection of one or more solvents contained in the binder is based at least in part on the foam particle formulation and composition, such as the type and amount of thermoplastic elastomers, additives, and fillers present, and performance parameters of the curing and attaching steps of the disclosed method, such as the desired rate of dissolving the thermoplastic elastomer in the foam particles, regardless of whether all or only some components of the foam particle formulation and composition should dissolve, cost, and compatibility with the additive manufacturing equipment used. It should be understood that the binder composition can be adjusted, for example, by the specific solvent or multiple specific solvents used and their relative amounts, to fine-tune or adjust the binder to the solubility index of the foam particle formulation and composition, such as the type and relative amount of thermoplastic elastomers present therein.

[0306] In other words, different solvents will dissolve different polymers more effectively, and therefore, a person skilled in the art using the disclosed methods will evaluate foam particle formulations and compositions, such as the type and relative amount of thermoplastic elastomers present therein, and modify or adjust the binder composition in a manner that matches the solvents that effectively dissolve that particular chemical or formulation. For example, binders containing tetrahydrofuran and dimethylformamide can be used for foam particles containing polyesters and / or low-melting-point thermoplastic elastomers; or alternatively, binders containing hexafluoroisopropanol and formic acid can be used for foam particles containing aliphatic polyethers and various copolymers. In the case where the foam particles contain polyamide (nylon), binders containing hexafluoroisopropanol can be used. The process for determining the solvents used in the binder can utilize experimental determinations, various polymer solubility databases, and predictive methods (including software) using Hildebrand solubility parameters and / or Hansen solubility parameters.

[0307] The bonding material may include water or an aqueous solution as a solvent. For example, an aqueous solution may include, but is not limited to, acetic acid, formic acid, trifluoroacetic acid, or combinations thereof.

[0308] The bonding material may include a solvent that is an organic solvent. For example, the organic solvent may include, but is not limited to, tetrahydrofuran, dimethylformamide, hexafluoroisopropanol, dichloromethane, or combinations thereof.

[0309] The bonding material may include a solvent, which is a mixed solvent system comprising a combination of at least two solvents. For example, the mixed solvent system may include, but is not limited to, a mixed solvent system comprising two or more of the following: acetic acid, formic acid, trifluoroacetic acid, tetrahydrofuran, chlorophenol, dimethylformamide, hexafluoroisopropanol, and dichloromethane. In certain non-limiting examples, the mixed solvent system may include formic acid and dichloromethane; formic acid and acetic acid; formic acid and chlorophenol; or formic acid and hexafluoroisopropanol.

[0310] The binder containing solvent may also contain compounds or materials that slow down the evaporation rate, thereby reducing deformation. For example, the evaporation rate of alcohols can be slowed down by adding a water-containing material such as monoethylene glycol to the binder. Alternatively, or in addition to the foregoing, the evaporation rate can be controlled by appropriately selecting the temperature used during the curing step.

[0311] Solvents or mixtures of solvents can be modified to optimize the evaporation rate. For example, higher alcohols (n-butanol, pentanol, hexanol, etc.) with higher boiling points and lower vapor pressures can provide a simple and effective way to reduce the evaporation rate.

[0312] The binding material may include one or more polymers that are dissolved or partially dissolved in water, aqueous solutions, or organic solvents. The binding material may include water-soluble materials such as starch, proteins, or salts.

[0313] The bonding material can be deposited and cured in a manner that provides at least a portion of more than one foam particle arranged in a relatively weak or temporary attachment within a target area. For example, an article can be used as a preform, which is then compression molded. Therefore, the required level of adhesion between the beads may only need to be sufficient for the preform to be handled, including robotically, for transfer to a compression mold. In contrast, if the article and the foam beads therein are used without a compression molding step, the attachment of at least a portion of more than one foam particle arranged within the target area may need to be relatively strong and / or durable.

[0314] The disclosed bonding materials may also include one or more colorants, such as any colorants disclosed herein, to provide a desirable appearance. Components may include two or more bonding materials, each with a different colorant.

[0315] additive.

[0316] According to this disclosure, the foam particles or binding materials, or both, may optionally include additives. Additives may be directly incorporated into the disclosed foam particles or binding materials, or optionally applied to the disclosed foam particles or binding materials. Additives that may be used in the disclosed foam particles or binding materials include, but are not limited to, dyes, pigments, colorants, ultraviolet absorbers, hindered amine light stabilizers, antioxidants, processing aids or processing agents, plasticizers, lubricants, emulsifiers, optical brighteners, rheological additives, catalysts, flow control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke suppressants, flameproofing agents, antistatic agents, fillers, or mixtures of two or more of the foregoing. When used, additives may be present in amounts from about 0.01 weight percent to about 10 weight percent, from about 0.025 weight percent to about 5 weight percent, or from about 0.1 weight percent to 3 weight percent, wherein the weight percentages are based on the total amount of material components in the thermoplastic composition, fiber, filament, yarn, or fabric.

[0317] Individual components can be blended with other components of a thermoplastic composition in a continuous or batch mixer, such as in an intermeshing rotor mixer like an intermix mixer, a twin-screw extruder, a tangential rotor mixer such as a Banbury mixer using a twin-roll mill, or some combination thereof, to produce a composition containing a thermoplastic polymer and additives. The mixer can blend the components together via a single step or multiple steps, and can combine the components via dispersion mixing or distribution mixing to form the resulting thermoplastic composition. This step is often referred to as “compounding”.

[0318] Optional additives may be antioxidants, such as ascorbic acid, alkylated monophenols, alkylthiomethylphenols, hydroquinone or alkylated hydroquinones, tocopherols, hydroxylated diphenyl ethers, alkylene bisphenols, benzyl compounds, hydroxylated malonic esters, aromatic hydroxybenzyl compounds, triazine compounds, benzylphosphonates, acylaminophenols, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, amine antioxidants, or mixtures of two or more of the foregoing.

[0319] Exemplary alkylated monophenols include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-ethylcyclohexyl)-4,6-dimethylphenol, 2,6-bis(octadecyl)-4-methylphenol, and 2, 4,6-Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols with straight or branched side chains such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundecane-1-yl)phenol, 2,4-dimethyl-6-(1-methylheptadecane-1-yl)phenol, 2,4-dimethyl-6-(1-methyltetrazane-1-yl)phenol, and mixtures of two or more of the foregoing.

[0320] Exemplary alkylthiomethylphenols include, but are not limited to, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures of two or more of the foregoing.

[0321] Exemplary hydroquinones and alkylated hydroquinones include, but are not limited to, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and mixtures of two or more of the foregoing.

[0322] Exemplary tocopherols include, but are not limited to, α-tocopherol, p-tocopherol, 7-tocopherol, 6-tocopherol, and mixtures of two or more of the foregoing.

[0323] Exemplary hydroxylated thiodiphenyl ethers include, but are not limited to, 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-disec-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide, and mixtures of two or more of the foregoing.

[0324] Exemplary alkylene bisphenols include, but are not limited to, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), and 2,2'-alkylene bisphenol. 2,2'-Ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-Methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol) 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3-tert-butyl)butane] [2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecyl mercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, and mixtures of two or more of the foregoing.

[0325] Exemplary benzyl compounds include, but are not limited to, 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, and 3,5-di-tert-butyl -4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethyl ester, and mixtures of two or more of the foregoing.

[0326] Exemplary hydroxybenzyl malonates include, but are not limited to, bis(octadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, bis(octadecyl-2-(3-tert-butyl-4-hydroxy-5-ethylbenzyl)malonate, bis(dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and mixtures of two or more of the foregoing.

[0327] Exemplary aromatic hydroxybenzyl compounds include, but are not limited to, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixtures of two or more of the foregoing.

[0328] Exemplary triazine compounds include, but are not limited to, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, and 1,3,5-tris(3 5-Di-tert-butyl-4-hydroxy-benzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, and mixtures of two or more of the foregoing.

[0329] Exemplary benzylphosphonates include, but are not limited to, calcium salts of dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures of two or more of the foregoing.

[0330] Exemplary acylaminophenols include, but are not limited to, 4-hydroxy-lauricoaniline, 4-hydroxy-stearicoaniline, 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, and mixtures of two or more of the foregoing.

[0331] Exemplary esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0332] Exemplary esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0333] Exemplary esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0334] Exemplary esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0335] Exemplary amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide, and mixtures of two or more of the foregoing.

[0336] Exemplary amine antioxidants include, but are not limited to, N,N′-diisopropyl-p-phenylene diamine, N,N′-disec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylene diamine, N,N′-bis(1-methylheptyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N,N′-diphenylp-phenylene diamine, N,N′-bis(2-naphthyl)-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenylp-phenylene diamine, and N-(1-methylheptyl)-N′-phenylp-phenylene diamine. Amines, N-cyclohexyl-N′-phenyl-p-phenylene diamine, 4-(p-toluenesulfonyl)diphenylamine, N,N′-dimethyl-N,N′-disec-butyl-p-phenylene diamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p′-ditert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-ditert-butyl-4-dimethylaminomethylphenol, 2,4 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanidine, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octyl diphenylamine, mixtures of monoalkylated and dialkylated nonyl diphenylamine, mixtures of monoalkylated and dialkylated dodecyl diphenylamine, mixtures of monoalkylated and dialkylated isopropyl diphenylamine / isohexyl diphenylamine, monoalkylated and dialkylated diphenylamine, etc. Mixtures of alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of monoalkylated and dialkylated tert-butylphenothiazine / tert-octylphenothiazine, mixtures of monoalkylated and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperidin-4-yl)-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol, and mixtures of two or more of the foregoing.

[0337] Optional additives may be UV absorbers and / or light stabilizers, including but not limited to 2-(2-hydroxyphenyl)-2H-benzotriazole compounds, 2-hydroxybenzophenone compounds, esters of substituted and unsubstituted benzoic acids, acrylate or malonate compounds, sterically hindered amine stabilizer compounds, oxamide compounds, triaryl-o-hydroxyphenyl-s-triazine compounds, or mixtures of two or more of the foregoing.

[0338] Exemplary 2-(2-hydroxyphenyl)-2H-benzotriazole compounds include, but are not limited to, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole. 2-(2-hydroxy-4-octoxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-(ω)-hydroxy-octa(ethyleneoxy)carbonyl-ethyl)-phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonyl)ethylphenyl)-2H-benzotriazole, deca- Dialkylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, (2-Ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazole-2-yl)phenol, 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,5-Di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamon Methyl benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and mixtures of two or more of the foregoing.

[0339] Exemplary 2-hydroxybenzophenone compounds include, but are not limited to, 4-hydroxy derivatives, 4-methoxy derivatives, 4-octoxy derivatives, 4-decoxy derivatives, 4-dodecoxy derivatives, 4-benzyloxy derivatives, 4,2′,4′-trihydroxy derivatives and 2′-hydroxy-4,4′-dimethoxy derivatives of 2-hydroxybenzophenone, as well as mixtures of two or more such derivatives.

[0340] Exemplary esters of substituted and unsubstituted benzoic acid include, but are not limited to, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresenol, bis(4-tert-butylbenzoyl)resenol, benzoylresenol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and mixtures of two or more of the foregoing.

[0341] Exemplary acrylate or malonic acid ester compounds include, but are not limited to, ethyl α-cyano-β,β-diphenylacrylate or isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbonylmethoxy-cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbonylmethoxy-p-methoxycinnamate, N-(β-carbonylmethoxy-β-cyanovinyl)-2-methyl-indoline, dimethyl-p-methoxybenzylmalonic acid ester, di(1,2,2,6,6-pentamethylpiperidin-4-yl)-p-methoxybenzylmalonic acid ester, and mixtures of two or more of the foregoing.

[0342] Exemplary sterically hindered amine stabilizer compounds include, but are not limited to, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, and bis(1,2,2,6,6-pentamethyl-4-piperidine). 1,2,2,6,6-Tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantoin triacetate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane-tetracarboxylic acid ester, 1,1′-(1,2- Ethylenediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyl-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione, bis (1-Octoxy-2,2,6,6-Tetramethylpiperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-piperidinyl) succinate, straight-chain or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4].5] Dec-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3 ,8-diaza-4-oxo-spiro[4,5]decane, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl Piperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate, and 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine, and mixtures of two or more of the foregoing.

[0343] Exemplary oxamide compounds include, but are not limited to, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-bis(dodecyloxy-5,5′-di-tert-butoxanilide, 2-ethyl Oxy-2′-ethyloxalaniline, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethyloxalaniline and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxalaniline, mixtures of o-methoxydisubstituted oxalaniline and p-methoxydisubstituted oxalaniline, mixtures of o-ethoxydisubstituted oxalaniline and p-ethoxydisubstituted oxalaniline, and mixtures of two or more of the foregoing.

[0344] Exemplary triaryl-o-hydroxyphenyl-s-triazine compounds include, but are not limited to, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-octoxyphenyl)-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, and 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl) 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-biphenyl)-6-(2-hydroxy-4-octyloxycarbonylethyleneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl]-6-2-hydroxy-4-(3-sec-pentoxy-2- [2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butoxyphenyl)-6-(2,4-di-n-butoxyphenyl)-s-triazine, methylenebis{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)-phenyl]-s-triazine}, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6- (2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine, 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine, and mixtures of two or more of the foregoing.

[0345] Optional additives may be peroxide scavengers, such as esters of β-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl ester, or tridecyl ester; mercaptobenzimidazole; and zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, or mixtures thereof.

[0346] Additives may be polyamide stabilizers, such as halogens like copper salts of iodine, and / or phosphorus compounds and salts of divalent manganese.

[0347] Optional additives may be alkaline stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.

[0348] Optional additives may be nucleating agents, such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates, or sulfates of alkaline earth metals, or mixtures thereof. Alternatively, nucleating agents may be monocarboxylic acids or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, sodium benzoate, or mixtures thereof. Additives may be nucleating agents comprising both inorganic and organic materials as disclosed above.

[0349] Optional additives can be rheological modifiers. Rheological modifiers can be nanoparticles, nanoclays, nanocarbons, graphite, nanosilica, etc., with a relatively high aspect ratio.

[0350] Optional additives can be fillers or reinforcing agents, such as clay, kaolin, talc, asbestos, graphite, and glass (such as glass fiber, glass particles, and glass bubbles). Bulbs, glass spheres or glass-like spheres, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates (such as calcium carbonate, magnesium carbonate, etc.), metals (such as titanium, tungsten, zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt, beryllium, and alloys thereof), metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, etc.), metal hydroxides, granular synthetic plastics (such as high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide, etc.), synthetic fibers (such as fibers containing high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide, etc.), granular carbonaceous materials (such as carbon black), wood flour and other natural product powders or fibers, as well as cotton lint, cellulose lint, cellulose pulp, leather fibers, and combinations thereof. Non-limiting examples of heavy filler components that can be used to increase the specific gravity of cured elastomeric compositions may include titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze, cobalt, beryllium, zinc, tin, metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, and zirconium oxide), metal sulfates (such as barium sulfate), metal carbonates (such as calcium carbonate), and combinations thereof. Non-limiting examples of light filler components that can be used to reduce the specific gravity of elastomeric compounds may include granular plastics, hollow glass spheres, ceramics and hollow spheres, regrinds, and foams, which may be used in combination.

[0351] Optional additives may be crosslinking agents. A variety of crosslinking agents are available that can be used in the disclosed thermoplastic compositions. For example, the crosslinking agent may be a free radical initiator. Free radical initiators can generate free radicals through thermal decomposition or UV radiation. Free radical initiators may be present in amounts from about 0.001 weight percent to about 1.0 weight percent. Various free radical initiators can be used as free radical sources to produce thermoplastic compositions having a crosslinked structure. Suitable free radical initiators applied include peroxides, sulfur, and sulfides. Exemplary peroxides include, but are not limited to, aliphatic and aromatic peroxides, such as diacetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(butylperoxy)-3-hexyne, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 1,4-bis(tert-butylperoxyisopropyl)benzene, tert-butylperoxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and bis(2,4-dichlorobenzoyl), or combinations of two or more of the foregoing.

[0352] Optional additives may be colorants, as further described herein. For example, colorant additives may be provided to the foam particle material before, during, or after the formation of the foam particles. Colorant additives may be provided to the binder material before, during, or after the deposition or curing of the binder material. Colorant additives may be provided to more than one foam particle during or after the arrangement or attachment of more than one foam particle, or after the formation of the component. It should be understood that a component may include more than one colorant additive. For example, a component may include a first colorant and a second colorant, wherein: the foam particles may include the first colorant, and the binder material may include the second colorant; a first portion of the foam particles may include the first colorant, and a second portion of the foam particles may include the second colorant; a first portion of the binder material may include the first colorant, and a second portion of the binder material may include the second colorant; or combinations thereof. In this case, it should be understood that the first colorant may include one or more dyes or pigments. Similarly, it should be understood that the second colorant may include one or more dyes or pigments.

[0353] decorate.

[0354] This disclosure relates to decorating more than a portion of a foam particle to provide a decorated component. Decoration may include applying a coating to at least a portion of the foam particle, embossing or debossing a portion of the foam particle, or a combination thereof.

[0355] Methods may include decorating foam particles before or during placement, before or during attachment, after placement and attachment, or a combination thereof. Where the method includes more than one iteration, decoration may be performed during one or more iterations, after one or more iterations, between two iterations, or a combination thereof. Decoration may be performed after the last iteration, for example, on a component.

[0356] Decoration may include embossing or debossing a portion of a component. Embossing or debossing can form a desired embossed or debossed surface pattern on a first surface or a portion thereof of the component. Embossing or debossing can be performed before, during, or after any other decoration. For example, the surface of a component may be decorated, such as by overcoating, dyeing, printing, etc., and then the decorated surface may be embossed or debossed. The surface of a component may be embossed or debossed, and then the embossed or debossed surface may be decorated in other ways, such as by overcoating, dyeing, printing, etc.

[0357] Embossing or debossing may involve contacting a first surface of a component with a second surface of an embossing or debossing medium having a relief or reverse side of a desired embossed or debossing pattern. The component can then be separated from or removed from the second surface of the medium, while the embossed or debossing surface pattern remains on the first surface of the component. The embossing or debossing medium may include release paper, a die, a roller, a plate, or a roll.

[0358] Contact between the first surface and the second surface of the embossing or embossing medium can occur during or after raising the temperature of the component to a first temperature at or above the component's softening or melting temperature, thus forming the embossed or embossed surface. For example, the first temperature can be at or above the creep relaxation temperature, heat distortion temperature, Vicat softening temperature, or melting temperature of the thermoplastic material of the first surface to at least partially melt or soften the first surface of the component. Subsequently, the temperature of the first surface of the component is lowered to a second temperature below the component's softening or melting temperature, causing the material at the first surface of the component to at least partially solidify. For example, the second temperature can be below the creep relaxation temperature, heat distortion temperature, Vicat softening temperature, or melting temperature of the thermoplastic material of the first surface to at least partially solidify the first surface of the component. The component can be removed or separated from the embossing or embossing medium before, during, or after the component's temperature is lowered to the second temperature. After removing the embossing or embossing medium from the first surface of the component, the first surface of the component retains the embossed or embossed surface pattern.

[0359] Embossing or debossing media can provide energy to raise the temperature of a first surface of the component. Embossing or debossing media can remove energy to lower the temperature of the first surface to a second temperature. In some embodiments, pressure or vacuum can be applied to increase the contact between the first surface of the component and the second surface of the embossing or debossing media.

[0360] Embossing media or debossing media are designed as raised or recessed surfaces of a desired embossed or debossed surface pattern. Embossing media or debossing media can be manufactured from materials that retain their surface design when the part is subjected to temperatures and pressures capable of forming the embossed or debossed surface pattern. Embossing media or debossing media can be manufactured from a single material or a combination of materials, such as polymers, metals, or ceramics.

[0361] Applying a coating to all or part of more than one foam particle or a component may include printing on the part, coating on the part, dyeing the part, applying a film on the part, or any combination thereof.

[0362] The coating may include one or more layers, such as a primer layer, a coating layer (e.g., dyes, pigments, and combinations thereof), an ink layer, a re-grinding layer, a polymer layer that is at least partially degraded, a metal layer, an oxide layer, or a combination thereof.

[0363] The coating can be formed using digital printing, inkjet printing, offset printing, pad printing, screen printing, flexographic printing, thermal transfer, and physical vapor deposition, including chemical vapor deposition, pulsed laser deposition, evaporation deposition, sputtering deposition (RF, DC, reactive, non-reactive), plasma-enhanced chemical vapor deposition, electron beam deposition, cathodic arc deposition, low-pressure chemical vapor deposition, and wet chemical techniques such as layer-by-layer deposition, sol-gel deposition, or Langmuir-Blodgett films. Alternatively or additionally, the coating can be applied by spraying, dip coating, brushing, spin coating, blade coating, etc.

[0364] The coating may have a percentage transmittance of about 40% or less, about 30% or less, about 20% or less, about 15% or less, about 10% or less, about 5% or less, or about 1% or less, where “less” may include about 0% (e.g., 0 to 0.01 or 0 to 0.1), about 1%, about 2.5%, or about 5%.

[0365] The coating may include a coating composition that forms a thin layer upon application to a structure. The thin layer may be a solid film containing a colorant. The coating composition may include known coating compositions that may contain one or more of the following components: one or more paint resins, one or more polymers, one or more dyes and one or more pigments, as well as water, film-forming solvents, desiccants, thickeners, surfactants, anti-skinning agents, plasticizers, mildew inhibitors, mar-resistant agents, anti-flooding agents, and combinations thereof.

[0366] The coating may include a re-milled and at least partially degraded polymer layer. The re-milled and at least partially degraded polymer layer may be colored, such as those described above.

[0367] The coating may include a metal layer or an oxide layer. The oxide layer may be a metal oxide, a doped metal oxide, or a combination thereof. The metal layer, metal oxide, or doped metal oxide may include transition metals, metalloids, lanthanides, and actinides, as well as nitrides, nitrides, sulfides, sulfates, selenides, tellurides, and combinations thereof. The metal oxide may include titanium oxide, aluminum oxide, silicon dioxide, tin dioxide, chromium oxide, iron oxide, nickel oxide, silver oxide, cobalt oxide, zinc oxide, platinum oxide, palladium oxide, vanadium oxide, molybdenum oxide, lead oxide, and combinations thereof, as well as their respective doping forms. The metal oxide may be doped with water, inert gases (e.g., argon), reactive gases (e.g., oxygen or nitrogen), metals, small molecules, and combinations thereof.

[0368] The coating can be applied to the surface of the component and / or foam particles. The coating can be chemically bonded (e.g., covalently bonded, ionicly bonded, hydrogen-bonded, and similarly bonded) to the surface of the component and / or foam particles.

[0369] The coating may include polymeric materials. The coating may be a product (or also referred to as a "crosslinking product") that crosslinks the polymer coating composition. The crosslinked coating may be a matrix of a crosslinked polymer (e.g., a crosslinked polyester polyurethane polymer or copolymer). For example, the coating may include an aqueous dispersion of a polymer, such as an aqueous dispersion of a polyurethane polymer (e.g., a polyester polyurethane copolymer), and the aqueous dispersion of the polymer may be crosslinked. The crosslinked coating may have a thickness of about 0.01 micrometers to 1000 micrometers. When the polymer coating composition or crosslinked product coating contains one or more colorants, such as solid pigment particles or dyes, the colorants may be embedded in the coating, including embedded in the crosslinked polymer matrix. For example, the coating may include an aqueous dispersion of a polymer containing one or more colorants, and the aqueous dispersion of the polymer may be crosslinked to embed the colorants. Solid pigment particles or dyes may be physically embedded in the crosslinked polymer matrix and may be chemically bonded to the coating or article (e.g., covalently bonded, ionicly bonded, hydrogen-bonded, or similarly bonded to the coating comprising the polymer matrix or to a material forming the surface of the article to which the coating is applied), or a combination of physical and chemical bonding.

[0370] The coating (e.g., a coating itself, a polymer coating composition (before curing), monomers and / or polymers of a crosslinked polymer matrix, or a precursor of the coating) may include a crosslinking agent used to crosslink the polymer components of the coating. The crosslinking agent may be an aqueous crosslinking agent. The crosslinking agent may include one or more of the following: polycarboxylic acid crosslinking agents, aldehyde crosslinking agents, polyisocyanate crosslinking agents, or combinations thereof. The polycarboxylic acid crosslinking agent may be a polycarboxylic acid having from 2 to 9 carbon atoms. For example, the crosslinking agent may include copolymers of polyacrylic acid, polymaleic acid, acids, maleic acid, fumaric acid, or 1,2,3,4-butanetetracarboxylic acid. The concentration of the crosslinking agent may be from about 0.01 weight percent to 5 weight percent or from 1 weight percent to 3 weight percent of the coating.

[0371] Coatings (e.g., coatings, polymer coating compositions (before curing), monomers and / or polymers of crosslinked polymer matrices, or precursors of coatings) may include solvents. Solvents may be organic solvents. Organic solvents may be water-miscible organic solvents. Coatings may not contain water, or may be substantially water-free. For example, solvents may be or may include acetone, ethanol, 2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethyl ketone, 1-butanol, tert-butanol, or any mixture thereof.

[0372] Decoration may include applying a film to the surface of a component. For example, the film may be adhered to the surface of the component.

[0373] Decoration may include printing onto a portion of more than one foam particle or component. The method may include printing one or more markers onto the surface of one or more foam particles, or onto the surface of a component. Printing may include depositing at least one ink, or optionally more than one ink, onto a target printing area of ​​the foam particle or component. The ink may include one or more colorants, pigments, or dyes as described herein. The ink may include CMYK formulations or RGB formulations. Printing may include screen printing, pad printing, inkjet printing, 3D printing, flexographic printing, thermal transfer, or any combination thereof. Printing may deposit markers directly onto a target area of ​​the foam particle or component. Printing may deposit one or more inks onto a transfer medium (e.g., release paper) and then transfer the ink from the transfer medium to the target area of ​​the foam particle or component.

[0374] The ink can be a sublimation ink formulation, and printing can include depositing the sublimation ink onto the outer surface of the part and then raising the temperature of the part above the sublimation temperature of the sublimation ink. The sublimation ink can be placed on a transfer medium such as release paper printed with sublimation ink and then transferred from the transfer medium to the part.

[0375] The ink may include an infrared radiation absorber, and printing may include depositing the ink on a target area that will be exposed to infrared radiation.

[0376] Printing can deposit one or more inks on top of another layer, such as a primer layer or a coating layer.

[0377] Printing can include attaching a printed film to the surface of a component.

[0378] Printing can include printing a three-dimensional structure onto the surface of a part. The printing can have a three-dimensional structure. Printing can include an additive manufacturing process that deposits polymer material onto the outer surface of the part, thereby creating a topology on the outer surface of the part with a larger surface area compared to the topology on the outer surface of the part before printing.

[0379] Printing may include: receiving a set of predetermined information about a three-dimensional structure; wherein the set of predetermined information includes a first thickness of a region of the three-dimensional structure and the thickness of structural layers; calculating the number of structural layers to be printed in the region to achieve the first thickness of the three-dimensional structure; instructing a printing apparatus to use the set of predetermined information to print one or more structural layers onto a component, wherein the number of structural layers is equal to the calculated number of structural layers; and printing one or more structural layers onto the component to provide a three-dimensional structure having the first thickness. Printing the three-dimensional structure may include printing one or more color layers, or adding a colorant to a polymer composition.

[0380] Coating may include dyeing foam particles, attached foam particles, optional bonding materials, components or a portion thereof, or any combination thereof. Dyeing may include providing a dye composition to the foam particles, attached foam particles, bonding materials, components or a portion thereof, or any combination thereof. Providing the dye composition may include spraying the foam particles or components or a portion thereof, immersing the foam particles or components in the dye composition, or a combination thereof.

[0381] Foam particles can be dyed before or during the infusion of a supercritical fluid, such as by dissolving or dispersing a nonionic or anionic dye in the supercritical fluid, which optionally contains a polar liquid. Foam particles can also be dyed while immersed in a heated fluid containing dye. Specifically, the heated fluid can be a heated aqueous dye solution that may contain quaternary ammonium salts and organic solvents as described. Foam particles can be dyed after foaming, such as by immersing the foam particles (e.g., in an unattached or attached state) in a dye solution. Foam particles can also be dyed after a component has been formed from attached foam particles, for example by immersing the component or a portion of a component in a dye solution.

[0382] Dyeing may include providing two or more dye compositions. For example, a first dye composition may be provided to a first target dye region of a component, and a second dye composition may be provided to a second dye region of the component. The first and second dye regions may independently include more than one foam particle or portion thereof, attached foam particles, optional bonding materials, components, coatings, or portions thereof. Dyeing may include applying a dye composition to a target region, wherein only a portion of the target region will retain dye. For example, some materials may be resistant to dye retention, or one or more additives may be provided to prevent dye retention in the predetermined region.

[0383] Colors and colorants.

[0384] As described herein, various embodiments of decorative components include providing one or more colorants to the component. For example, foam particles, bonding materials, coatings, ink compositions, etc., may each independently include one or more colorants. As used herein, the term "colorant" refers to a compound that provides color to a substrate. Colorants can be organic or inorganic pigments, dyes, or mixtures or combinations thereof.

[0385] Colorants may include one or more inorganic pigments or inorganic dyes. Pigments or dyes may be inorganic materials, such as metal oxides, for example, iron oxide or titanium dioxide. Alternatively, inorganic pigments or dyes may be metal compounds such as strontium chromate or barium sulfate, or metallic pigments such as aluminum flakes or aluminum particles. Inorganic pigments or dyes may be homogeneous inorganic pigments, core-shell pigments, and the like. Inorganic pigments or dyes may be carbon pigments (e.g., carbon black), clay pigments, or ultramarine pigments. In some cases, the metal compound is not a cadmium-containing metal compound. In some cases, it may be desirable that the inorganic pigment or dye is not an inorganic pigment or dye containing lead compounds, cadmium compounds, and chromium (VI) compounds. Pigments may be of the type referred to in the art as extender pigments, including but not limited to calcium carbonate, calcium silicate, mica, clay, silica, barium sulfate, and the like. Pigments may include any of those sold by KPPigments, such as pearl pigments, color-shift pigments (e.g., CALYPSO, JEDI, VERO, BLACKHOLE, LYNX, ROSE GOLD, and the like), hypershift pigments, interference pigments, and similar pigments. Pigments or dyes may be organic compounds, such as perylene, phthalocyanine derivatives (e.g., copper phthalocyanine), indigoanthraquinone, benzimidazolone, quinacridone, perinone, and azobenzene derivatives.

[0386] Coloring agents can be dyes, such as anionic dyes, cationic dyes, direct dyes, metal complex dyes, basic dyes, disperse dyes, solvent dyes, polymer dyes, polymer dye colorants, or nonionic dyes, or combinations thereof. Dyes can be water-miscible. Dyes can be dissolved dyes. Anionic dyes can be acid dyes.

[0387] Colorants can include acid dyes. Acid dyes are water-soluble anionic dyes. There are many types of acid dyes, ranging from dull tones to brilliant shades. Chemically, acid dyes include azo compounds, anthraquinone compounds, and triarylmethane compounds. The Color Index (CI), jointly published by the Society of Dyers and Colourists (UK) and the American Association of Textile Chemists and Colorists (USA), is the most comprehensive abbreviation for dyes and pigments used for large-scale coloring purposes, encompassing 12,000 products under 2,000 CI common names. In the CI, each compound is provided with two numbers, referring to both the color classification and chemical classification. The "common name" indicates the application area and / or coloring method, 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, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246, and 250; and Acid Red 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183, 184, 186, and 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 thereof. Acid dyes can be used alone or in any combination in dye solutions.

[0388] Acid dyes and nonionic disperse dyes are commercially available from a number of sources, including Dystar LP, Charlotte, North Carolina, under the trade name TELON; Huntsman Corporation, Woodlands, Texas, USA, under the trade names ERIONYL and TECTILON; BASF SE, Ludwigshafen, Germany, under the trade name BASACID; Clariant International Ltd., Muttenz, Switzerland, under the trademarks SOLVAPERM, HOSTASOL, POLYSYNTHREN, and SAVINYL; and Bezema AG, Montlingen, Switzerland, under the trade name BEMACID.

[0389] Acidic disperse dye solutions or nonionic disperse dye solutions used for staining substrates (e.g., foam particles, bonding materials, coatings) may include, for example, acidic disperse dye compounds or nonionic disperse dye compounds, or combinations thereof, from about 0.001 g / L to about 5.0 g / L, preferably from about 0.01 g / L to about 2 g / L. The amount of acidic disperse dye compound or nonionic disperse dye compound used will determine how strong the color is and how quickly the substrate (e.g., foam particles, bonding materials, coatings) or other articles are stained, and can be optimized in a direct manner; generally, more concentrated dye solutions can provide more intense (deeper, darker, more intense) staining colors and can stain small balls or other articles containing thermoplastic elastomers more quickly.

[0390] Dye solutions may include one or more solvents. Acidic metal complex dyes are generally soluble in water and are therefore dissolved in an aqueous solvent system before use. Solvent-metal complex dyes are insoluble in water and are therefore dissolved in an aqueous / organic solvent system before use. The solvent system used for metal complex dyes should both dissolve the dye and promote the diffusion of dye molecules into the elastomer substrate under mild conditions. Some organic solvents not only dissolve water-insoluble dyes, such as solvent-metal complex dyes, but also promote or facilitate the diffusion of both acidic and solvent-metal complex dyes into the polymer substrate.

[0391] Solvents may include water-soluble solvents. The water solubility of a particular organic solvent used in a specific amount in the dye solution is determined at 20°C and 1 atm at the concentration in the alcohol to be used in the dye solution; an organic solvent is water-soluble if it is completely soluble or completely miscible in water at 20°C and 1 atm at the concentration in the alcohol to be used in the dye solution and does not form any separate phase or layer. Suitable non-limiting examples of water-soluble organic solvents that may be used include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and glycerol; ketones such as acetone and methyl ethyl ketone; esters such as butyl acetate, which is soluble in water in limited amounts; and ethylene glycol ethers and ethylene glycol ether esters (especially acetates), such as ethylene glycol phenyl ether (EGPE) acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Water-soluble organic solvents may be contained in concentrations of up to about 50 percent, or up to about 25 percent, or from about 1 percent to about 50 percent, or from about 5 percent to about 40 percent, or from about 10 percent to about 30 percent, or from about 15 percent to about 25 percent by volume, of the aqueous medium used to manufacture the dye solution. Whether and how much organic solvent is used may vary depending on the type of dye used and the application method used to contact the dye solution with the substrate.

[0392] Solvent systems for solvent-metal complex dyes may also include a third component, such as an additional organic solvent, to increase the dye's solubility. Suitable additional organic solvents include, but are not limited to, alcohols, ethers, esters, and ketones.

[0393] Alternatively, a two-phase solvent system can be used, wherein the dye is soluble in an organic solvent but insoluble in water, and the organic solvent is only partially miscible with water or insoluble or almost insoluble in water. Suitable organic solvents for forming a two-phase system include polar organic solvents that are insoluble in water, such as suitable hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, amides, acids, and halogenated compounds. Examples include, but are not limited to, n-butanol, cyclohexanol, butyl acetate, and ethylene glycol phenyl ether. In a two-phase solvent system, a solution containing a large amount of water and a small amount of organic solvent is prepared. The organic solvent is partially miscible with water or almost insoluble in water, such that water and organic solvent form a two-phase system. The dye can first be dissolved in the organic solvent to form a homogeneous solution, and then the solution can be dispersed as droplets in water under agitation or stirring. Alternatively, the organic solvent can be combined with water to form a two-phase solvent. The dye is then added to the two-phase solvent under agitation or stirring to form droplets. Two-phase solvent compositions may contain 1 to 30 volume percent, for example 1 to 25 volume percent, of an organic solvent and 70 to 99 volume percent, for example 75 to 99 volume percent, of water. These two-phase solvent compositions are particularly suitable for solvent dyes that have high solubility in organic solvents. Typically, dyes suitable for this embodiment include dyes that are highly soluble in organic solvents but practically insoluble in water.

[0394] Colorants may include dyes and quaternary (tetraalkyl)ammonium salts, particularly when the dye is an acid dye and the substrate (e.g., foam particles, bonding materials, or coatings) comprises thermoplastic polyurethane elastomers or thermoplastic polyurea elastomers. Quaternary (tetraalkyl)ammonium salts may react with dyes (e.g., acid dyes) to form complex dyes that can be used in coatings. The "alkyl" group may include C1 to C10 alkyl groups. Quaternary (tetraalkyl)ammonium salts may be selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds. Colorant compounds may comprise anionic dye compounds, quaternary ammonium salts selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds, and optionally water-soluble organic solvents.

[0395] The counter ion of the quaternary ammonium salt should be selected so that the quaternary ammonium salt forms a stable solution with the dye (e.g., anionic dye). Quaternary ammonium compounds can be, for example, halides (such as chlorides, bromides, or iodides), hydroxides, sulfates, sulfites, carbonates, perchlorates, chlorates, bromates, iodates, nitrates, nitrites, phosphates, phosphites, hexafluorophosphites, borates, tetrafluoroborates, cyanides, isocyanates, azides, thiosulfates, thiocyanates, or carboxylates (such as acetates or oxalates). Tetraalkylammonium compounds can be or may include tetrabutylammonium halide or tetrahexylammonium halide, particularly tetrabutylammonium bromide or tetrabutylammonium chloride or tetrahexylammonium bromide or tetrahexylammonium chloride.

[0396] When an acidic dye solution is used to dye foam particles, bonding materials, or coatings containing thermoplastic polyurethane elastomers or thermoplastic polyurea elastomers, the acidic dye solution may contain from about 0.1 equivalents to about 5 equivalents of a soluble tetraalkylammonium compound per equivalent of the dye compound. In various embodiments, the acidic dye solution may contain from about 0.5 equivalents to about 4 equivalents, preferably from about 1 equivalent to about 4 equivalents of a tetraalkylammonium compound per equivalent of the dye compound. The amount of tetraalkylammonium compound used with a particular acidic dye compound depends on the rate at which the dye diffuses into the substrate and can be optimized in a direct manner. The process of dyeing foam particles or bonding materials containing thermoplastic polyurethane elastomers or thermoplastic polyurea elastomers with this dye solution containing a soluble tetraalkylammonium compound can produce a strong color intensity in the dyed foam particles.

[0397] When used in coatings, the coating (e.g., a coating, a polymer coating composition (before curing)) may include about 1 to 15 percent by weight of a quaternary ammonium salt. The molar ratio of the acid dye to the quaternary ammonium compound may be in the range of about 3:1 to 1:3 or about 1.5:1 to 1:1.5.

[0398] Having described several instances of decorating parts and objects by adding colorants, we now turn to a discussion of the various ways color can be represented. The “color” of an object as perceived by an observer may differ from the object’s actual color. The color perceived by an observer depends not only on the object’s physical properties but also on the object’s environment and the characteristics of the perceiving eye and brain. For example, the color perceived by an observer is determined by the object’s actual color (e.g., the color of light leaving the object’s surface), the observer’s ability to detect the wavelength of light reflected or emitted by the object, the wavelength of light used to illuminate the object, and other factors such as the color of the object’s environment and the type of incident light (e.g., sunlight, fluorescence, and similar light). As a result, the color of an object perceived by an observer may differ from the object’s actual color.

[0399] "Hue" is a term typically used to describe the color properties that can be distinguished based on the dominant wavelength of visible light, and is usually described using terms such as magenta, red, orange, yellow, green, cyan, blue, indigo, violet, etc., or can be described as being related to one of these colors (e.g., similar or dissimilar). The hue of a color is generally considered independent of its intensity or lightness. For example, in the Munsell color system, the properties of a color include hue, lightness (brightness), and chromaticity (color purity). Specific hues are typically associated with specific wavelength ranges in the visible spectrum: wavelengths in the range of approximately 700 nm to 635 nm are associated with red, approximately 635 nm to 590 nm with orange, approximately 590 nm to 560 nm with yellow, approximately 560 nm to 520 nm with green, approximately 520 nm to 490 nm with cyan, approximately 490 nm to 450 nm with blue, and approximately 450 nm to 400 nm with violet.

[0400] Color can be a polychromatic color, wherein two or more hues are assigned by the color. For example, color can be an iridescent polychromatic color, wherein the hue of the color varies within a large number of hues (e.g., 4, 5, 6, 7, 8 or more hues) when viewed from a single viewpoint or from two or more different viewpoints at least 15 degrees apart. Color can also be a finite iridescent polychromatic color, wherein the hue of the color varies or significantly (e.g., about 90 percent, about 95 percent or about 99 percent) within a finite number of hues (e.g., 2 or 3 hues) when viewed from two or more different viewpoints at least 15 degrees apart. Colors with limited iridescence are limited to two, three, or four hues selected from the following: primary RYB colors of red, yellow, and blue; primary and secondary RYB colors of red, yellow, blue, green, orange, and purple; or primary, secondary, and tertiary RYB colors of red, yellow, blue, green, orange-purple, greenish-yellow, yellow-orange, orange-red, red-purple, purple-blue, and blue-green.

[0401] The color (including hue, lightness, and / or chroma) of the decorated foam particles or components remains largely unchanged, if any, depending on the angle at which the object is observed or illuminated. In cases like these, the color can be angle-independent, because the observed hue, hue and lightness, or hue, lightness and chroma, are largely independent of the observation angle or independent of the observation angle.

[0402] Other properties of color, such as brightness, saturation, and purity, may be substantially the same and independent of the angle of observation or lighting, or may vary depending on the angle of observation or lighting. Colors may have a matte appearance, a glossy appearance, a metallic appearance, or a combination thereof.

[0403] There are various methodologies for defining color coordinate systems. One example is the L*a*b* color space, where, for a given lighting condition, L* is a luminance value, and a* and b* are values ​​based on the color-opposite dimensions of CIE coordinates (CIE 1976 color space or CIELAB). In some embodiments, the decorated portion of a foam particle or component may have two or more colors that are not significantly different. That is, when measured and assigned values ​​in the L*a*b* system, the two or more colors have coordinates that differ by less than 10 percent of the numerical range of a* and b* coordinates, or by less than 5 percent of the numerical range of a* and b* coordinates. In some embodiments, the decorated portion of a foam particle or component may have two or more distinct colors. That is, when measured and assigned values ​​in the L*a*b* system, the two or more distinct colors have coordinates that differ by at least 5 percent of the numerical range of a* and b* coordinates, or by at least 10 percent of the numerical range of a* and b* coordinates. When measured according to the CIE 1976 color space at viewing angles between -15 degrees and +60 degrees under given lighting conditions, the decorated portion of a foam particle or component has a first color and a second color, the first color having a first color measurement value having coordinates L1* and a1* and b1*, and the second color having a second color measurement value having coordinates L2* and a2* and b2*, wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the a1* coordinate value is at least 10 percent larger or smaller than the a2* coordinate value; the b1* coordinate value is at least 10 percent larger or smaller than the b2* coordinate value; or a combination thereof.

[0404] In CIELAB space, the comparison of two color measurements can be determined mathematically. For example, a first color can have a first measurement with coordinates L1*, a1*, and b1*, and a second color can have a second measurement with coordinates L2*, a2*, and b2*. The total difference between these two measurements over the CIELAB numerical range can be expressed as ΔE*. ab Its calculation is as follows: ΔE* ab =[(L1*-L2*) 2 +(a1*–a2*) 2 +(b1*-b2*) 2 ] 1 / 2 Generally, if two colors have a ΔE* less than or equal to 1, abIf the color difference is imperceptible to the human eye, and if the two colors have a ΔE* greater than 100, then the difference is negligible. ab If the color is considered to be an opposite color, then the ΔE* is approximately 2-3. ab The threshold considered to be a perceptible color difference. In some embodiments, the decorated portion of the foam particles or component has a first color and a second color different from the first color, wherein, when measured according to the CIE 1976 color space under given lighting conditions at viewing angles between -15 degrees and +60 degrees, the first color has a first color measurement value having coordinates L1* and a1* and b1*, and the second color has a second color measurement value having coordinates L2* and a2* and b2*, wherein the L1* and L2* values ​​may be the same or different, wherein the a1* and a2* coordinate values ​​may be the same or different, wherein the b1* and b2* coordinate values ​​may be the same or different, and wherein ΔE*ab between the first color measurement value and the second color measurement value is greater than or equal to about 60, where ΔE*ab = [(L1* - L2*)]. 2 +(a1*–a2*) 2 +(b1*-b2*) 2 ] 1 / 2 Optionally greater than or equal to approximately 80, or optional greater than or equal to approximately 100. When ΔE* ab Under certain lighting conditions, when the light intensity is less than 60, or less than 50, or less than 40, or less than 30, the two colors can be considered to have no significant difference.

[0405] Another example of a range of color values ​​is the CIELCH color space, where, for a given lighting condition, L* is the luminance value, C* is the chromaticity value, and h° represents the hue as an angular measurement. When measured in this color space, two colors are considered to have no significant difference if, under given lighting conditions, their h° angular coordinates differ by less than 10 degrees or less than 5 degrees (higher or lower). In some implementations, colors are considered different when the measured and assigned values ​​in the CIELCH system differ by at least 45 degrees (higher or lower) in the h° measurement. In some embodiments, the decorated portion of the foam particles or components has at least a first color and a second color different from the first color, wherein, when measured according to the CIELCH color space at an observation angle between -15 degrees and +60 degrees under given lighting conditions, the first color has a first color measurement value having coordinates L1* and C1* and h1°, and the second color has a second color measurement value having coordinates L2* and C2* and h2°, and wherein: the L1* value is at least 10 percent larger or smaller than the L2* value; the C1* coordinate value is at least 10 percent larger or smaller than the C2* coordinate value; the h1° coordinate value is at least 10 percent larger or smaller than the h2° coordinate value; or a combination thereof. In the h° measurement value of the CIELCH system, the first color and the second color may have a difference greater than about 10 degrees, or greater than about 20 degrees, or greater than about 30 degrees, or greater than about 40 degrees, or greater than about 50 degrees, or greater than about 60 degrees.

[0406] Another system used to characterize color includes the PANTONE matching system (Pantone LLC, Carlstadt, New Jersey, USA), which provides a visual color standard system, offering an accurate method for selecting, specifying, disseminating, and matching colors across any medium. In an example, a decorated portion of a foam particle or component may have a first color and a second color, the second color having a different PANTONE standard value than the first color, or more than a certain number of neighboring standard values ​​for the first color. If the color measured on a component falls within a certain number of neighboring standard values ​​for another color, such as within 20 neighboring PANTONE standard values, the two colors can be considered indistinguishable.

[0407] Other manufacturing.

[0408] The disclosed method may also include one or more additional manufacturing methods as needed or desired. For example, the disclosed method may also include compression molding. That is, the part manufactured using the disclosed method may be a preform for manufacturing footwear. It should be understood in the art that it may be a foamed article, which is then compression molded in a closed mold under heat and pressure. The compression molding process produces an outer surface layer on the molded article. The outer surface layer can provide a desirable aesthetic for the part used in manufacturing footwear, for example, it can impart a more uniform appearance and a more controllable topology, as well as modify the properties of the part, such as its compression deformation. Conventionally, preforms are cut from foam sheetstock or simultaneously injection molded and foamed. This document discloses a method for manufacturing preforms using foam particles using the disclosed additive manufacturing method, and then compression molding the preforms using compression molding methods known to those skilled in the art. The disclosed method provides a surprisingly effective way to reduce waste typically associated with components used in the manufacture of footwear, such as unused portions of sheet material or runners from injection molding. If the preform is made from sheet material, the disclosed method also typically eliminates the need for cutting tools, or alternatively, if the preform is an injection-molded preform, the disclosed method eliminates significant costs associated with tooling.

[0409] The disclosed method may also include directly constructing the foam particle structure as described herein on elements such as textile elements, membrane elements, molded resin elements, and similar elements, thereby bonding or adhering the structure to the element. Optionally or additionally, elements such as textile elements, membrane elements, molded resin elements, and similar elements may be positioned in contact with attached or unattached granular foam, and then further particles may be attached to the top of the element and / or attached around the element. This process can be used to create a layered structure comprising one or more layered elements between one or more layers of fused foam particles. Optionally or additionally, one or more elements may be wholly or partially surrounded by attached foam particles. Optionally, the attached foam particles may be adhered to the element. For example, foam particles can be bonded to an element by physical bonding formed during the attachment process or by applying an adhesive to at least a portion of the element. Physical bonding formed during the attachment process can be achieved by melting or softening the foam particles during the attachment process and then re-solidifying the foam particles, or by melting or softening a portion of the element (e.g., the thermoplastic material forming the body of the element, or the thermoplastic material forming the outer layer of the element).

[0410] The attached foam particle structure can be built onto flexible elements, such as textile elements or membrane elements. For example, the flexible element can be a component of footwear articles, such as a straddle or upper, and the attached foam particle structure built on the flexible element can be a cushioning element, such as a midsole component, ankle cushioning, or tongue for footwear articles. Alternatively, the flexible element can be a component of clothing or sports equipment articles, and the foam particle structure built on the flexible element can be a cushioning element or shock-absorbing element. Using additive manufacturing processes to fuse foam particles to form a component allows the attached foam particle portion of the component to be easily customized based on individual measurements, the desired cushioning layer or shock-absorbing layer, or both.

[0411] The attached foam particle structure can be incorporated into an element that includes a membrane element such as a bladder. The bladder can be a sealed, fluid-filled bladder, or it can be a bladder that is not yet filled with fluid and is sealed. The membrane portion of the bladder can be a barrier membrane formed from multiple layers of different polymer materials. For example, the membrane element can be a component of footwear articles, such as a bladder, and the combination of the attached foam particle structure and the membrane element can be a sole structure for footwear articles, such as a component of a sole interlayer or sole layer for footwear articles. Alternatively, the membrane element can be a component of clothing or sports equipment articles, and the foam particle structure constructed on the membrane element can be a cushioning element or a shock-absorbing element. Using the disclosed additive manufacturing process to fuse foam particles to form a component allows the attached foam particle portion of the component to be easily customized based on individual measurements, the desired cushioning layer or shock-absorbing layer, or both.

[0412] The attached foam particle structure can be a rigid element, such as a molded resin element, including injection-molded or extruded resin elements. For example, the rigid element can be a component of footwear articles, such as a midsole component (e.g., a support or plate structure) or a heel stabilizer, and the attached foam particle structure built on the rigid element can be a cushioning element, such as a midsole component or ankle cushioning for footwear articles. Alternatively, the rigid element can be a component of clothing or sports equipment articles, and the foam particle structure built on the rigid element can be a cushioning element or shock-absorbing element. For example, the rigid element can be a component of protective equipment articles, and the attached foam particle structure can be directly built onto the rigid element to form a cushioning element or shock-absorbing element for protective equipment articles. Using the disclosed manufacturing process to fuse the foam particles to form the cushioning or shock-absorbing portion of the article allows the attached foam particle structure to be easily customized based on individual measurements, the desired cushioning layer or shock-absorbing layer, or both.

[0413] The disclosed method may also include directly attaching foam particles prepared as described herein, and thereby adhering to and entering a variety of structures. In one example, the attached foam particles may be attached to form a structure having inner and outer surfaces. The attached foam particle structure may be a structure having more than one inner surface and more than one outer surface, such as a honeycomb structure. The attached foam particle structure may include sealed or open hollow regions. Optionally, the hollow regions may be filled with more than one unattached foam particle or with one or more rigid elements. The attached foam particle structure may have a cylindrical or polygonal geometry. In one example, the attached foam particle structure may be a sealed structure with inner and outer surfaces and may have a spherical, ellipsoidal, cylindrical, or polygonal geometry. Using a hollow foam particle structure allows for a reduction in the overall structural density compared to a solid structure with the same geometry. Hollow or sealed foam particle structures can be used to form support elements, such as support columns. In one instance, based on the degree to which the foam particles are attached in specific areas of the column structure, the column can be designed to bend in a specific direction or under a specific load. More than one hollow foam particle structure or sealed foam particle structure can be grouped or attached together to form a larger structure, such as a shoe sole interlayer or other cushioning component.

[0414] Elastomer thermoplastic polymer.

[0415] Various methods for forming and decorating components comprising more than one foam particle have been described, and now we describe the elastomeric thermoplastic polymers mentioned herein in more detail. The foam particles of this disclosure can be prepared from suitable thermoplastic elastomers. For example, the thermoplastic elastomer can be selected from thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, thermoplastic polyether elastomers, thermoplastic copolyether ester elastomers, thermoplastic polyamide elastomers, thermoplastic polystyrene elastomers, thermoplastic polyolefin elastomers, thermoplastic copolyether amide elastomers, thermoplastic styrene diene copolymer elastomers, thermoplastic styrene block copolymer elastomers, thermoplastic polyamide elastomers, thermoplastic polyimide elastomers, any copolymers thereof, and any blends thereof.

[0416] Thermoplastic elastomers used to prepare foam particles may include thermoplastic copolyether ester elastomers. It should be understood that, as used herein, "thermoplastic copolyether ester elastomer" can be used interchangeably with "thermoplastic polyether-polyester block copolymer," "thermoplastic polyester / polyether block copolymer," "copolyester elastomer," "poly-ether-ester block copolymer," "block poly-ether-ester," "polyester elastomer," "thermoplastic poly-ether-ester," "copoly(ether ester)," and "copolyester thermoplastic elastomer." Thermoplastic copolyether ester elastomers may include hard (or crystalline) polyester segments dispersed in soft (or amorphous) polyether segments. Thermoplastic copolyether ester elastomers may be block copolymers. Thermoplastic copolyether ester elastomers may be segment block copolymers. Thermoplastic copolyether ester elastomers may be block copolymers comprising polyester segments or blocks and polyether segments or blocks.

[0417] Thermoplastic copolyether ester elastomers used to prepare foam particles may include polyester segments and polyether segments (such as polyalkylene(ether) glycol or polyalkylene(ether) polyol), the polyester segments being produced by the reaction of dicarboxylic acid derivatives (such as terephthalate) and diols (such as butanediol).

[0418] Polyester segments may include polybutylene terephthalate (PBT). Polyester segments may include polyethylene terephthalate (PET). Polyester segments may have a molecular weight of about 3,000 Daltons to about 9,000 Daltons. Polyester segments may have a molecular weight of about 5,000 Daltons to about 7,000 Daltons.

[0419] Polyether segments may contain long-chain polyols. Polyether segments may be polyethylene glycol (PEG), polypropylene glycol (PPG), polypropylene ether glycol (PPEG), polytetramethylene glycol (PTMG or PTHF), polytetramethylene ether glycol, or combinations thereof. Polyether segments may have a molecular weight of approximately 200 Daltons to approximately 4000 Daltons. Polyether segments may also have a molecular weight of approximately 1000 Daltons to approximately 3000 Daltons.

[0420] Thermoplastic coether ester elastomers may include soft segments of polytetramethylene ether terephthalate and hard segments of polybutylene terephthalate. Thermoplastic coether ester elastomers are commercially available, and non-limiting examples are available under the trade names HYTREL (DuPont Company, Wilmington, Delaware), ARNITEL (DSM Engineering Plastics, Evansville, Indiana), and PELPRENE (Toyobo Co., Ltd., Osaka, Japan).

[0421] Thermoplastic coether ester elastomer polymers may include polyether segments obtained by polymerization of tetrahydrofuran (i.e., poly(tetramethylene ether)) and polyester segments obtained by polymerization of tetramethylene glycol and phthalic acid (i.e., 1,4-butanediol terephthalate). Generally, the more polyether units incorporated into the coether ester, the softer the polymer. The poly(tetramethylene ether) glycol used to prepare the coether ester may have a molecular weight from about 500 Daltons to about 3500 Daltons, or from about 800 Daltons to about 2500 Daltons.

[0422] Thermoplastic copolyether ester elastomers may comprise repeating units derived from 30 to 70 wt% of 1,4-butanediol terephthalate and 10 to 70 wt% of poly(tetramethylene ether) terephthalate. Thermoplastic copolyether ester elastomers may comprise repeating units derived from 55 to 60 wt% of 1,4-butanediol terephthalate, 23 to 27 wt% of 1,4-butanediol isophthalate, 10 to 15 wt% of poly(tetramethylene ether) terephthalate, and 3 to 7 wt% of poly(tetramethylene ether) isophthalate. The poly(tetramethylene ether) glycol used to prepare the copolyether ester may have a molecular weight from about 800 Daltons to about 1200 Daltons.

[0423] The thermoplastic copolyether ester elastomer polymer may comprise repeating units derived from 30 to 40 wt% 1,4-butanediol terephthalate and 60 to 70 wt% poly(tetramethylene ether) terephthalate. The poly(tetramethylene ether) diol used to prepare the copolyether ester preferably has a molecular weight from 1500 Daltons to about 2500 Daltons.

[0424] Thermoplastic coether ester elastomers can be block copolymers of short-chain terephthalate glycol esters and long-chain terephthalate glycol esters, comprising approximately 60 weight percent of hard segments of polybutylene terephthalate and approximately 40 weight percent of soft segments of polytetramethylene terephthalate. These thermoplastic coether ester elastomers have a Shore hardness of 55D (ASTM D-2240), a melting point of 211°C (ASTM D-2117), a Vicat softening point of 180°C (ASTM D1525), and a flexural modulus of 207 MPa (ASTM D790). Suitable materials possessing the aforementioned properties are commercially available under the trade name HYTRELO 5556 (DuPont Company, Wilmington, Delaware).

[0425] Thermoplastic coether ester elastomers can be block copolymers of short-chain terephthalate glycol esters and long-chain terephthalate glycol esters, the block copolymer comprising about 42 weight percent of hard segments of polybutylene terephthalate and about 58 weight percent of soft segments of polytetramethylene terephthalate. These thermoplastic coether ester elastomers have a hardness of 92A / 40D, a melting point of 168°C, a Vicat softening point of 112°C, and a flexural modulus of 48.3 MPa. Suitable materials having the aforementioned properties are commercially available under the trade name HYTREL 4056 (DuPont Company, Wilmington, Delaware).

[0426] Thermoplastic coether ester elastomers can be block copolymers of short-chain terephthalate glycol esters and long-chain terephthalate glycol esters, the block copolymer comprising about 80 weight percent of hard segments of polybutylene terephthalate and about 20 weight percent of soft segments of polytetramethylene terephthalate. These thermoplastic coether ester elastomers have a hardness of about 72D, a melting point of 219°C, a Vicat softening point of 207°C, and a flexural modulus of 585 MPa. Suitable materials having the aforementioned properties are commercially available under the trade name HYTRELO 7246 (DuPont Company, Wilmington, Delaware).

[0427] Thermoplastic coether ester elastomers may contain long-chain ester units of Formula I:

[0428]

[0429] Short-chain ester units of formula II:

[0430]

[0431] Where R 1 Includes divalent groups remaining after removing terminal hydroxyl groups from the poly(alkylene ether), said poly(alkylene ether) having a carbon-to-oxygen ratio from about 2.0 to about 4.3 and a number-average molecular weight from about 400 Daltons to about 6000 Daltons; wherein R 2 This includes the divalent group remaining after removing the carboxyl group from a dicarboxylic acid having a molecular weight of less than about 300 Daltons; wherein R 3 This includes the divalent groups remaining after removing the hydroxyl groups from low molecular weight diols having a molecular weight of less than about 250 Daltons; wherein R 4It includes the divalent group remaining after removing the carboxyl group from a dicarboxylic acid having a molecular weight of less than about 300 Daltons; wherein the long-chain ester unit represented by Formula I constitutes about 5% to about 95% by weight of the thermoplastic coether ester elastomer; and wherein the short-chain ester unit represented by Formula II constitutes about 95% to about 5% by weight of the thermoplastic coether ester elastomer.

[0432] R 1 It may include the divalent groups remaining after removing the terminal hydroxyl groups from poly(tetramethylene ether). R 1 It may have a number average molecular weight ranging from about 500 Daltons to about 3,500 Daltons; about 600 Daltons to about 3,000 Daltons; about 800 Daltons to about 1,200 Daltons; about 800 Daltons to about 2,000 Daltons; about 800 Daltons to about 2,500 Daltons; about 800 Daltons to about 3,000 Daltons; about 800 Daltons to about 3,500 Daltons; about 800 Daltons to about 4,000 Daltons; about 1,000 Daltons to about 3,000 Daltons; or about 1,500 Daltons to about 2,500 Daltons.

[0433] R 2 It can include the divalent group remaining after removing the carboxyl group from an aromatic dicarboxylic acid. R 2 It may include the divalent groups remaining after removing the carboxyl group from 1,4-phthalic acid.

[0434] R 3 It may include the divalent groups remaining after removing the hydroxyl groups from C2-C6 alkyl diols. 3 It may include the divalent groups remaining after the hydroxyl groups have been removed from 1,4-butanediol.

[0435] R 4 It can be the divalent group remaining after removing the carboxyl group from an aromatic dicarboxylic acid. In another aspect, R... 4 It can be the divalent group remaining after removing the carboxyl group from 1,4-phthalic acid.

[0436] The long-chain ester unit represented by Formula I can constitute about 10 to about 60% by weight of thermoplastic coether ester elastomer; about 20 to about 60% by weight of thermoplastic coether ester elastomer; about 30 to about 60% by weight of thermoplastic coether ester elastomer; about 10 to about 70% by weight of thermoplastic coether ester elastomer; about 20 to about 70% by weight of thermoplastic coether ester elastomer; about 30 to about 70% by weight of thermoplastic coether ester elastomer; about 10 to about 80% by weight of thermoplastic coether ester elastomer; about 20 to about 80% by weight of thermoplastic coether ester elastomer; or about 30 to about 80% by weight of thermoplastic coether ester elastomer.

[0437] The short-chain ester unit represented by Formula II can constitute about 20 to about 90% by weight of thermoplastic coether ester elastomer; about 40 to about 90% by weight of thermoplastic coether ester elastomer; about 20 to about 80% by weight of thermoplastic coether ester elastomer; about 40 to about 80% by weight of thermoplastic coether ester elastomer; about 20 to about 70% by weight of thermoplastic coether ester elastomer; about 40 to about 70% by weight of thermoplastic coether ester elastomer; about 40 to about 60% by weight of thermoplastic coether ester elastomer; or about 20 to about 60% by weight of thermoplastic coether ester elastomer.

[0438] Optionally, at least about 50% by weight of the short-chain ester units represented by Formula II may be identical.

[0439] Thermoplastic coether ester elastomers may comprise polybutylene terephthalate blocks and poly(tetramethylene ether) terephthalate blocks, wherein the thermoplastic coether ester elastomer comprises from about 95 wt% to about 5 wt% of polybutylene terephthalate blocks and from about 5 wt% to about 95 wt% of poly(tetramethylene ether) terephthalate blocks, and wherein the poly(tetramethylene ether) terephthalate blocks have a number average molecular weight from about 200 Daltons to about 6000 Daltons.

[0440] Thermoplastic coether ester elastomers may comprise polybutylene terephthalate blocks and poly(tetramethylene ether) terephthalate blocks, wherein the thermoplastic coether ester elastomer comprises from about 70 wt% to about 20 wt% of polybutylene terephthalate blocks and from about 5 wt% to about 95 wt% of poly(tetramethylene ether) terephthalate blocks, and wherein the poly(tetramethylene ether) terephthalate blocks have a number average molecular weight from about 200 Daltons to about 6000 Daltons.

[0441] Thermoplastic coether ester elastomers may comprise polybutylene terephthalate blocks and poly(tetramethylene ether) terephthalate blocks, wherein the thermoplastic coether ester elastomer comprises from about 80 wt% to about 30 wt% of polybutylene terephthalate blocks and from about 5 wt% to about 95 wt% of poly(tetramethylene ether) terephthalate blocks, and wherein the poly(tetramethylene ether) terephthalate blocks have a number average molecular weight from about 200 Daltons to about 6000 Daltons.

[0442] Thermoplastic copolyether elastomers may comprise polybutylene terephthalate blocks and poly(tetramethylene ether) terephthalate blocks, wherein the thermoplastic copolyether elastomer comprises from about 70 wt% to about 20 wt% of polybutylene terephthalate blocks and from about 30 wt% to about 80 wt% of poly(tetramethylene ether) terephthalate blocks, and wherein the poly(tetramethylene ether) terephthalate blocks have a number average molecular weight from about 200 Daltons to about 6000 Daltons.

[0443] The poly(tetramethylene ether) terephthalate block can have a number average molecular weight from about 800 Daltons to about 1200 Daltons; from about 1500 Daltons to about 2500 Daltons; or from about 1000 Daltons to about 3000 Daltons.

[0444] Thermoplastic elastomers used in the preparation of foam particles may include thermoplastic polyurethane elastomers. Thermoplastic polyurethane elastomers may be selected from thermoplastic polyester-polyurethane elastomers, thermoplastic polyether-polyurethane elastomers, thermoplastic polycarbonate-polyurethane elastomers, thermoplastic polyolefin-polyurethane elastomers, any copolymers thereof, and any blends thereof. Thermoplastic polyurethane elastomers may be thermoplastic polyester-polyurethane elastomers. Thermoplastic polyurethane elastomers may be thermoplastic polyether-polyurethane elastomers. Thermoplastic polyurethane elastomers may be thermoplastic polycarbonate-polyurethane elastomers.

[0445] The thermoplastic polyurethane used to prepare the foam particles can have a melt index (also known as melt flow index or melt flow rate) of at least about 160 g / 10 min (at 190°C, 21.6 kg), as measured according to ASTM D1238. The melt index can be from about 160 g / 10 min to about 250 g / 10 min (at 190°C, 21.6 kg) or from about 160 g / 10 min to about 220 g / 10 min (at 190°C, 21.6 kg), in each case as measured according to ASTM D1238.

[0446] Thermoplastic polyurethanes can be produced via (a) the reaction of a diisocyanate with a bifunctional compound reactive to isocyanates. Typically, the bifunctional compound has two hydroxyl groups (diols) and can have a molar mass from 62 Daltons (molar mass of ethylene glycol) to about 10,000 Daltons, although bifunctional compounds with other isocyanate groups (e.g., secondary amines) can generally be used in small amounts, and trifunctional and monofunctional isocyanate-reactive compounds in limited molar fractions can be used. Preferably, the polyurethane is linear. Including a bifunctional compound having a molar mass of about 400 or greater introduces soft segments into the polyurethane. The increased ratio of soft to hard segments in the polyurethane causes it to become increasingly flexible and eventually elastic. In some instances, such as when the molded article is for the outsole of a footwear article, the particles can be advantageously prepared using rigid thermoplastic polyurethanes or combinations of thermoplastic polyurethanes. When the molded article is for the midsole layer of footwear, the granules can be advantageously prepared using elastomeric thermoplastic polyurethane or a combination of elastomeric thermoplastic polyurethane.

[0447] Suitable thermoplastic polyurethanes include thermoplastic polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes. Non-limiting suitable examples of these include, but are not limited to, polyurethanes polymerized using the following as diol reactants: polyester diols prepared from diols and dicarboxylic acids or anhydrides; polylactone polyester diols (e.g., polycaprolactone diol); polyester diols prepared from hydroxy acids that are monocarboxylic acids containing a hydroxyl group; polytetrahydrofuran diol; polyether diols prepared from ethylene oxide, propylene oxide, or a combination of ethylene oxide and propylene oxide; and polycarbonate diols such as polyhexamethylene carbonate diol and poly(hexamethylene-co-pentamethylene) carbonate diol. Elastomeric thermoplastic polyurethanes can be prepared by reacting one or more of these polymeric diols (polyester diol, polyether diol, polylactone diol, polytetrahydrofuran diol, or polycarbonate diol) with one or more polyisocyanates and optionally one or more monomeric chain extenders. The chain-extended compound is a compound having two or more functional groups that react with isocyanate groups, preferably two functional groups. Preferably, the elastomeric thermoplastic polyurethane is substantially linear (i.e., substantially all reactants are bifunctional).

[0448] Non-limiting examples of polyester diols used to form elastomeric thermoplastic polyurethanes include polyester diols prepared by polycondensation of dicarboxylic acid compounds, their anhydrides, and their polymerizable esters (e.g., methyl esters) with diol compounds. Preferably, all reactants are bifunctional, although small amounts of monofunctional, trifunctional, and higher-functionality materials may be included (potentially up to a few molar percentages). Suitable dicarboxylic acids include, but are not limited to, glutaric acid, succinic acid, malonic acid, oxalic acid, phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, anhydrides of these dicarboxylic acids, and mixtures thereof. Suitable polyols include, but are not limited to, wherein the extender is selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, cyclohexanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,3-propanediol, butanediol, neopentanediol, and combinations thereof. Sometimes, small amounts of triols or higher-functionality polyols, such as trimethylolpropane or pentaerythritol, are included. Carboxylic acids may include adipic acid, and diols may include 1,4-butanediol. Typical catalysts for esterification polymerization are protic acids, Lewis acids, titanium alkoxides, and dialkyltin oxides.

[0449] Hydroxycarboxylic acid compounds such as 12-hydroxystearic acid can also be polymerized to produce polyester diols. Such reactions can be carried out with or without an initiating diol, such as one of the diols already mentioned.

[0450] Polylactone diol reactants can also be used to prepare thermoplastic polyurethane elastomers. Polylactone diols can be prepared by reacting a diol initiator, such as a diol like ethylene glycol or propylene glycol, or another of the diols already mentioned, with a lactone. Lactones that can be ring-opened by active hydrogen can be polymerized, such as, but not limited to, ε-caprolactone, γ-caprolactone, β-butyrolactone, β-propiolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-decylactone, δ-decylactone, γ-nonylactone, γ-octylactone, and combinations thereof. The lactone ring can be substituted with an alkyl group having 1 to 7 carbon atoms. The lactone can be ε-caprolactone. Useful catalysts include those mentioned above regarding polyester synthesis. Alternatively, the reaction can be initiated by forming a sodium salt of the hydroxyl group on the molecule that will react with the lactone ring.

[0451] Tetrahydrofuran can be produced by using counterions such as SbF6. - AsF6 - PF6 - SbCl6 - BF4 - CF3SO3 - FSO3 - and ClO4 - Polymerization is achieved through a cationic ring-opening reaction. Initiation occurs via the formation of tertiary oxonium ions. Polytetrahydrofuran segments can be prepared as “living polymers” and terminated by reaction with the hydroxyl groups of a diol, such as any of the diols mentioned above.

[0452] Aliphatic polycarbonates can be prepared by polycondensation of aliphatic diols with dialkyl carbonates (such as diethyl carbonate), cyclic diol carbonates (such as cyclic carbonates with five- and six-membered rings), or diphenyl carbonate in the presence of catalysts such as alkali metals, tin catalysts, or titanium compounds. Another method of producing aliphatic polycarbonates is the ring-opening polymerization of cyclic aliphatic carbonates catalyzed by organometallic catalysts. Polycarbonate diols can also be produced by copolymerization of epoxides with carbon dioxide. Aliphatic polycarbonate diols are prepared by reacting diols with dialkyl carbonates (such as diethyl carbonate), diphenyl carbonate, or dioxolanones (such as cyclic carbonates with five- and six-membered rings) in the presence of catalysts such as alkali metals, tin catalysts, or titanium compounds. Useful diols include, but are not limited to, any diols already mentioned. Aromatic polycarbonates are typically prepared by reacting bisphenols, such as bisphenol A, with phosgene or diphenyl carbonate.

[0453] Polymer diols used in the manufacture of thermoplastic polyurethane elastomers, such as the polymeric polyester diols and polyether diols described above, preferably have a number-average molecular weight (e.g., determined by the ASTM D-4274 method) of about 300 Daltons to about 8,000 Daltons, or from about 300 Daltons to about 5,000 Daltons, or from about 300 Daltons to about 3,000 Daltons.

[0454] The synthesis of thermoplastic polyurethane can be carried out by reacting one or more compounds having at least two (preferably two) isocyanate groups in a polymeric diol with, optionally, one or more chain extenders. The elastomeric thermoplastic polyurethane is preferably linear, and therefore the polyisocyanate component is preferably substantially bifunctional. Useful diisocyanate compounds for the preparation of thermoplastic polyurethane elastomers include, but are not limited to, methylene bis-4-cyclohexyl isocyanate; cyclohexyl diisocyanate (CHDI); isophorone diisocyanate (IPDI); m-tetramethylxylyl diisocyanate (m-TMXDI); p-tetramethylxylyl diisocyanate (p-TMXDI); ethylene diisocyanate; 1,2-diisocyanatopropane; 1,3-diisocyanatopropane; 1,6-diisocyanatohexane (hexamethylene diisocyanate or HDI); 1,4-butylene diisocyanate; lysine diisocyanate; 1,4-methylene bis(cyclohexyl isocyanate); 2,4-methylphenylene (“toluene”) diisocyanate and 2,6-methylphenylene diisocyanate (TDI); 2,4'-methylene diphenyl diisocyanate (MDI); 4,4'- Methylene diphenyl diisocyanate (MDI); o-xylene diisocyanate, m-xylene diisocyanate, and p-xylene diisocyanate (XDI); 4-chloro-1,3-phenylene diisocyanate; naphthylene diisocyanates, including 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, and 2,6-naphthylene diisocyanate. Esters; 4,4'-dibenzyl diisocyanate; 4,5'-diphenyl diisocyanate; 4,4'-diisocyanatodibenzyl; 3,3'-dimethoxy-4,4'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenyl diisocyanate; 1,3-diisocyanobenzene, 1,4-diisocyanobenzene, and combinations thereof. Particularly useful is diphenylmethane diisocyanate (MDI).

[0455] Useful chain extenders containing active hydrogen typically contain at least two active hydrogen groups, such as glycols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkyl thiols, and hydroxyalkyl thiols, among others. The molecular weight of chain extenders can range from about 60 g / mol to about 400 g / mol. Chain extenders can include alcohols and amines. Typical examples of useful diols used as polyurethane chain extenders include, but are not limited to, 1,6-hexanediol; cyclohexanediol (sold by Eastman Chemical Co. as CHDM); 2-ethyl-1,6-hexanediol; 1,4-butanediol; lower oligomers of ethylene glycol and ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; lower oligomers of propylene glycol and propylene glycol, including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; 1,3-propanediol; neopentyl glycol; dihydroxyalkylated aromatic compounds, such as hydroquinone and resorcinol bis(2-hydroxyethyl) ethers; p-xylene-α,α′-diol; p-xylene-α,α′-diol bis(2-hydroxyethyl) ethers; m-xylene-α,α′-diol and bis(2-hydroxyethyl) ethers; 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate; and mixtures thereof. Suitable diamine extenders include, but are not limited to, p-phenylene diamine, m-phenylene diamine, benzidine, 4,4'-methylenediphenylamine, 4,4'-methylenebis(2-chloroaniline), ethylenediamine, and combinations thereof. Other typical chain extenders are amino alcohols, such as ethanolamine, propanolamine, butanolamine, and combinations thereof. Preferred extenders include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and combinations thereof.

[0456] In addition to the bifunctional expanders described above, small amounts of trifunctional expanders such as trimethylolpropane, 1,2,6-hexanetriol, and glycerol, and / or monofunctional active hydrogen compounds such as butanol or dimethylamine may also be present. The amount of trifunctional expanders and / or monofunctional compounds used will preferably be based on a few equivalent percentages or less of the total weight of the reaction products and active hydrogen-containing groups used.

[0457] The reaction of polyisocyanate, polymeric glycol, and optionally chain extender is typically carried out by heating the components in the presence of a catalyst. Typical catalysts used for this reaction include organotin catalysts, such as stannous octoate or dibutyltin dilaurate. Generally, the ratio of polymeric glycol, such as polyester glycol, to the extender can vary over a relatively wide range, depending heavily on the desired hardness of the elastomeric thermoplastic polyurethane. For example, the equivalent ratio of polyester glycol to extender can range from 1:0 to 1:12, and more preferably from 1:1 to 1:8. Preferably, the diisocyanate used is proportioned such that the overall ratio of the isocyanate equivalent to the equivalent of the hydrogen-containing material is in the range of 0.95:1 to 1.10:1, and more preferably from 0.98:1 to 1.04:1. The polymeric glycol segment is typically from about 25% by weight to about 65% by weight of the elastomeric thermoplastic polyurethane, and preferably from about 25% by weight to about 50% by weight of the elastomeric thermoplastic polyurethane.

[0458] Thermoplastic polyurethane elastomers used to prepare foam particles may contain long-chain polyols. Long-chain polyols may be selected from polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polypropylene polyols, and any copolymers thereof. Long-chain polyols may be polyether polyols, polyester polyols, and any copolymers thereof. Long-chain polyols may be polyether polyols. Long-chain polyols may be polyester polyols. Long-chain polyols may have a number average molecular weight of not less than about 500 Daltons. Long-chain polyols may have a number average molecular weight of about 500 Daltons to about 10,000 Daltons; about 600 Daltons to about 6,000 Daltons; or about 800 Daltons to about 4,000 Daltons.

[0459] A non-limiting example of a commercially available elastomeric thermoplastic polyurethane suitable for manufacturing thermoplastic polyurethane foam particles, having a melt flow index from about 160 g / 10 min to about 220 g / 10 min (at 190 degrees Celsius, 21.6 kg), is ELASTOLLAN SP9213 (200 g / 10 min melt flow index (at 190 degrees Celsius, 21.6 kg)) available from BASF Polyurethanes GmbH.

[0460] More rigid thermoplastic polyurethanes can be synthesized in the same manner but with a lower content of polymeric diol segments. Rigid thermoplastic polyurethanes can, for example, comprise polyester diol segments, polyether diol segments, or polycarbonate diol segments from about 0% by weight to about 25% by weight. The synthesis of rigid polyurethanes is well known in the art and has been described in numerous references. Rigid thermoplastic polyurethanes having a melt index of at least about 160 g / 10 min (at 190°C, 21.6 kg) as measured according to ASTM D 1238 are commercially available and include those marketed under the trade name Lubrizol Corp., Wickliffe, Ohio. Those sold by ETPU.

[0461] Suitable thermoplastic polyurea elastomers can be prepared by reacting one or more polymeric diamines or polyols with one or more of the polyisocyanates already mentioned and one or more diamine extenders. Non-limiting examples of suitable diamine extenders include ethylenediamine, 1,3-propanediamine, 2-methylpentanediamine, hexamethylenediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imide-bis(propylamine), N-(3-aminopropyl)-N-methyl-1,3-propanediamine, 1,4-bis(3-aminopropoxy)butane, diethylene glycol di(aminopropyl) ether, 1-methyl-2,6-diamino-cyclohexane, 1,4-diamino... The diamines used include 1,3-bis(methylamino)cyclohexane, 1,4-bis(methylamino)cyclohexane, isophorone diamine, 1,2-bis(sec-butylamino)cyclohexane, 1,4-bis(sec-butylamino)cyclohexane, N,N'-diisopropylisophorone diamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, N,N'-dialkylaminodicyclohexylmethane, and 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodicyclohexylmethane. Polymer diamines include polyoxyethylene diamine, polyoxypropylene diamine, poly(ethylene oxide-oxypropylene) diamine, and poly(tetramethylene ether) diamine. Amine-functionalized and hydroxyl-functionalized extenders already mentioned may also be used. Typically, as in the past, trifunctional reactants are restricted and can be used in combination with monofunctional reactants to prevent cross-linking.

[0462] Thermoplastic elastomers may include thermoplastic polyamide elastomers. Optionally, thermoplastic polyamide elastomers may include nylon 6, nylon 12, or combinations thereof.

[0463] Suitable thermoplastic polyamide elastomers can be obtained by: (1) (a) polycondensation of dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid or any other dicarboxylic acid mentioned with (b) diamines such as ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine or decanediamine, 1,4-cyclohexanediamine, m-xylylenediamine or any other diamine mentioned; (2) ring-opening polymerization of cyclic lactams such as ε-caprolactam or ω-laurolactam; (3) polycondensation of aminocarboxylic acids such as 6-aminohexanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid; or (4) copolymerization of cyclic lactams with dicarboxylic acids and diamines to prepare carboxylic acid-functionalized polyamide blocks, followed by reaction with polymeric ether glycols (polyoxyalkylene glycols) such as any polymeric ether glycols mentioned. Polymerization can be carried out, for example, at temperatures ranging from about 180 degrees Celsius to about 300 degrees Celsius. Specific examples of suitable polyamide blocks include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, copolymerized nylon, nylon MXD6, and nylon 46.

[0464] Thermoplastic elastomers may include at least one thermoplastic polystyrene elastomer. Thermoplastic polystyrene elastomers may be styrene block copolymer elastomers. Thermoplastic styrene block copolymer elastomers may be styrene-ethylene-butene-styrene block copolymers. Styrene block copolymer elastomers may be poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), poly(styrene-isoprene-styrene), any copolymers thereof, and any blends thereof.

[0465] When determined using differential scanning calorimetry, the thermoplastic elastomer used to prepare foam particles can be characterized by a broad peak that indicates the melting temperature (T0). m The melting temperature can be characterized by a melting range of about 15 degrees Celsius to about 200 degrees Celsius or about 50 degrees Celsius to about 90 degrees Celsius. The melting temperature of thermoplastic elastomers can be characterized by a melting range of about 30 degrees Celsius to about 150 degrees Celsius from the initial melting point to the peak melting temperature. The melting temperature can also be characterized by a melting range of at least about 30 degrees Celsius or by a melting range of at least about 50 degrees Celsius.

[0466] Methods for representing disclosed items.

[0467] Several methods exist in the art for measuring the elasticity and / or energy return of foam. One method for measuring the elasticity of foam is based on ASTM D 2632-92, a test for solid rubber materials. For use with foam, the test sample is prepared as described in ASTM D2632-92, but a foam sample is used instead of a solid rubber sample. The test uses a plunger that is guided by a vertical rod and dropped from a height onto the test sample. The drop height is divided into 100 equal parts, and the height of the plunger's rebound is measured using this 100-part scale to determine the elasticity of the sample. Alternative methods can also be used, which employ a ball of standard weight dropped onto the sample and measure the ball's rebound height to determine the sample's elasticity. Elasticity and / or energy return can be determined using force / displacement behavior, which is determined using methods known to those skilled in the art.

[0468] The force / displacement behavior of the disclosed articles can be measured using an Instron Electropuls E10000 (Instron, Norwood, Massachusetts, USA) with a stainless steel 45 mm circular cross-section impact geometry. The test foam board can be approximately 10 mm thick, although thinner or thicker foam boards can also be used. Each sample can be evaluated using two different compression cycles: a “run” and a “walk”. The “run” compression cycle consists of the sample being compressed from 0 Newtons to 300 Newtons and back to 0 Newtons within 180 ms under displacement control, followed by a 400 ms pause, for a total of ~1.7 Hz. The “walk” compression cycle consists of the sample being compressed from 0 Newtons to 144 Newtons and back to 0 Newtons within 600 ms, followed by a 400 ms pause, for a total of ~1 Hz.

[0469] Compression can be measured by preparing samples of foam with a standard thickness (e.g., 10 mm). Samples with a thickness less than the standard can be stacked to create a sample with a standard thickness. The sample is loaded onto a metal compression plate and compressed to a height of 50 percent of its original thickness (e.g., 5 mm). The sample is placed in an oven at 50 degrees Celsius with its sides facing down for 6 hours. At the end of 6 hours, the sample is removed from the oven and from the metal compression plate and allowed to cool for 30 minutes. After cooling, the thickness of the sample is measured. The percentage of compression deformation (CS) is calculated by: (a) subtracting the final sample thickness from the original sample thickness, and (b) subtracting the thickness of the 50 percent compression from the original sample thickness, (c) dividing (a) by (b), and (d) multiplying the result by 100 to obtain the percentage of compression deformation (where all thicknesses are measured in millimeters).

[0470] Energy input can be viewed as the integral of the force-displacement curve during compressive loading. Hysteresis is considered as a ratio: (energy output) / (energy input), which can also be viewed as the energy efficiency of the foam. Fatigue behavior is judged by the change in foam displacement at the maximum load of the cycle. All properties—stiffness, hysteresis, and fatigue—are measured over multiple cycles for both running and walking compression cycles. A typical characterization using the compression sequence described above can run for 5000 cycles, simulating approximately ~5-10 miles of walking / running, and taking about 45 minutes of testing time on an Instron Electropuls E10000 instrument. Longer runs of up to 100,000 compression cycles can be performed to simulate the accelerated material response used at ~100-200 miles.

[0471] Tensile strength can be measured on a punched sample of a dumbbell-shaped article of standard dimensions, such as a width of 2.5 cm, a length of 11.5 cm, and a minimum thickness of 3 mm to 4 mm. The dumbbell conforms to the shape described in ASTM D412, Die C. The sample is symmetrically loaded onto a long-stroke extensometer such as the Instron 2603-080 and tested using this long-stroke extensometer, which allows for a minimum of 1000 percent strain, with a gauge length of 25 mm and a resolution of at least 0.1 mm. The tensile value at the failure point of the sample (the point at which the load initially falls during the test) is recorded.

[0472] The melt flow index is determined according to the test method described in ASTM D1238-13, specifically for the melt flow rate of thermoplastics extruded through an extrusion plasticizer, using procedure A as described therein. In short, the melt flow index measures the rate at which thermoplastics are extruded through an orifice under specified temperature and load. In the test method, approximately 7 grams of material are loaded into a barrel of a melt flow apparatus that has been heated to a specified temperature for the material. A specified weight for the material is applied to the plunger, and the molten material is forced through the die. The extrudate is collected at timed intervals and weighed. The melt flow index value is calculated in cubic centimeters per 10 minutes or grams per 10 minutes.

[0473] Unless otherwise expressly stated, it is not intended that any method described herein require its steps to be performed in a particular order. Therefore, no order is intended to be inferred in any respect where a method claim does not actually describe the order in which its steps are followed, or where the claims or specification do not otherwise specifically state that these steps are restricted to a particular order. This applies to any possible non-express basis of interpretation, including: logical questions concerning the arrangement of steps or the flow of operations; simple meanings derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0474] definition

[0475] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will also be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having the meaning consistent with their meaning in the context of the specification and in the relevant field, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0476] As used herein, “comprising” is inclusive and is interpreted as specifying the presence of a feature, integer, step, or component as stated in the references, but does not preclude the presence or addition of one or more features, integers, steps, or components, or combinations thereof. Furthermore, each of the terms “by,” “comprising,” “comprises,” “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “included,” and “such as” is used in its open, non-restrictive sense and may be used interchangeably. Moreover, the term “comprising” is intended to include instances and aspects covered by the terms “consisting essentially of” and “consisting of.” Similarly, the term “essentially constitutes” is intended to include instances covered by the term “consisting of.”

[0477] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural indicators. Thus, for example, references to “foam particles,” “sole interlayer,” or “adhesive” include, but are not limited to, two or more such foam particles, sole interlayers, or adhesives.

[0478] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0479] As used herein, substantially means at least 50 percent, 60 percent, 75 percent, 90 percent, 95 percent or more, as determined based on weight or volume.

[0480] The terms first, second, third, etc., may be used herein to describe different elements, components, regions, layers, and / or segments. These elements, components, regions, layers, and / or segments should not be limited by these terms. These terms may be used only to distinguish one element, component, region, layer, or segment from another. Terms such as “first,” “second,” and other numerical terms do not imply sequence or order unless the context clearly indicates otherwise. Therefore, a first element, first component, first region, first layer, or first segment discussed below may be referred to as a second element, second component, second region, second layer, or second segment without departing from the teachings of the embodiment configuration.

[0481] As used herein, the modifiers “up,” “down,” “top,” “bottom,” “upward,” “downward,” “vertical,” “horizontal,” “longitudinal,” “lateral,” “front,” “back,” etc., unless otherwise defined or clearly stated from this disclosure, are relative terms referring to the various structures or orientations of footwear placed in the context of footwear worn by a user standing on a flat, horizontal surface.

[0482] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. Where a stated range contains one or both extreme values, the range excluding any one or both of those extreme values ​​is also included in this disclosure; for example, the phrase “x to y” includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. Ranges may also be expressed as upper limits, such as 'about x, y, z, or less' and should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'less than x', 'less than y', and 'less than z'. Similarly, the phrase 'about x, y, z, or greater' should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'greater than x', 'greater than y', and 'greater than z'. Furthermore, the phrase “about 'x' to 'y'”, where 'x' and 'y' are numerical values, includes “about 'x' to about 'y'”. It should be understood that this range format is used for convenience and brevity, and therefore should be interpreted flexibly to include not only the values ​​explicitly stated as extreme values ​​of the range, but also all individual values ​​or subranges covered within that range, as if each value and subrange were explicitly stated. For example, the range of numbers “about 0.1 percent to 5 percent” should be interpreted to include not only the explicitly stated values ​​of about 0.1 percent to about 5 percent, but also the individual values ​​(e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and subranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent, and 4.4 percent) within the indicated range.

[0483] As used herein, the terms “about,” “approximate,” “at or about,” and “generally” mean that the quantity or value in question can be an exact value or a value that provides an equivalent result or effect to that described in the claims or taught herein. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, resulting in an equivalent result or effect. In some cases, the value providing an equivalent result or effect cannot be reasonably determined. In such cases, it should generally be understood that, as used herein, “about” and “at or about” mean a nominal value indicated plus or minus 10 percent variation, unless otherwise indicated or inferred. Generally, quantities, sizes, formulations, parameters, or other quantities or characteristics are “about,” “approximately,” or “at or about,” whether or not explicitly stated as such. It should be understood that when “about,” “approximately,” or “in or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless otherwise specifically stated.

[0484] The reference to “a(a)” to a chemical compound refers to one or more molecules of the chemical compound, and is not limited to a single molecule of that chemical compound. Furthermore, the one or more molecules may or may not be identical, as long as they fall under the category of that chemical compound. Thus, for example, “a” polyamide is interpreted as including one or more polymer molecules of polyamide, wherein the polymer molecules may or may not be identical (e.g., different molecular weights and / or isomers).

[0485] The terms "at least one" and "one or more" are used interchangeably and have the same meaning, encompassing both single and multiple elements, and can also be indicated by a suffix (one or more) at the end of the element. For example, "at least one polyamide," "one or more polyamides," and "(one or more) polyamides" are used interchangeably and have the same meaning. Expressions such as "at least one of..." modify the entire list of elements when preceding it, without modifying any individual element within the list.

[0486] When used in the claims, the term "receive," such as in "receive uppers for footwear articles," is not intended to require any specific delivery or receipt of the received items. Rather, the term "receive" is used merely to describe items that will be referred to in subsequent elements of the claims for clarity and readability purposes.

[0487] As used herein, the interchangeable terms "percentage by weight," "weight percentage," "wt%," and "wt.%" indicate the weight percentage of a given component based on the total weight of the composition or article, unless otherwise indicated. That is, unless otherwise indicated, all weight percentage values ​​are based on the total weight of the composition. It should be understood that the sum of the weight percentage values ​​of all components in the disclosed composition or formulation equals 100. Similarly, the interchangeable terms "percentage by volume," "vol%," and "vol.%" indicate the volume percentage of a given component based on the total volume of the composition or article, unless otherwise indicated. That is, unless otherwise indicated, all volume percentage values ​​are based on the total volume of the composition or article. It should be understood that the sum of the volume percentage values ​​of all components in the disclosed composition, formulation, or article equals 100.

[0488] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the attachment point for a substituent. For example, -CHO is attached by the carbonyl group. Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0489] As used herein, the term "effective amount" refers to an amount sufficient to achieve the desired change in the physical properties of a composition or material. For example, the "effective amount" of a filler refers to an amount sufficient to achieve the desired improvement in properties regulated by the formulation components, such as achieving a desired modulus level. The specific level of the composition as an effective amount will depend on a variety of factors, including the amount and type of components, the amount and type of composition, and the end use of the article made using the composition.

[0490] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes both scenarios in which the event or situation occurs and scenarios in which the event or situation does not occur.

[0491] As used herein, the term "unit" can be used to refer to a single (co)monomer unit, such that, for example, a styrene repeating unit refers to a single styrene (co)monomer unit in the polymer. Furthermore, the term "unit" can be used to refer to a polymer block unit, such that, for example, "styrene repeating unit" can also refer to a polystyrene block; "polyethylene unit" refers to a polyethylene block unit; "polypropylene unit" refers to a polypropylene block unit; "polybutene unit" refers to a polybutene block unit, and so on. Such usage will be clear from the context.

[0492] The term "polymer" refers to a polymer having two or more monomeric substances, and includes terpolymers (i.e. copolymers having three monomeric substances).

[0493] Unless otherwise stated, the temperatures mentioned in this article are determined at standard atmospheric pressure (i.e., 1 atmosphere).

[0494] The components used to prepare the compositions of the present invention and the compositions themselves used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that while specific references cannot be explicitly disclosed for every variety of individual and collective combinations and arrangements of these materials, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and many modifications that can be made to a number of molecules including that compound are discussed, then each and every combination and arrangement of that compound, and possible modifications, are specifically contemplated unless otherwise specifically indicated. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and examples of the combination molecule AD are disclosed, then even though each is not described individually, each is considered to be a combination of meanings contemplated individually and collectively, and thus AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups of AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including but not limited to the steps in methods of making and using the compositions of the present invention. Therefore, if there are multiple additional steps that can be performed, it should be understood that each of these additional steps can be performed using any particular aspect or combination of aspects of the method of the present invention.

[0495] In this specification and concluding claims, references to specific elements or components in a composition or article indicate the weight relationship between that element or component and any other element or component in the composition or article whose weight parts are indicated. Therefore, in a compound comprising 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and in such a ratio regardless of whether other components are included in the compound.

[0496] As used herein, the term "alkyl group" refers to a branched or unbranched saturated hydrocarbon group with 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetradecyl, etc. "Lower alkyl" groups are alkyl groups containing 1 to 6 carbon atoms.

[0497] As used herein, the term "aryl group" refers to any carbon-based aromatic group, including but not limited to benzene, naphthalene, etc. The term "aromatic" also includes "heteroaryl group," which is defined as an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted by one or more groups, including but not limited to alkyl, alkynyl, alkenyl, aryl, halides, nitro, amino, esters, ketones, aldehydes, hydroxyl, carboxylic acids, or alkoxy groups.

[0498] As used herein, the term "aralkyl" refers to an aryl group having an alkyl group, alkynyl group, or alkenyl group as defined above attached to an aromatic group. An example of an aralkyl group is a benzyl group.

[0499] The term "organic residue" is defined as a carbon-containing residue, that is, a residue containing at least one carbon atom, and includes, but is not limited to, carbon-containing groups, residues, or groups defined above. Organic residues may contain various heteroatoms, or may be bonded to another molecule via heteroatoms, including oxygen, nitrogen, sulfur, phosphorus, etc. Examples of organic residues include, but are not limited to, alkyl or substituted alkyl groups, alkoxy or substituted alkoxy groups, monosubstituted or disubstituted amino groups, amide groups, etc. Organic residues may preferably contain 1 to 18 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Organic residues may contain 2 to 18 carbon atoms, 2 to 15 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

[0500] A very close synonym for the term "residue" is the term "radical," which, as used in the specification and concluding claims, refers to a fragment, group, or substructure of the molecule described herein, regardless of how the molecule is prepared. For example, the 2,4-dihydroxyphenyl group in a particular compound has the following structure:

[0501]

[0502] Regardless of whether 2,4-dihydroxyphenyl is used to prepare the compound, the group (e.g., alkyl) can be further modified (i.e., substituted alkyl) by having one or more "substituent groups" bonded to it. The number of atoms in a given group is not critical to the invention unless otherwise indicated herein.

[0503] As used in this article, the terms "number-average molecular weight" or "M" are used... n"These terms can be used interchangeably and refer to the statistical average molecular weight of all polymer chains in the sample, defined by the following formula:"

[0504]

[0505] Where M i It is the molecular weight of the chain, and N i This refers to the number of chains at that molecular weight. The M of a polymer, such as a polycarbonate polymer, can be determined using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards, by methods well known to those skilled in the art. n .

[0506] As will be seen from the foregoing, the aspects of this paper are well suited to achieving all the goals and objectives stated above, as well as other advantages that are evident and inherent to the structure.

[0507] It will be understood that certain features and sub-combinations are practical and can be employed without reference to other features and sub-combinations. This is contemplated by and within the scope of the claims.

[0508] Since many possible aspects can be made without departing from the scope of this document, it should be understood that everything stated herein or shown in the accompanying figures should be interpreted illustratively rather than in a restrictive sense.

[0509] While specific elements and steps are discussed in conjunction with each other, it should be understood that any element and / or step provided herein is contemplated as being combinable with any other element and / or step, whether expressly stated or not, and remains within the scope provided herein. Because many possible aspects can be formed by this disclosure without departing from its scope, it should be understood that all content stated herein or shown in the accompanying drawings is to be interpreted illustratively and not in a limiting sense. Example

[0510] Having described aspects of this disclosure, the following embodiments illustrate some additional aspects of this disclosure. While aspects of this disclosure have been described in conjunction with the following embodiments and the corresponding text and drawings, it is not intended to limit the aspects of this disclosure to this description. Rather, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of this disclosure.

[0511] The exemplary articles are manufactured using the methods and materials disclosed above (see [link]). Figures 14-16The component is made of foam particles prepared using a thermoplastic block copolyester containing crystalline (or hard) segments of polybutylene terephthalate and amorphous (or soft) segments of polyether (referred to herein as "thermoplastic COPE foam particles"). Figure 14 Articles comprising more than one attached foam particle are shown. The foam particles (referred to as "thermoplastic COPE foam particles") are prepared using a thermoplastic block copolyester comprising crystalline (or hard) segments containing polybutylene terephthalate and amorphous (or soft) segments containing polyether. The foam particles are arranged and attached in a series of layers, which are sintered to create four solid pier structures rising from the surface of the foam particle having a central cavity with highly sintered edges. Figure 15 and Figure 16 The sole interlayer of a shoe containing thermoplastic COPE foam particles is shown. Figure 15 The midsole layer in the shoe is immediately visible after production on the sintering platform, surrounded by loose, unsintered foam particles. After removing the unsintered foam particles, the cleaned midsole layer... Figure 16 As shown in the image.

[0512] It should be emphasized that the aspects described above in this disclosure are merely possible examples of implementation methods and are only presented for the purpose of clearly understanding the principles of this disclosure. Many variations and modifications can be made to the aspects described above without departing substantially from the spirit and principles of this disclosure. All such modifications and variations are intended to be included within the scope of this disclosure. This specification and embodiments are intended to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. An article comprising: A component formed of more than one attached foam particle, wherein each individual foam particle in the more than one attached foam particle is formed of a thermoplastic elastomer material and includes one or more bonding regions on the outer surface of the individual foam particle, the bonding regions attaching the individual foam particle to one or more adjacent foam particles, the one or more adjacent foam particles comprising thermoplastic elastomer material, the component formed of the more than one attached foam particle including more than one gap between the foam particles; wherein prior to attachment, the more than one foam particle has a number-average particle size of 0.04 mm to 10 mm in its longest dimension; and wherein a portion of the more than one attached foam particle of the component comprises a coating, or the surface of the component including a portion of the foam particle is embossed or embossed, or both, wherein the bonding region comprises a portion of the thermoplastic elastomer material from the surface of the individual foam particle, which is mixed with a portion of the thermoplastic elastomer material from the surface of the one or more adjacent foam particles.

2. The article of claim 1, wherein the gaps between the foam particles occupy at least 10% of the total volume of the component.

3. The article of claim 1, wherein, prior to attachment, at least 20% of the more than one foam particle is spherical or ellipsoidal in shape, and at least 20% of the spherical or ellipsoidal foam particles in the component retain a generally spherical or ellipsoidal shape.

4. The article of claim 1, wherein the more than one attached foam particle comprises layers of attached foam particles, and the average number of layers per millimeter in the component is from 0.1 layers per millimeter to 2.5 layers per millimeter.

5. The article of claim 4, wherein the average number of layers per millimeter in the component is from 0.3 layers per millimeter to 2 layers per millimeter.

6. The article of claim 1, wherein the component comprises layers of attached foam particles from 3 to 100 layers.

7. The article of claim 1, wherein the coating comprises ink, paint, dye, film or any combination thereof.

8. The article of claim 7, wherein the individual foam particles of the more than one attached foam particles of the component have a first color, and the coating has a second color different from the first color.

9. The article of claim 7, wherein each individual foam particle of the more than one attached foam particle of the component has a first color, and the coating has a second color different from the first color.

10. The article of claim 1, wherein the bonding region comprises a bonding material, a portion of the thermoplastic elastomer material from the individual foam particles, or a portion of the thermoplastic elastomer material from at least one of the one or more adjacent foam particles, or any combination thereof.

11. The article of claim 1, wherein the bonding region comprises a dissolved and resolidified thermoplastic elastomer material from the individual foam particles, from at least one of the one or more adjacent foam particles, or both.

12. The article of claim 1, wherein the bonding region comprises a dissolved and resolidified binder material from the individual foam particles, from at least one of the one or more adjacent foam particles, or both.

13. The article of claim 7, wherein at least one of the inks comprises a formulation containing an infrared radiation absorber.

14. The article according to claim 1, wherein, The coating of the portion of the foam particles includes printed markings on the outer surface of the article, and the article also includes a primer layer disposed between the outer surface of the article and the printed markings.

15. The article of claim 14, wherein the primer layer comprises pigment, dye, or both.

16. The article of claim 14, wherein the primer layer comprises a coating, an ink, or both.

17. The article of claim 15, wherein the primer layer comprises a re-ground and at least partially degraded polymer.

18. The article of claim 15, wherein the primer layer is in the form of a coating, wherein the coating of the primer layer comprises a polymer coating composition.

19. The article of claim 18, wherein the coating of the primer layer is a cross-linked coating comprising a cross-linked polymer matrix.

20. The article of claim 19, wherein the coating of the primer layer comprises more than one solid pigment particle embedded in the crosslinked polymer matrix.

21. The article of claim 1, wherein the article is characterized by more than one sub-region, the more than one sub-region comprising a first sub-region characterized by a first property and a second sub-region characterized by a second property, wherein the first property is not equal to the second property, and wherein the first property and the second property are flexural modulus, stiffness, bulk density or elasticity.

22. The article of claim 21, wherein the first property is at least 10% greater than the second property.

23. The article of claim 21, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first flexural modulus and a second sub-region characterized by a second flexural modulus, wherein the first flexural modulus is not equal to the second flexural modulus.

24. The article of claim 1, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first packing density and a second sub-region characterized by a second packing density, wherein the first packing density is not equal to the second packing density.

25. The article of claim 1, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first stiffness and a second sub-region characterized by a second stiffness, wherein the first stiffness is not equal to the second stiffness.

26. The article of claim 1, wherein the article is characterized by more than one cross-sectional sub-region, the more than one cross-sectional sub-region including a first sub-region characterized by a first elasticity and a second sub-region characterized by a second elasticity, wherein the first elasticity is not equal to the second elasticity.

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