阅读说明：本技术 可再循环的结构着色的结构和物品以及使结构和物品再循环的方法 (Recyclable structure colored structures and articles and methods of recycling structures and articles ) 是由 杰里米·甘茨 王袁敏 于 2020-03-11 设计创作，主要内容包括：在一个方面中,方法包括形成包括第一组合物的物品,所述第一组合物包含从约1重量百分比至约100重量百分比的再循环的热塑性组合物,该再循环的热塑性组合物包含第一热塑性材料和多于一个第一光学元件或其片段。其他方面包括通过该方法形成的物品、使结构着色的物品再循环的方法以及可再循环的结构着色的部件或物品。(In one aspect, a method includes forming an article comprising a first composition comprising from about 1 weight percent to about 100 weight percent of a recycled thermoplastic composition comprising a first thermoplastic material and more than one first optical element or fragment thereof. Other aspects include articles formed by the method, methods of recycling structurally colored articles, and recyclable structurally colored parts or articles.)

1. A method of forming an article, the method comprising:

forming a first article comprising a first composition, wherein the first composition comprises from about 1 weight percent to about 100 weight percent of a recycled thermoplastic composition, wherein the recycled thermoplastic composition comprises a first thermoplastic material and more than one first optical element or fragment thereof dispersed therein.

2. The method of claim 1, further comprising applying a second optical element to a side of the first article to impart a color to the side structure.

3. The method of claim 1, further comprising:

Converting a structurally colored second article into the recycled thermoplastic composition, wherein the structurally colored second article comprises the first thermoplastic material and the sides of the structurally colored second article have optical elements disposed thereon that impart a structural color to the sides.

4. The method of claim 1, wherein the first optical element and the fragments in the first composition do not impart an optical effect to the first article that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first article.

5. The method of claim 3, wherein:

the side of the second article having the optical element has a second minimum visible light transmittance or a second minimum visible light reflectance or both as measured in a visible light range having a wavelength from 400 to 700 nanometers; and is

The first article has a first minimum visible light transmittance or a first minimum visible light reflectance or both that is less than 40 percent of the second minimum visible light transmittance or the second minimum visible light reflectance or both, respectively.

6. The method of claim 3, wherein:

the side of the second article without the optical element has a third minimum visible light transmittance or a third minimum visible light reflectance or both as measured in a visible light range having a wavelength from 400 to 700 nanometers, and

the first article has a first minimum visible light transmittance or a first minimum visible light reflectance or both that is within about 10 percent of the third minimum visible light transmittance or the third minimum visible light reflectance or both, respectively.

7. The method of claim 3, wherein the converting step comprises: grinding the second article or part thereof; cutting the second article or portion thereof; melting the second article or a portion thereof; or a combination of the foregoing.

8. The method of claim 3, wherein the recycled thermoplastic composition is in solid or molten form.

9. The method of claim 3, wherein the recycled thermoplastic composition is in the form of pellets.

10. The method of claim 3, wherein the recycled thermoplastic composition comprises more than one segment of the second article.

11. The method of claim 1 or claim 3, further comprising mixing the recycled thermoplastic composition with an additional amount of the first thermoplastic material.

12. The method of claim 1 or claim 3, further comprising increasing the temperature of the recycled thermoplastic composition to a temperature above the softening point of the first thermoplastic material to provide a molten recycled thermoplastic composition.

13. The method of claim 1 or claim 3, wherein the first thermoplastic material comprises substantially no colorant.

14. The method of claim 1 or claim 3, wherein the first thermoplastic material comprises a colorant.

15. The method of claim 14, wherein the colorant imparts a second color to the second article in the absence of the optical element and imparts a first color to the first article, wherein the second color and the first color have one or more of the same hue, shade, or chroma.

16. The method of claim 1 or claim 3, wherein the method does not comprise altering, modifying, reducing, or removing a colorant.

17. The method of claim 1 or claim 3, wherein the recycled thermoplastic composition, the first composition, or both comprise from about 0.01 percent to about 20 percent of the first optical element or segment, respectively, based on the total weight of the recycled composition or the first composition.

18. The method of claim 1 or claim 3, wherein the more than one first optical element or segment comprises from about 1 percent to about 80 percent segments based on the total weight of the more than one optical element or segment.

19. A method according to claim 1 or claim 3, wherein the more than one first optical element or segment has an average size, measured along a largest dimension, of less than 400 nanometers.

20. The method of any one of claims 1 to 19, wherein the second article, the first article, or both are films or sheets.

Background

Structural color is caused by the physical interaction of light with micro-or nano-features of surfaces and bulk materials, in contrast to the color resulting from the presence of dyes or pigments that absorb or reflect light of a particular wavelength based on the chemical nature of the dye or pigment. Color from dyes and pigments can be problematic in many respects. For example, dyes and pigments and their related chemicals used in the manufacture and incorporation into textiles may not be environmentally friendly.

Brief Description of Drawings

In order that the disclosure may be better understood, its various forms, by way of example, will now be described with reference to the accompanying drawings, in which:

fig. 1A-1M illustrate footwear, apparel, athletic equipment, content (container), electronic equipment, and visual shield (vision wear) that include the optical elements of the present disclosure, while fig. 1N-1P illustrate additional details regarding different types of footwear.

Fig. 2A-2B illustrate side views of exemplary optical elements of the present disclosure.

Fig. 3 shows an image of an exemplary film structure comprising the recycled thermoplastic composition of the present disclosure compared to a control film structure.

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

Detailed Description

The present disclosure generally provides recyclable structurally colored articles and components that exhibit a structural color through the use of optical elements disposed on a thermoplastic material, wherein the structural color is a visible color produced at least in part by an optical effect imparted by the optical elements. The structural color imparts an aesthetically appealing color to the article, and when the structurally colored article or part is recycled, it produces a recycled thermoplastic composition having optical elements or segments thereof that impart substantially no optical effect, or significantly reduced optical effect. In particular embodiments, the recycled thermoplastic composition can be characterized by one or more of a visible light reflectance or visible light transmittance or color measurement that is within about 10 percent of the visible light reflectance or visible light transmittance or color measurement, respectively, of a similar composition without the optical element or segment.

The recycling of colored articles colored with one or more colorants (e.g., pigments and dyes) in thermoplastic materials or in coatings on thermoplastic materials produces recycled materials that retain the colorant unless additional steps are taken to remove the colorant from the recycled materials. The recycling of recycled material may require finding a suitable use for colored recycled material, such as applications where the build-up of colorant is tolerable, or alternatively require removal or modification of the colorant in the recycled material to form a recycled material with less color. In some cases, the colorant is not environmentally friendly, such that removal of the colorant presents additional handling and disposal problems.

In contrast, the compositions, components, and methods herein eliminate the need to reduce or remove colorants prior to recycling the recycled material. By recycling, the optical element that imparts the structural color to the article can be converted into a recycled optical element or segment of an optical element that degrades and does not retain the ability to produce the same optical effect as the original optical element. Thus, the recycled thermoplastic composition can be combined with another thermoplastic material with little or no effect on the reflectivity, light transmittance, or color of the thermoplastic material.

The present disclosure relates to a composition comprising a first thermoplastic material and more than one optical element or fragment thereof dispersed in the first thermoplastic material. The first thermoplastic material has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers that is within about 10 percent or about 5 percent of a second minimum visible light transmittance or a second minimum visible light reflectance, or both, respectively, of the composition. Optionally, the optical elements and segments are degraded and do not impart an optical effect to the composition. Optionally, the optical elements and segments do not impart an optical effect to the composition that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the composition.

Further, the present disclosure relates to a component comprising a first structure comprising recycled thermoplastic material and optionally at least about 1 percent by weight, or at least about 10 percent by weight, or 20 percent, or 25 percent, or 50 percent, or 75 percent of a second thermoplastic material. The recycled thermoplastic composition comprises a first thermoplastic material and more than one optical element or fragment thereof dispersed in the first thermoplastic material. The first structure has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers that is within about 10 percent or about 5 percent of a second minimum visible light transmittance or a second minimum visible light reflectance, or both, respectively, of a second structure comprising the first thermoplastic material but substantially free of optical elements or segments. Optionally, the optical elements and segments are degraded and do not impart optical effects to the component. Optionally, the optical elements and segments do not impart an optical effect to the component that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the component.

Further embodiments of the present disclosure relate to a colored or structurally colored part comprising a first structure comprising a first thermoplastic material and having an optical element disposed on a first side of the first structure. The optical element imparts a color to the first structure. The first structure has a recycled Optical Property difference (Recycle Optical Property difference) of greater than about 40 percent, or greater than about 50 percent, or greater than about 60 percent, or greater than about 70 percent. The recycling optical property difference, as further described herein, is a measure of the optical property (e.g., visible light transmittance, or visible light reflectance, or color measurement) measured before and after recycling. The recycling optical property difference can be calculated using the following formula:

additional embodiments of the present disclosure relate to a recycling method comprising converting a structurally colored first article into a recycled thermoplastic composition, wherein the structurally colored first article comprises a first thermoplastic material and the first side of the structurally colored article has disposed thereon an optical element imparting a structural color to the first side. The recycled thermoplastic composition comprises a first thermoplastic material and more than one optical element or fragment thereof dispersed therein. The method also includes forming a second article of a second composition, wherein the second composition comprises from about 1 weight percent to about 100 weight percent of the recycled thermoplastic composition, and optionally from about 1 weight percent to about 99 weight percent of a second thermoplastic material.

According to some methods, the converting step comprises: abrading a first article or portion thereof; cutting the first article or portion thereof; melting the first article or a portion thereof; or a combination of the foregoing. Optionally, the optical elements and fragments are degraded and do not impart an optical effect to the recycled thermoplastic composition, the second composition, or both. Optionally, the optical elements and segments do not impart an optical effect to the recycled thermoplastic composition or the second article, or both, that is visible to an observer having a visual acuity of 20/20 and normal color vision at a distance of about 1 meter from the recycled thermoplastic composition or the second article, or both.

According to some methods, the first side of the first article has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, as measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers; and the second article has a second minimum visible light transmittance or a second minimum visible light reflectance or both that is less than 40 percent or less than 20 percent, or less than 10 percent, or less than 5 percent of the first minimum visible light transmittance or the first minimum visible light reflectance, or both, respectively.

According to some methods, the first side of the first article without the optical element has a third minimum visible light transmittance or a third minimum visible light reflectance, or both, as measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers; and the second article has a second minimum visible light transmittance or a second minimum visible light reflectance or both that are within about 10 percent or within about 5 percent of a third minimum visible light transmittance or a third minimum visible light reflectance or both, respectively.

The present disclosure will be better understood upon reading the following numbered aspects, which should not be confused with the claims. In some cases, any of the following numbered aspects may be combined with aspects described elsewhere in the disclosure, and such combinations are intended to form part of the disclosure.

Aspect 1 a composition comprising:

a first thermoplastic material and more than one optical element or fragment thereof dispersed in the first thermoplastic material, wherein optionally the optical elements and fragments are degraded and do not impart an optical effect to the composition, or optionally the optical elements and fragments do not impart an optical effect to the composition that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the composition;

Wherein the first thermoplastic material has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, measured in terms of visible light having a wavelength from 400 nanometers to 700 nanometers that is within about 10 percent or about 5 percent of a second minimum visible light transmittance or a second minimum visible light reflectance, or both, respectively, of the composition.

The composition of aspect 2. the composition of aspect 1, wherein the composition is a recycled thermoplastic composition.

Aspect 3. the composition of any of the preceding aspects, further comprising a second thermoplastic material.

Aspect 4. the composition of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the second thermoplastic material is the same or substantially the same as the polymer component comprising all of the polymers present in the first thermoplastic material.

The composition of aspect 5. the composition of any of the preceding aspects, wherein the composition comprises at least 25 weight percent, or at least 50 weight percent, or at least 75 weight percent, or at least 90 weight percent, or at least 95 weight percent of the second thermoplastic material.

The composition of aspect 6. the composition of any of the preceding aspects, wherein the first minimum visible light transmittance or the second minimum visible light transmittance or both is at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent.

The composition of aspect 7. the composition of any of the preceding aspects, wherein the composition or the first thermoplastic material, or both, is substantially free of colorant, optionally wherein the thermoplastic material is substantially free of pigment or dye, or both.

Aspect 8. the composition of any of the preceding aspects, wherein the first thermoplastic material has a coordinate L when measured according to the CIE 1976 color space under given lighting conditions at a first observation angle between-15 degrees and +60 degrees₁A and a₁A and b₁A first color measurement, and the composition has a coordinate of L₂A and a₂A and b₂Second color measurement of, wherein Δ E between the first color measurement and the second color measurement_abLess than or equal to about 4, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Or optionally Δ E_abLess than or equal to about 3, or optionally less than or equal to about 2, or optionally less than or equal to about 1.

The composition of any of the preceding aspects, wherein the first composition comprises from about 0.01 percent to about 20 percent of the optical elements or segments, or from about 1 percent to about 10 percent of the optical elements or segments, based on the total weight of the first composition.

The composition of any of the preceding aspects, wherein the recycled thermoplastic composition comprises less than 20 weight percent, or less than 10 weight percent, or less than 5 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of optical elements or segments.

The composition of any of the preceding aspects, wherein the more than one optical element or segment comprises from about 1 percent to about 80 percent segments, or from about 10 percent to about 50 percent segments, based on the total weight of the more than one optical element or segment.

The composition of any of the preceding aspects, wherein more than one optical element or segment has an average size, as measured along the largest dimension, of less than 400 nanometers, optionally less than 300 nanometers, or less than 200 nanometers, or less than 100 nanometers.

The composition of any of the preceding aspects, wherein the first thermoplastic material or the second thermoplastic material, or both, comprises at least one thermoplastic polymer, optionally at least one thermoplastic elastomer.

The composition of any of the preceding aspects, wherein the at least one thermoplastic polymer comprises one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

The composition of aspect 15. the composition of any of the preceding aspects, wherein the first thermoplastic material or the second thermoplastic material or both comprise one or more thermoplastic polyurethanes.

The composition of aspect 16. the composition of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material or both comprises or consists essentially of a polyester polyurethane copolymer.

The composition of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyester.

The composition of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyether.

The composition of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers.

The composition of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate polymers or ethylene-vinyl alcohol polymers.

The composition of any of the preceding aspects, wherein the first thermoplastic material or the second thermoplastic material, or both, is substantially free of pigments or dyes, and optionally wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyurethane.

The composition of aspect 22. in any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the second thermoplastic material comprises or consists essentially of thermoplastic polyurethane, and the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a mixture of thermoplastic polyurethane and thermoplastic ethylene vinyl alcohol polymer.

Aspect 23. a method of making an article comprising forming an article using the composition of aspects 1 to 22.

Aspect 24. a component, comprising:

a first structure comprising a recycled thermoplastic composition and optionally at least about 1 percent by weight, or at least about 10 percent by weight, or 20 percent, or 25 percent, or 50 percent, or 75 percent of a second thermoplastic material;

wherein the recycled thermoplastic composition comprises a first thermoplastic material and more than one optical element or fragment thereof dispersed in the first thermoplastic material, wherein optionally the optical elements and fragments are degraded and do not impart an optical effect to the component, or optionally the optical elements and fragments do not impart an optical effect to the component or the composition or both, which optical effect is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the component; and is

Wherein the first structure has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers that is within about 10 percent or about 5 percent, respectively, of a second structure comprising the first thermoplastic material but substantially free of optical elements or segments.

Aspect 25 the component of any of the preceding aspects, wherein the recycled thermoplastic composition is the product of recycling a structure-pigmented article having a side, wherein the optical element is disposed on the side, and the side compositionally comprises the first thermoplastic material.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition comprises a milled, comminuted, shredded, cut or reflowed thermoplastic composition comprising optical elements or fragments thereof.

Aspect 27. a method of manufacturing an article comprising forming an article using the component of aspects 23 to 26.

Aspect 28. a component, comprising:

a first structure comprising a first composition;

wherein the first composition comprises a recycled thermoplastic composition and optionally at least about 1 percent by weight, or at least about 10 percent by weight, or 20 percent by weight, or 25 percent by weight, or 50 percent by weight, or 75 percent of a second thermoplastic material;

wherein the recycled thermoplastic composition is the recycled product of a structurally colored article compositionally comprising a first thermoplastic material and having optical elements that impart a structural color to the structurally colored article; and is

Wherein the first structure has a first minimum visible light transmittance or a first minimum visible light reflectance, or both, measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers that is within about 10 percent or about 5 percent, respectively, of a second structure comprising the first thermoplastic material but substantially free of optical elements or segments.

Aspect 29. the component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the second thermoplastic material is the same or substantially the same as the polymer component comprising all of the polymers present in the first thermoplastic material.

The component of any of the preceding aspects, wherein recycling comprises melting the structurally colored article or portion thereof and forming a molten recycled thermoplastic composition comprising the molten first thermoplastic material and more than one optical element or fragment thereof dispersed in the molten first thermoplastic material, wherein optionally the optical elements and fragments are degraded and do not impart an optical effect to the component, or optionally the optical elements and fragments do not impart an optical effect to the component or the composition, or both, which optical effect is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the component.

The component of any of the preceding aspects, wherein recycling comprises grinding, shredding, or cutting the structurally colored article or portion thereof, and melting the ground, shredded, or cut portion of the structurally colored article.

The component of any of the preceding aspects, wherein recycling comprises curing the molten recycled thermoplastic composition into a solid recycled thermoplastic composition.

The component of any of the preceding aspects, wherein recycling comprises extruding and solidifying the molten recycled thermoplastic composition into pellets.

The component of any of the preceding aspects, wherein recycling comprises injection molding and curing the molten recycled thermoplastic composition to form the component.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition comprises at least 25 weight percent, or at least 50 weight percent, or at least 75 weight percent, or at least 90 weight percent, or at least 95 weight percent of the first thermoplastic material.

Aspect 36. the component of any of the preceding aspects, wherein the first minimum visible light transmittance or the second minimum visible light transmittance or both is at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition or the second thermoplastic material, or both, is substantially free of colorant, optionally wherein the recycled thermoplastic composition or the second thermoplastic material, or both, is substantially free of pigment or dye, or both.

The component of any of the preceding aspects, wherein the first structure has a coordinate L when measured according to CIE 1976 color space at a first viewing angle between-15 degrees and +60 degrees under given lighting conditions₁A and a₁A and b₁A first color measurement of, and a second structure having coordinates L₂A and a₂A and b₂Second color measurement of, wherein Δ E between the first color measurement and the second color measurement_abLess than or equal to about 4, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Or optionally Δ E_abLess than or equal to about 3, or optionally less than or equal to about 2, or optionally less than or equal to about 1.

The component of any of the preceding aspects, wherein the first structure is a film or sheet.

Aspect 40 the component of any of the preceding aspects, wherein the structurally colored article comprises a container, an article of apparel, an article of footwear, an article of sports or recreational equipment, an article of recreation, an article of outdoor recreation, an article of education, a home decoration or ornament, an article of electronic equipment, an article of construction, or any component thereof, or any material produced or assembled therefrom.

The component of any of the preceding aspects, wherein the component comprises a container, an article of apparel, an article of footwear, an article of sports or recreational equipment, an article of entertainment, an outdoor entertainment article, an educational article, a home decoration or ornament, an article of electronic equipment, an article of construction, or any component thereof, or any material produced or assembled therefrom.

Aspect 42. the component of any one of the preceding aspects, wherein the contents comprise a bag, a bottle, a liquid receptacle, a package, a backpack, a suitcase, or a component thereof.

Aspect 43 the component of any one of the preceding aspects, wherein the sporting or recreational articles comprise sporting equipment, protective equipment, locomotive equipment, fishing equipment, hunting equipment, camping equipment, or a component thereof.

Aspect 44. the component of any of the preceding aspects, wherein the sporting or amusement article comprises a bat, racket, stick, club, golf club, paddle, striking device, ball, puck, golf bag, baseball glove, football glove, soccer ball restriction structure, mat, helmet, shield, visor, bicycle, motorcycle, skateboard, car, truck, boat, surfboard, ski, snowboard, sail, parachute, or a component thereof.

Aspect 45. the component of any of the preceding aspects, wherein the entertainment item comprises a toy, a gaming machine, or a component thereof.

Aspect 46. the component of any of the preceding aspects, wherein the article of apparel comprises a shirt, a jersey, pants, shorts, gloves, socks, a hat, a cap, a jacket, underwear, eye shields, a timepiece, jewelry, or a component thereof.

Aspect 47. the component of any one of the preceding aspects, wherein the home decoration or ornament comprises a decorative item for furniture, a bedding item, a tablecloth, a towel, a curtain, a banner, or a component thereof.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition does not impart an optical effect to the component, wherein the optical effect is a structural color, an iridescent appearance, or a metallic appearance.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition does not impart a structural color to the component.

The component of any of the preceding aspects, wherein the first structure exhibits no structural color.

The component of any of the preceding aspects, wherein the component further comprises an optical element disposed on at least one side of the first structure, and the optical element imparts a color to the component structure when disposed on the first structure.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition comprises from about 0.01 percent to about 20 percent of the optical elements or segments, or from about 1 percent to about 10 percent of the optical elements or segments, based on the total weight of the first composition.

The component of any of the preceding aspects, wherein the recycled thermoplastic composition comprises less than 20 weight percent, or less than 10 weight percent, or less than 5 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of the optical elements or segments.

The component of any of the preceding aspects, wherein the more than one optical element or segment comprises from about 1 percent to about 80 percent segments, or from about 10 percent to about 50 percent segments, based on the total weight of the more than one optical element or segment.

The component of any of the preceding aspects, wherein more than one optical element or segment has an average size, as measured along the largest dimension, of less than 400 nanometers, optionally less than 300 nanometers, or less than 200 nanometers, or less than 100 nanometers.

The component of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material or both comprises at least one thermoplastic polymer, optionally at least one thermoplastic elastomer.

The component of any of the preceding aspects, wherein the polymer component comprising all polymers present in the at least one thermoplastic polymer comprises one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

The component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises one or more thermoplastic polyurethanes.

The component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material or both comprises or consists essentially of a polyester polyurethane copolymer.

Aspect 60. the component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyester.

Aspect 61 the component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyether.

The component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers.

The component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate or ethylene-vinyl alcohol polymers.

The component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyurethane.

Aspect 65. the component of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the second thermoplastic material comprises or consists essentially of thermoplastic polyurethane, and the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a mixture of thermoplastic polyurethane and thermoplastic ethylene vinyl alcohol polymer.

The component of any of the preceding aspects, wherein the optical element is a coating on a side of the structurally colored article.

Aspect 67. the component of any of the preceding aspects, wherein the optical element of the structurally colored article comprises more than one optical layer.

Aspect 68. the component of any of the preceding aspects, wherein the optical element of the structurally colored article comprises a single layer reflector, a single layer filter, a multilayer reflector, a multilayer filter, or a combination thereof.

Aspect 69 the component of any of the preceding aspects, wherein the optical element of the structurally colored article has at least two optical layers, including at least two adjacent layers having different refractive indices.

Aspect 70. the component of any of the preceding aspects, wherein at least one of the layers of the optical element of the structurally colored article has a thickness that is about one quarter of the wavelength of visible light to be reflected by the optical element to produce the structural color.

The component of any of the preceding aspects, wherein at least one of the layers of the optical element of the structurally colored article comprises a material selected from the group consisting of: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, and combinations thereof.

The component of any of the preceding aspects, further comprising a textured surface on the first side of the optical element of the structurally colored article.

Aspect 73. the component of any of the preceding aspects, wherein the textured surface has more than one contour feature and more than one flat region.

The component of any of the preceding aspects, wherein the textured surface comprises more than one contour feature and a planar region that is flat, wherein the contour feature extends over the planar region of the textured surface.

The component of any of the preceding aspects, wherein the size of the contour features, the shape of the contour features, the spacing between more than one contour feature, and the optical layer combine to impart a color to the structure.

The component of any of the preceding aspects, wherein the contour features are at random positions relative to each other over an area of the textured surface having a surface area of at least 5 square millimeters.

The component of any of the preceding aspects, wherein the spacing between the contour features reduces distortion effects resulting from the contour features interfering with one another when imparting a structural color to the structurally colored article.

The component of any of the preceding aspects, wherein the profile features and the planar regions result in at least one optical layer of the optical element having an undulating topology, wherein the optical layer has planar regions between adjacent depressions and/or projections that are planar with the planar regions of the textured surface.

Aspect 79. the component of any of the preceding aspects, wherein the structurally colored article comprises a first side and the optical element is disposed on at least a portion of the first side.

Aspect 80 the component of any of the preceding aspects, wherein the structural color of the structurally colored article is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first structure.

The component of any of the preceding aspects, wherein the structural color of the structurally colored article has a single hue.

The component of any of the preceding aspects, wherein the structural color of the structurally colored article comprises two or more hues.

The component of any of the preceding aspects, wherein the structural color of the structurally colored article has a single or multi-colored appearance.

Aspect 84. the component of any of the preceding aspects, wherein the optical elements disposed on the structurally colored article impart a structural color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L ₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b₃The coordinate values may be the same or different, and a combined therein₁Value, a₂Value sum a₃The range of values is less than about 40% of the total range of possible a values, optionally less than about 30% of the total range of possible a values, optionally less than about 20% of the total range of possible a values, or optionally less than about 10% of the total range of possible a values.

Aspect 85. the component of any of the preceding aspects, wherein the optical elements disposed on the structurally colored article impart a structural color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L ₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b₃Coordinate values may be the same or different, and wherein b is combined₁Value, b₂Value and b₃The range of values is less than about 40% of the total range of possible b values, optionally less than about 30% of the total range of possible b values, optionally less than about 20% of the total range of possible b values, or optionally 10% of the total range of possible b values.

Aspect 86. the component of any of the preceding aspects, wherein the optical elements disposed on the structurally colored article impart a structural color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at two viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurementOf magnitude, wherein L₁Value sum L₂The values may be the same or different, wherein a₁Coordinate values and a₂Coordinate values may be the same or different, wherein b₁Coordinate values and b ₂The coordinate values may be the same or different, and wherein Δ E between the first and second color measurements_abLess than or equal to about 100, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Optionally less than or equal to about 80, or optionally less than or equal to about 60.

The component of any of the preceding aspects, wherein the optical elements disposed on the structurally colored article impart a structural color having a coordinate L when measured according to CIELCH color space at three viewing angles between-15 degrees and +60 degrees under given lighting conditions₁A and C₁A and h₁A first viewing angle of DEG has a first color measurement and has a coordinate L₂A and C₂A and h₂A second viewing angle of DEG has a second color measurement and has a coordinate L₃A and C₃A and h₃A third observation angle of DEG has a third color measurement value, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein C₁Coordinate value, C₂Coordinate values and C₃The coordinate values may be the same or different, wherein h₁Coordinate value of degree, h₂Coordinate value of DEG and h₃The coordinate values may be the same or different, and h in combination therein₁Value of degree, h₂Value of and h₃The range of values is less than about 60 degrees, optionally less than about 50 degrees, optionally less than about 40 degrees, optionally less than about 30 degrees, or optionally less than about 20 degrees.

Aspect 88. the component of any of the preceding aspects, wherein the structural color of the structurally colored article is iridescent.

The component of any of the preceding aspects, wherein the structural color has a limited iridescence.

Aspect 90. the component of any of the preceding aspects, wherein the structural color is not iridescent.

The component of any of the preceding aspects, wherein the structural colors have limited iridescence such that when each color visible at each possible viewing angle is assigned to a single color phase selected from the group consisting of primary, secondary and tertiary colors on a red-yellow-blue (RYB) color wheel, all assigned hues fall into a single color phase group, wherein the single color phase group is one of the following: a) green yellow, yellow and yellow-orange; b) yellow, yellow-orange and orange; c) yellow-orange, orange and orange-red; d) orange red and magenta; e) red, magenta and violet; f) magenta, purple and violet blue; g) violet, violet-blue and blue; h) violet, blue and blue-green; i) blue, cyan and green; and j) cyan, green, and lime.

The component of any of the preceding aspects, wherein the structural color with limited iridescence is limited to two or three of: green yellow, yellow orange hue; or the hues violet blue, blue and blue-green; or the hues orange red, red and magenta; or the hues cyan, green, and greenish yellow; or the hues yellow orange, orange and red-orange; or the hues magenta, purple and violet blue.

Aspect 93. a method of manufacturing an article comprising forming an article using the component of aspects 28 to 92.

Aspect 94. a structural colored part, comprising:

a first structure comprising a first thermoplastic material and having an optical element disposed on a first side of the first structure; wherein the optical element imparts a color to the first structure; and is

Wherein the first structure has a difference in recycled optical properties greater than about 40 percent, or greater than about 50 percent, or greater than about 60 percent, or greater than about 70 percent.

Aspect 95 the structurally colored part of any one of the preceding aspects wherein the first structure is a film or sheet.

Aspect 96 the structurally colored component of any one of the preceding aspects, wherein the structurally colored component comprises a container, an article of apparel, an article of footwear, an article of athletic or recreational equipment, an entertainment article, an outdoor entertainment article, an educational article, a home decoration or ornament, an article of electronic equipment, an article of construction, or any component thereof, or any material produced or assembled therefrom.

Aspect 97 the structurally colored component of any of the preceding aspects wherein the contents comprise a bag, bottle, liquid receptacle, package, backpack, suitcase, or component thereof.

Aspect 98. the structurally colored component of any one of the preceding aspects, wherein the sporting or recreational articles comprise sporting equipment, protective equipment, locomotive equipment, fishing equipment, hunting equipment, camping equipment, or a component thereof.

Aspect 99. the structural colored part of any of the preceding aspects, wherein the sporting or amusement article comprises a bat, racket, stick, club, golf club, paddle, striking device, ball, hockey, golf bag, baseball glove, soccer ball restriction structure, mat, helmet, guard, visor, face mask, visor, bicycle, motorcycle, skateboard, automobile, truck, boat, surfboard, ski, snowboard, sail, parachute, or a part thereof.

Aspect 100. the structural colored part of any of the preceding aspects, wherein the entertainment item comprises a toy, a gaming machine, or a part thereof.

Aspect 101. the structurally colored component of any one of the preceding aspects, wherein the article of apparel comprises a shirt, a jersey, pants, shorts, gloves, socks, hat bands, caps, jackets, undergarments, eye shields, watches, jewelry, or a component thereof.

Aspect 102. the structural colored component of any of the preceding aspects, wherein the home decoration or adornment comprises a decorative item for furniture, bedding, tablecloth, towel, curtain, banner, or a component thereof.

Aspect 103 the structurally colored part of any of the preceding aspects, wherein the first thermoplastic material comprises substantially no colorant, optionally wherein the first thermoplastic material is substantially free of pigment or dye, or both.

Aspect 104 the structurally colored part of any one of the preceding aspects, wherein the first thermoplastic material comprises a colorant, optionally wherein the first thermoplastic material comprises a pigment or a dye or both.

Aspect 105 the structurally colored component of any of the preceding aspects wherein the colorant imparts a first color to the first structure in the absence of an optical element.

The structurally colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises at least one thermoplastic polymer, optionally at least one thermoplastic elastomer.

Aspect 107. the structurally colored part of any one of the preceding aspects, wherein the polymer component comprising all polymers present in the at least one thermoplastic polymer comprises one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

The structurally colored part of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises one or more thermoplastic polyurethanes.

Aspect 109. the structurally colored part of any one of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a polyester polyurethane copolymer.

Aspect 110 the structurally colored part of any one of the preceding aspects wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyester.

Aspect 111 the structurally colored part of any one of the preceding aspects wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyether.

Aspect 112 the structurally colored part of any one of the preceding aspects wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers.

Aspect 113 the structurally colored part of any one of the preceding aspects wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material or both comprises or consists essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate or ethylene-vinyl alcohol polymers.

Aspect 114. the structurally colored part of any one of the preceding aspects wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyurethane.

Aspect 115. the structurally colored component of any one of the preceding aspects, wherein the optical element is a coating on the first side of the first structure.

Aspect 116. the structurally colored component of any of the preceding aspects, wherein the optical element comprises more than one optical layer.

Aspect 117 the structurally colored component of any one of the preceding aspects, wherein the optical element comprises a single layer reflector, a single layer filter, a multilayer reflector, a multilayer filter, or a combination thereof.

The structurally colored component of any of the preceding aspects, wherein the optical element has at least two optical layers, including at least two adjacent layers having different refractive indices.

Aspect 119. the structurally colored component of any of the preceding aspects, wherein at least one of the layers of the optical element has a thickness that is about one quarter of a wavelength of visible light to be reflected by the optical element to produce the structural color.

Aspect 120 the structurally colored component of any of the preceding aspects, wherein at least one of the layers of the optical element comprises a material selected from the group consisting of: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, and combinations thereof.

Aspect 121 the structurally colored component of any of the preceding aspects, further comprising a textured surface on the first side of the optical element.

The structurally colored component of any of the preceding aspects, wherein the textured surface has more than one contour feature and more than one flat region.

The structurally colored component of any of the preceding aspects, wherein the textured surface comprises more than one contour feature and a planar region, wherein the contour features extend over the planar region of the textured surface.

The structurally colored component of any of the preceding aspects, wherein the size of the contour features, the shape of the contour features, the spacing between more than one contour feature, and the optical layer combine to impart a color to the structure.

Aspect 125 the structurally colored component of any of the preceding aspects wherein the contour features are in random positions relative to each other over an area of the textured surface having a surface area of at least 5 square millimeters.

Aspect 126. the structural colored part of any of the preceding aspects, wherein the spacing between the contour features reduces distortion effects resulting from the contour features interfering with each other when imparting a structural color to the structural colored part.

The structurally colored component of any of the preceding aspects, wherein the contour features and the planar regions result in at least one optical layer of the optical element having an undulating topology, wherein the optical layer has planar regions between adjacent depressions and/or projections that are planar to the planar regions of the textured surface.

Aspect 128. the structural colored component of any of the preceding aspects, wherein the structural color of the first structure is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first structure.

The structurally colored part of any of the preceding aspects wherein the structural color of the first structure has a single hue.

Aspect 130. the structurally colored part of any of the preceding aspects wherein the structural color of the first structure comprises two or more hues.

Aspect 131 the structural colored part of any of the preceding aspects, wherein the structural color of the first structure has a single or multi-colored appearance.

Aspect 132. the structurally colored component of any one of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b ₁Coordinate value, b₂Coordinate values and b₃The coordinate values may be the same or different, and a combined therein₁Value, a₂Value sum a₃The range of values is less than about 40% of the total range of possible a values, optionally less than the total number of possible a valuesAbout 30% of the range, optionally less than about 20% of the total range of possible a values, or optionally less than about 10% of the total range of possible a values.

Aspect 133. the structurally colored component of any of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b ₃Coordinate values may be the same or different, and wherein b is combined₁Value, b₂Value and b₃The range of values is less than about 40% of the total range of possible b values, optionally less than about 30% of the total range of possible b values, optionally less than about 20% of the total range of possible b values, or optionally 10% of the total range of possible b values.

Aspect 134 the structurally colored component of any one of the preceding aspects wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIE 1976 color space at two viewing angles between-15 degrees and +60 degrees under given lighting conditions₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle of has a second color measurement, wherein L₁Value sum L₂The values may be the same or different, wherein a₁Coordinate values and a₂Coordinate values may be the same or different, wherein b₁Coordinate values and b₂The coordinate values may be the same or different, and wherein Δ E between the first and second color measurements_abLess than or equal to about 100, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Optionally less than or equal to about 80, or optionally less than or equal to about 60.

Aspect 135. the structurally colored component of any of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIELCH color space at three viewing angles between-15 degrees and +60 degrees under given lighting conditions₁A and C₁A and h₁A first viewing angle of DEG has a first color measurement and has a coordinate L₂A and C₂A and h₂A second viewing angle of DEG has a second color measurement and has a coordinate L₃A and C₃A and h₃A third observation angle of DEG has a third color measurement value, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein C₁Coordinate value, C₂Coordinate values and C₃The coordinate values may be the same or different, wherein h₁Coordinate value of degree, h₂Coordinate value of DEG and h₃The coordinate values may be the same or different, and h in combination therein₁Value of degree, h₂Value of and h₃The range of values is less than about 60 degrees, optionally less than about 50 degrees, optionally less than about 40 degrees, optionally less than about 30 degrees, or optionally less than about 20 degrees.

Aspect 136. the structural colored component of any of the preceding aspects, wherein the structural color of the first structure is iridescent.

The structurally colored component of any of the preceding aspects, wherein the structural color has limited iridescence.

Aspect 138. the structurally colored component of any of the preceding aspects, wherein the structural color is not iridescent.

Aspect 139 a structurally colored component as in any of the preceding aspects, wherein the structural colors have limited iridescence such that when each color visible at each possible viewing angle is assigned to a single color phase selected from the group consisting of primary, secondary and tertiary colors on a red-yellow-blue (RYB) color wheel, all assigned hues fall into a single color phase group, wherein the single color phase group is one of: a) green yellow, yellow and yellow-orange; b) yellow, yellow-orange and orange; c) yellow-orange, orange and orange-red; d) orange red and magenta; e) red, magenta and violet; f) magenta, purple and violet blue; g) violet, violet-blue and blue; h) violet, blue and blue-green; i) blue, cyan and green; and j) cyan, green, and lime.

Aspect 140. the structural colored component of any of the preceding aspects, wherein the structural color with limited iridescence is limited to two or three of: green yellow, yellow orange hue; or the hues violet blue, blue and blue-green; or the hues orange red, red and magenta; or the hues cyan, green, and greenish yellow; or the hues yellow orange, orange and red-orange; or the hues magenta, purple and violet blue.

Aspect 141 a method of manufacturing an article comprising forming an article using a structurally colored part of any of aspects 94 to 140.

Aspect 142. a colored part, comprising:

a first structure comprising a first thermoplastic material and having a visible color;

wherein the first structure has a difference in recycled optical properties greater than about 40 percent, or greater than about 50 percent, or greater than about 60 percent, or greater than about 70 percent.

Aspect 143. the colored part of any one of the preceding aspects, wherein the first structure is a film or a sheet.

Aspect 144 the colored part of any of the preceding aspects, wherein the visible color is a structural color.

Aspect 145 the colored part of any of the preceding aspects, wherein the first structure comprises an optical element disposed on the first side of the first structure, and the optical element imparts a color to the colored part structure.

Aspect 146. the colored part of any one of the preceding aspects, wherein the part comprises a container, an article of apparel, an article of footwear, an article of sports or recreational gear, an article of entertainment, an outdoor entertainment article, an educational article, a home decoration or ornament, an article of electronic equipment, an article of construction, or any part thereof, or any material produced or assembled therefrom.

Aspect 147. the colored part of any one of the preceding aspects, wherein the contents comprise a bag, a bottle, a liquid receptacle, a package, a backpack, a suitcase, or a part thereof.

Aspect 148. the colored component of any one of the preceding aspects, wherein the sporting or recreational item comprises sporting equipment, protective equipment, locomotive equipment, fishing equipment, hunting equipment, camping equipment, or a component thereof.

Aspect 149. the colored part of any one of the preceding aspects, wherein the sporting or amusement article comprises a bat, racket, stick, club, golf club, paddle, striking device, ball, hockey, golf bag, baseball glove, football glove, soccer ball restriction structure, mat, helmet, guard, visor, goggle, bicycle, motorcycle, skateboard, automobile, truck, boat, surfboard, ski, snowboard, sail, parachute, or a part thereof.

Aspect 150. the colored part of any one of the preceding aspects, wherein the entertainment item comprises a toy, a gaming machine, or a part thereof.

Aspect 151. the colored component of any one of the preceding aspects, wherein the article of apparel comprises a shirt, a jersey, pants, shorts, gloves, socks, a hat, a cap, a jacket, underwear, eye shields, a timepiece, jewelry, or a component thereof.

Aspect 152. the colored part of any one of the preceding aspects, wherein the home decoration or ornament comprises a decorative item for furniture, a bedding item, a tablecloth, a towel.

Aspect 153. the colored part of any of the preceding aspects, wherein the first thermoplastic material comprises substantially no colorant, optionally wherein the first thermoplastic material comprises substantially no pigment or dye, or both.

Aspect 154. the colored part of any of the preceding aspects, wherein the first thermoplastic material comprises a colorant, optionally wherein the first thermoplastic material comprises a pigment or a dye, or both.

Aspect 155 the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises at least one thermoplastic polymer, optionally at least one thermoplastic elastomer.

Aspect 156. the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the at least one thermoplastic polymer comprises one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

Aspect 157. the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises one or more thermoplastic polyurethanes.

Aspect 158 the colored part of any one of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises or consists essentially of a polyester polyurethane copolymer.

Aspect 159. the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyester.

Aspect 160. the colored part of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyether.

Aspect 161. the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material comprises or consists essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers.

Aspect 162. the colored part of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material or both comprises or consists essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate or ethylene-vinyl alcohol polymers.

Aspect 163. the colored part of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a thermoplastic polyurethane.

Aspect 164. the colored part of any of the preceding aspects, wherein the optical element is a coating on the first side of the first structure.

Aspect 165. the colored part of any of the preceding aspects, wherein the optical element comprises more than one optical layer.

Aspect 166. the colored component of any of the preceding aspects, wherein the optical element comprises a single layer reflector, a single layer filter, a multilayer reflector, a multilayer filter, or a combination thereof.

Aspect 167 the colored component of any of the preceding aspects, wherein the optical element has at least two optical layers, including at least two adjacent layers having different refractive indices.

Aspect 168. the colored component of any of the preceding aspects, wherein at least one of the layers of the optical element has a thickness that is about one quarter of a wavelength of visible light to be reflected by the optical element to produce the structural color.

Aspect 169 the colored part of any one of the preceding aspects, wherein at least one of the layers of the optical element comprises a material selected from the group consisting of: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, and combinations thereof.

Aspect 170. the colored component of any of the preceding aspects, further comprising a textured surface on the first side of the optical element.

The painted component of any of the preceding aspects, wherein the textured surface has more than one contour feature and more than one flat area.

The colored component of any of the preceding aspects, wherein the textured surface comprises more than one contour feature and a planar region that is flat, wherein the contour features extend above the planar region of the textured surface.

Aspect 173. the colored part of any of the preceding aspects, wherein the size of the contour features, the shape of the contour features, the spacing between more than one contour feature, and the optical layer combine to impart a color to the structure.

Aspect 174. the colored component of any of the preceding aspects, wherein the contour features are in random positions relative to each other over an area of the textured surface having a surface area of at least 5 square millimeters.

The colored component of any of the preceding aspects, wherein the spacing between the contour features reduces distortion effects resulting from the contour features interfering with one another when imparting a structural color to the first structure.

Aspect 176. the colored component of any of the preceding aspects, wherein the contour features and the planar regions result in at least one optical layer of the optical element having an undulating topology, wherein the optical layer has planar regions between adjacent depressions and/or projections that are planar with the planar regions of the textured surface.

The colored component of any of the preceding aspects, wherein the structural color of the first structure is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first structure.

The colored part of any of the preceding aspects, wherein the structural color of the first structure has a single hue.

Aspect 179. the colored part of any of the preceding aspects, wherein the structural color of the first structure comprises two or more hues.

Aspect 180. the colored part of any of the preceding aspects, wherein the structural color of the first structure has a monochromatic or polychromatic appearance.

Aspect 181. the colored component of any of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b ₁Coordinate value, b₂Coordinate values and b₃The coordinate values may be the same or different, and a combined therein₁Value, a₂Value sum a₃The range of values is less than about 40% of the total range of possible a values, optionally less than about 30% of the total range of possible a values, optionally less than about 20% of the total range of possible a values, or optionally less than about 10% of the total range of possible a values. The colored part of any of the preceding aspects, wherein a colored layer is disposedThe optical elements on the first structure impart a structural color having a coordinate L when measured according to the CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b₃Coordinate values may be the same or different, and wherein b is combined ₁Value, b₂Value and b₃The range of values is less than about 40% of the total range of possible b values, optionally less than about 30% of the total range of possible b values, optionally less than about 20% of the total range of possible b values, or optionally 10% of the total range of possible b values.

Aspect 183. the colored part of any of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIE 1976 color space at two viewing angles between-15 degrees and +60 degrees under given lighting conditions₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle of has a second color measurement, wherein L₁Value sum L₂The values may be the same or different, wherein a₁Coordinate values and a₂Coordinate values may be the same or different, wherein b₁Coordinate values and b₂The coordinate values may be the same or different, and wherein Δ E between the first and second color measurements_abLess than or equal to about 100, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Optionally less than or equal to about 80, or optionally less than or equal to about 60.

Aspect 184. the colored part of any of the preceding aspects, wherein the optical elements disposed on the first structure impart a structure color having a coordinate L when measured according to CIELCH color space at three viewing angles between-15 degrees and +60 degrees under given lighting conditions ₁A and C₁A and h₁A first viewing angle of DEG has a first color measurement and has a coordinate L₂A and C₂A and h₂A second viewing angle of DEG has a second color measurement and has a coordinate L₃A and C₃A and h₃A third observation angle of DEG has a third color measurement value, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein C₁Coordinate value, C₂Coordinate values and C₃The coordinate values may be the same or different, wherein h₁Coordinate value of degree, h₂Coordinate value of DEG and h₃The coordinate values may be the same or different, and h in combination therein₁Value of degree, h₂Value of and h₃The range of values is less than about 60 degrees, optionally less than about 50 degrees, optionally less than about 40 degrees, optionally less than about 30 degrees, or optionally less than about 20 degrees.

Aspect 185. the colored component of any of the preceding aspects, wherein the structural color of the first structure is iridescent.

Aspect 186. the colored component of any of the preceding aspects, wherein the structural color has limited iridescence.

Aspect 187. the colored part of any of the preceding aspects, wherein the structural color is not iridescent.

Aspect 188. the colored component of any of the preceding aspects, wherein the structural colors have limited iridescence such that when each color visible at each possible viewing angle is assigned to a single color phase selected from the group consisting of primary, secondary, and tertiary colors on a red-yellow-blue (RYB) color wheel, all assigned hues fall into a single color phase group, wherein the single color phase group is one of: a) green yellow, yellow and yellow-orange; b) yellow, yellow-orange and orange; c) yellow-orange, orange and orange-red; d) orange red and magenta; e) red, magenta and violet; f) magenta, purple and violet blue; g) violet, violet-blue and blue; h) violet, blue and blue-green; i) blue, cyan and green; and j) cyan, green, and lime.

Aspect 189 a colored component as described in any of the preceding aspects, wherein the structural color with limited iridescence is limited to two or three of: green yellow, yellow orange hue; or the hues violet blue, blue and blue-green; or the hues orange red, red and magenta; or the hues cyan, green, and greenish yellow; or the hues yellow orange, orange and red-orange; or the hues magenta, purple and violet blue.

Aspect 190. a method of manufacturing an article, comprising forming an article using the colored component of any of aspects 142-189.

An aspect 191. a method of recycling, the method comprising:

converting the structurally colored first article into a recycled thermoplastic composition, wherein the structurally colored first article comprises a first thermoplastic material and the first side of the structurally colored article has disposed thereon an optical element imparting a structural color to the first side;

wherein the recycled thermoplastic composition comprises a first thermoplastic material and more than one optical element or fragment thereof dispersed therein, wherein optionally the optical elements and fragments are degraded and do not impart an optical effect to the composition, or optionally wherein the optical elements and fragments do not impart an optical effect to the composition that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the composition; and

Forming a second article of a second composition, wherein the second composition comprises from about 1 weight percent to about 100 weight percent of the recycled thermoplastic composition, and optionally from about 1 weight percent to about 99 weight percent of a second thermoplastic material, optionally wherein the optical elements and segments in the composition do not impart an optical effect to the second article that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the second article.

Aspect 192. the method of any of the preceding aspects, wherein

The first side of the first article has a first minimum visible light transmittance or a first minimum visible light reflectance or both as measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers; and is

The second article has a second minimum visible light transmittance or a second minimum visible light reflectance or both that is less than 40 percent or less than 20 percent, or less than 10 percent, or less than 5 percent of the first minimum visible light transmittance or the first minimum visible light reflectance, or both, respectively.

Aspect 193 the method of any of the preceding aspects, wherein

The first side of the first article without the optical element has a third minimum visible light transmittance or a third minimum visible light reflectance, or both, as measured in a visible light range having a wavelength from 400 nanometers to 700 nanometers; and is

The second article has a second minimum visible light transmittance or a second minimum visible light reflectance or both that are within about 10 percent or within about 5 percent of a third minimum visible light transmittance or a third minimum visible light reflectance or both, respectively.

The method of any of the preceding aspects, wherein the second article has a second minimum visible light transmittance of at least 10 percent, or at least 20 percent, or at least 40 percent, or at least 60 percent, or at least 80 percent.

Aspect 195. the method of any of the preceding aspects, wherein the converting step comprises: abrading a first article or portion thereof; cutting the first article or portion thereof; melting the first article or a portion thereof; or a combination of the foregoing.

Aspect 196 the method of any of the preceding aspects, wherein the recycled thermoplastic composition is in solid or molten form.

Aspect 197. the method of any of the preceding aspects, wherein the recycled thermoplastic composition is in the form of pellets, optionally extruded pellets.

The method of any of the preceding aspects, wherein the recycled thermoplastic composition comprises more than one segment of the first article.

Aspect 199. the method of any of the preceding aspects, further comprising mixing the recycled thermoplastic composition with an additional amount of the first thermoplastic material or with the optional second thermoplastic material, or both.

The method of any of the preceding aspects, further comprising increasing the temperature of the recycled thermoplastic composition to a temperature above the softening point of the first thermoplastic material to provide a molten recycled thermoplastic composition.

Aspect 201. the method of any of the preceding aspects, wherein the first article of structural coloration is a film or sheet.

Aspect 202. the method of any of the preceding aspects, wherein the structurally colored first article comprises a container, an article of apparel, an article of footwear, an article of athletic or recreational equipment, an entertainment article, an outdoor entertainment article, an educational article, a home decoration or ornament, an article of electronic equipment, an article of construction, or any component thereof, or any material produced or assembled therefrom.

Aspect 203. the method of any of the preceding aspects, wherein the contents comprise a bag, a bottle, a liquid receptacle, a package, a backpack, a suitcase, or a component thereof.

Aspect 204. the method of any of the preceding aspects, wherein the sporting or amusement article comprises sporting equipment, protective equipment, locomotive equipment, fishing equipment, hunting equipment, camping equipment, or a component thereof.

Aspect 205. the method of any one of the preceding aspects, wherein the sporting or amusement article comprises a bat, racket, stick, club, golf club, paddle, striking device, ball, puck, golf bag, baseball glove, football glove, soccer ball restriction structure, mat, helmet, guard, visor, goggle, bicycle, motorcycle, skateboard, automobile, truck, boat, surfboard, ski, snowboard, sail, parachute, or a component thereof.

Aspect 206. the method of any of the preceding aspects, wherein the entertainment item comprises a toy, a gaming machine, or a component thereof.

Aspect 207 the method of any of the preceding aspects, wherein the article of apparel comprises a shirt, a jersey, pants, shorts, gloves, socks, a hat, a cap, a jacket, underwear, eye shields, a timepiece, jewelry, or a component thereof.

Aspect 208. the method of any of the preceding aspects, wherein the home decoration or adornment comprises a decorative item for furniture, a bedding item, a tablecloth, a towel, a curtain, a banner, or a component thereof.

Aspect 209. the method of any of the preceding aspects, wherein the first thermoplastic material comprises substantially no colorant, optionally wherein the first thermoplastic material comprises substantially no pigment or dye, or both.

Aspect 210 the method of any of the preceding aspects, wherein the first thermoplastic material comprises a colorant, optionally wherein the first thermoplastic material comprises a pigment or a dye, or both.

The method of any of the preceding aspects, wherein the method does not comprise altering, modifying, reducing, or removing a colorant.

Aspect 212. the method of any of the preceding aspects, wherein the colorant imparts a first color to the first article in the absence of the optical element and imparts a second color to the second article, wherein the first color and the second color have one or more of the same hue, value, or chroma.

Aspect 213. the method of any of the preceding aspects, wherein the first article without optical elements has a coordinate L when measured according to CIE 1976 color space at a first viewing angle between-15 degrees and +60 degrees under given lighting conditions ₁A and a₁A and b₁First color measurement and second article having coordinates L₂A and a₂A and b₂Second color measurement of, wherein Δ E between the first color measurement and the second color measurement_abLess than or equal to about 4, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^1/2Or optionally Δ E_abLess than or equal to about 3, or optionally less than or equal to about 2, or optionally less than or equal to about 1.

Aspect 214. the method of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material or both comprises at least one thermoplastic polymer, optionally at least one thermoplastic elastomer.

Aspect 215 the method of any of the preceding aspects, wherein the polymer component comprising all polymers present in the at least one thermoplastic polymer comprises one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

The method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises one or more thermoplastic polyurethanes.

Aspect 217. the method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material or both comprises or consists essentially of a polyester polyurethane copolymer.

Aspect 218. the method of any one of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyester.

Aspect 219 the method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyether.

The method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers.

Aspect 221. the method of any of the preceding aspects, wherein the polymer component comprising all polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate or ethylene-vinyl alcohol polymers.

The method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the first thermoplastic material or the second thermoplastic material, or both, comprises or consists essentially of a thermoplastic polyurethane.

Aspect 223 the method of any of the preceding aspects, wherein the polymer component comprising all of the polymers present in the second thermoplastic material comprises or consists essentially of thermoplastic polyurethane, and the polymer component comprising all of the polymers present in the first thermoplastic material comprises or consists essentially of a mixture of thermoplastic polyurethane and thermoplastic ethylene vinyl alcohol polymer.

The method of any of the preceding aspects, wherein the optical element of the structurally colored first article comprises more than one optical layer.

Aspect 225 the method of any of the preceding aspects, wherein the optical element of the structurally colored first article comprises a single layer reflector, a single layer filter, a multilayer reflector, a multilayer filter, or a combination thereof.

Aspect 226. the method of any of the preceding aspects, wherein the optical element of the structurally colored first article has at least two optical layers, including at least two adjacent layers having different refractive indices.

Aspect 227 the method of any of the preceding aspects, wherein at least one of the layers of the optical element of the structurally colored first article comprises a material selected from the group consisting of: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, and combinations thereof.

Aspect 228. the method of any of the preceding aspects, further comprising a textured surface on the first side of the optical element of the first article of structural coloration.

The method of any of the preceding aspects, wherein the textured surface has more than one contour feature and more than one flat region.

The method of any of the preceding aspects, wherein the textured surface includes more than one contour feature and a planar region that is flat, wherein the contour feature extends over the planar region of the textured surface.

The method of any of the preceding aspects, wherein the size of the contour feature, the shape of the contour feature, the spacing between more than one contour feature, and the optical layer combine to impart a color to the structure.

The method of any of the preceding aspects, wherein the contour features are in random positions relative to each other over a region of the textured surface having a surface area of at least 5 square millimeters.

Aspect 233. the method of any of the preceding aspects, wherein the spacing between the profile features reduces distortion effects that the profile features interfere with each other when imparting a structural color to the first article to which the structure is colored.

The method of any of the preceding aspects, wherein the profile features and the planar regions result in at least one optical layer of the optical element having an undulating topology, wherein the optical layer has planar regions between adjacent depressions and/or projections that are planar with the planar regions of the textured surface.

The method of any of the preceding aspects, wherein the recycled thermoplastic composition comprises more than one optical segment in solid or molten form.

The method of any of the preceding aspects, wherein the recycled thermoplastic composition comprises less than 20 weight percent, or less than 10 weight percent, or less than 5 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of optical elements or segments.

The method of any of the preceding aspects, wherein the second composition comprises from about 0.01 percent to about 20 percent of the optical elements or segments, or from about 1 percent to about 10 percent of the optical elements or segments, based on the total weight of the second composition.

The method of any of the preceding aspects, wherein the more than one optical element or segment comprises from about 1 percent to about 80 percent segments, or from about 10 percent to about 50 percent segments, based on the total weight of the more than one optical element or segment.

Aspect 239 the method of any of the preceding aspects, wherein more than one optical element or segment has an average size, as measured along the largest dimension, of less than 400 nanometers, optionally less than 300 nanometers, or less than 200 nanometers, or less than 100 nanometers.

Aspect 240 the method of any of the preceding aspects, wherein the structural color of the first article is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first structure.

Aspect 241 the method of any of the preceding aspects, wherein the structural color of the first article has a single hue.

The method of any of the preceding aspects, wherein the structural color of the first article comprises two or more hues.

The method of any of the preceding aspects, wherein the structural color of the first article has a monochromatic or polychromatic appearance.

Aspect 244. the method of any of the preceding aspects, wherein the optical elements disposed on the first article impart a structure color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at three viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L ₁Value, L₂Value sum L₃The values may be the same or different, wherein a₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b₃The coordinate values may be the same or different, and a combined therein₁Value, a₂Value sum a₃The range of values is less than about 40% of the total range of possible a values, optionally less than about 30% of the total range of possible a values, optionally less than about 20% of the total range of possible a values, or optionally less than about 10% of the total range of possible a values.

Aspect 245 the method of any of the preceding aspects, wherein the optical element disposed on the first article imparts a color to the structure when the color is according to CIE 1976The structure color has a coordinate L when measured at three observation angles between-15 degrees and +60 degrees under given illumination conditions₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle has a second color measurement and has a coordinate L₃A and a₃A and b₃The third observation angle of has a third color measurement, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein a ₁Coordinate value, a₂Coordinate values and a₃Coordinate values may be the same or different, wherein b₁Coordinate value, b₂Coordinate values and b₃Coordinate values may be the same or different, and wherein b is combined₁Value, b₂Value and b₃The range of values is less than about 40% of the total range of possible b values, optionally less than about 30% of the total range of possible b values, optionally less than about 20% of the total range of possible b values, or optionally 10% of the total range of possible b values.

Aspect 246. the method of any of the preceding aspects, wherein the optical element disposed on the first article imparts a structure color having a coordinate L when measured according to CIE 1976 color space under given lighting conditions at two viewing angles between-15 degrees and +60 degrees₁A and a₁A and b₁The first observation angle has a first color measurement and has a coordinate L₂A and a₂A and b₂The second observation angle of has a second color measurement, wherein L₁Value sum L₂The values may be the same or different, wherein a₁Coordinate values and a₂Coordinate values may be the same or different, wherein b₁Coordinate values and b₂The coordinate values may be the same or different, and wherein Δ E between the first and second color measurements _abLess than or equal to about 100, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Optionally less than or equal to about 80, or optionally less than or equal to about 60.

Aspect 247. the method of any of the preceding aspects, wherein the optical elements disposed on the first article impart a structure color having a coordinate L when measured according to CIELCH color space at three viewing angles between-15 degrees and +60 degrees under given lighting conditions₁A and C₁A and h₁A first viewing angle of DEG has a first color measurement and has a coordinate L₂A and C₂A and h₂A second viewing angle of DEG has a second color measurement and has a coordinate L₃A and C₃A and h₃A third observation angle of DEG has a third color measurement value, wherein L₁Value, L₂Value sum L₃The values may be the same or different, wherein C₁Coordinate value, C₂Coordinate values and C₃The coordinate values may be the same or different, wherein h₁Coordinate value of degree, h₂Coordinate value of DEG and h₃The coordinate values may be the same or different, and h in combination therein₁Value of degree, h₂Value of and h₃The range of values is less than about 60 degrees, optionally less than about 50 degrees, optionally less than about 40 degrees, optionally less than about 30 degrees, or optionally less than about 20 degrees.

Aspect 248. the method of any of the preceding aspects, wherein the structural color of the first article is iridescent.

Aspect 249. the method of any of the preceding aspects, wherein the structural color of the first article has limited iridescence.

Aspect 250. the method of any of the preceding aspects, wherein the structural color of the first article is not iridescent.

Aspect 251 the method of any one of the preceding aspects, wherein the structural color of the first article has limited iridescence such that when each color visible at each possible viewing angle is assigned to a single color phase selected from the group consisting of primary, secondary and tertiary colors on a red-yellow-blue (RYB) color wheel, all assigned hues fall into a single color phase group, wherein the single color phase group is one of: a) green yellow, yellow and yellow-orange; b) yellow, yellow-orange and orange; c) yellow-orange, orange and orange-red; d) orange red and magenta; e) red, magenta and violet; f) magenta, purple and violet blue; g) violet, violet-blue and blue; h) violet, blue and blue-green; i) blue, cyan and green; and j) cyan, green, and lime.

Aspect 252. the method of any of the preceding aspects, wherein the structural color with limited iridescence is limited to two or three of: green yellow, yellow orange hue; or the hues violet blue, blue and blue-green; or the hues orange red, red and magenta; or the hues cyan, green, and greenish yellow; or the hues yellow orange, orange and red-orange; or the hues magenta, purple and violet blue.

The method of any of the preceding aspects, wherein the second article exhibits no structural color.

Aspect 254 the method of any of the preceding aspects, further comprising disposing an optical element on a side of the second article, wherein the optical element imparts a structural color to the second article.

Aspect 255. a structure comprising a second article manufactured according to the method of any of aspects 191-254.

Aspect 256. the method, component, color component, structurally colored component, structure, and/or article of any of the preceding aspects, wherein the article is a fiber.

Aspect 257. the method and/or article of any one of the preceding aspects, wherein the article is a yarn.

Aspect 258. the method and/or article of any of the preceding aspects, wherein the article is a monofilament yarn.

Aspect 259. the method and/or article of any of the preceding aspects, wherein the article is a textile.

Aspect 260. the method and/or article of any of the preceding aspects, wherein the article is a knitted textile.

Aspect 261. the method and/or article of any of the preceding aspects, wherein the article is a non-woven textile.

Aspect 262. the method and/or article of any of the preceding aspects, wherein the article is a non-woven synthetic leather.

Aspect 263. the method and/or article of any of the preceding aspects, wherein the article is a film.

The method and/or article of any of the preceding aspects, wherein the article is an article of footwear, a component of footwear, an article of apparel, a component of apparel, an article of athletic equipment, or a component of athletic equipment.

Aspect 265. the method and/or article of any of the preceding aspects, wherein the article is an article of footwear.

Aspect 266. the method and/or article of any of the preceding aspects, wherein the article is a sole component of an article of footwear.

Aspect 267. the method and/or article of any of the preceding aspects, wherein the article is an upper component of an article of footwear.

Aspect 268. the method and/or article of any of the preceding aspects, wherein the article is a knitted upper component of an article of footwear.

Aspect 269. the method and/or article of any of the preceding aspects, wherein the article is a non-woven synthetic leather upper for an article of footwear.

Aspect 270. the method and/or article of any of the preceding aspects, wherein the article is a bladder comprising a volume of fluid, wherein the bladder has a first bladder wall having a first bladder wall thickness, wherein the first bladder wall has a 15cm to nitrogen average wall thickness of 20 mils ³/m²Atm · day or less.

Aspect 271. the method and/or article of any of the preceding aspects, wherein the article is a capsule and the inorganic optical elements are optionally on an inner surface of the capsule, or optionally the inorganic optical elements are on an outer surface of the capsule.

Aspect 272. the method and/or article of any of the preceding aspects, wherein each of the component layers and the reflective layer is a three-dimensional planar surface or a substantially three-dimensional planar surface.

The article and/or method of any of the preceding aspects, wherein the contour features have at least one dimension greater than 500 microns and optionally greater than about 600 microns.

Aspect 274 the article and/or method of any of the preceding aspects, wherein at least one of the length and width of the contour feature is greater than 500 micrometers, or optionally both the length and width of the contour feature are greater than 500 micrometers.

Aspect 275 the article and/or method of any one of the preceding aspects, wherein the height of the contour feature can be greater than 50 microns or optionally greater than about 60 microns.

Aspect 276 the article and/or method of any of the preceding aspects, wherein at least one of the length and width of the contour feature is less than 500 microns, or both the length and width of the contour feature are less than 500 microns and the height is greater than 50 microns.

Aspect 277 the article and/or method of any of the preceding aspects, wherein at least one of the length and width of the contour feature is greater than 500 microns, or both the length and width of the contour feature are greater than 500 microns and the height is greater than 50 microns.

Aspect 278 the article and/or method of any one of the preceding aspects, wherein at least one dimension of the topographical features is in the nanometer range and at least one other dimension is in the micrometer range.

The article and/or method of any of the preceding aspects, wherein the nanometers range from about 10 nanometers to about 1000 nanometers and the micrometers range from about 5 micrometers to 500 micrometers.

Aspect 280 the article and/or method of any of the preceding aspects, wherein at least one of the length and width of the profile feature is in the nanometer range and the other of the length and width of the profile feature is in the micrometer range.

The aspect 281 the article and/or method of any of the preceding aspects, wherein the height of the topographical features is greater than 250 nanometers.

Aspect 282 the article and/or method of any of the preceding aspects, wherein at least one of the length and width of the contour feature is in the nanometer range, and the other is in the micrometer range, wherein the height is greater than 250 nanometers.

Aspect 283 the article and/or method of any one of the preceding aspects, wherein the spatial orientation of the contour features is periodic.

The article and/or method of any of the preceding aspects, wherein the spatial orientation of the contour features is a semi-random pattern or a defined pattern.

Aspect 285 the article and/or method of any one of the preceding aspects, wherein the surface of the layer of inorganic optical elements is a substantially three-dimensionally planar surface or a three-dimensionally planar surface.

Aspect 286. a method of forming an article, the method comprising: forming a first article comprising a first composition, wherein the first composition comprises from about 1 weight percent to about 100 weight percent of a recycled thermoplastic composition, wherein the recycled thermoplastic composition comprises a first thermoplastic material and more than one first optical element or fragment thereof dispersed therein.

Aspect 287 the method of any of the preceding aspects, further comprising applying a second optical element to a side of the first article to impart a color to the side structure.

The method of any of the preceding aspects, further comprising: converting the structurally colored second article into a recycled thermoplastic composition, wherein the structurally colored second article comprises the first thermoplastic material and the sides of the structurally colored second article have optical elements disposed thereon that impart a structural color to the sides.

Aspect 289 the method of any of the preceding aspects, wherein the first optical element and the fragments in the first composition do not impart an optical effect to the first item that is visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the first item.

The method of any of the preceding aspects, wherein: the side of the second article having the optical element has a second minimum visible light transmittance or a second minimum visible light reflectance or both as measured in a visible light range having a wavelength from 400 to 700 nanometers; and the first article has a first minimum visible light transmittance or a first minimum visible light reflectance or both that is less than 40 percent of a second minimum visible light transmittance or a second minimum visible light reflectance or both, respectively.

The method of any one of the preceding aspects, wherein: the side of the second article without the optical element has a third minimum visible light transmittance or a third minimum visible light reflectance or both as measured in a visible light range having a wavelength from 400 to 700 nanometers; and the first article has a first minimum visible light transmittance or a first minimum visible light reflectance or both that are within about 10 percent of a third minimum visible light transmittance or a third minimum visible light reflectance or both, respectively.

Aspect 292 the method of any one of the preceding aspects, wherein the converting step comprises: grinding the second article or part thereof; cutting the second article or part thereof; melting the second article or a portion thereof; or a combination of the foregoing.

The method of any of the preceding aspects, wherein the recycled thermoplastic composition is in solid or molten form; optionally in the form of pellets.

Aspect 294. the method of any of the preceding aspects, wherein the recycled thermoplastic composition comprises more than one segment of the second article.

Aspect 295. the method of any of the preceding aspects, further comprising mixing the recycled thermoplastic composition with an additional amount of the first thermoplastic material.

Aspect 296. the method of any of the preceding aspects, further comprising increasing the temperature of the recycled thermoplastic composition to a temperature above the softening point of the first thermoplastic material to provide a molten recycled thermoplastic composition.

Aspect 297 the method of any of the preceding aspects, wherein the first thermoplastic material comprises substantially no colorant.

The method of any of the preceding aspects, wherein the first thermoplastic material comprises a colorant.

The method of any of the preceding aspects, wherein the colorant imparts a second color to the second article in the absence of the optical element and imparts a first color to the first article, wherein the second color and the first color have one or more of the same hue, shade, or chroma.

The method of any of the preceding aspects, wherein the method does not comprise altering, modifying, reducing, or removing a colorant.

The method of any of the preceding aspects, wherein the recycled thermoplastic composition, the first composition, or both comprise from about 0.01 percent to about 20 percent of the first optical element or segment, respectively, based on the total weight of the recycled composition or the first composition.

The aspect 302. the method of any of the preceding aspects, wherein the more than one first optical element or segment comprises from about 1 percent to about 80 percent segments based on the total weight of the more than one first optical element or segment.

Aspect 303 the method of any of the preceding aspects, wherein the more than one first optical element or segment has an average size, measured along a largest dimension, of less than 400 nanometers.

Aspect 304. the method of any of the preceding aspects, wherein the second article, the first article, or both are films or sheets.

Having now generally described aspects of the present disclosure, additional discussion regarding the aspects will be described in more detail.

The present disclosure is not limited to the particular aspects described and, thus, may, of course, vary. The terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting, as the scope of the present disclosure will be limited only by the appended claims.

When a range of values is provided, each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where a stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

It will be apparent to those skilled in the art upon reading this disclosure that each of the various aspects described and illustrated herein has discrete components and features that may be readily separated from or combined with the features of any of the other several aspects without departing from the scope or spirit of the present disclosure. Any recited method may be performed in the order of the recited events or in any other order that is logically possible.

Unless otherwise indicated, aspects of the present disclosure will employ techniques of material science, chemistry, weaving, polymer chemistry, and the like, which are within the skill of the art. Such techniques are explained fully in the literature.

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

As used in the specification and the appended claims, the singular forms "a", "an" and "the" may include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a support" includes more than one support.

As used herein, the phrases "consisting essentially of … … (of) or" consisting essentially of … … (of) "in the context of a composition or thermoplastic means that the composition or thermoplastic may vary from the recited composition in a manner that does not substantially affect the functional properties of the recited composition or thermoplastic. Examples of changes that do not substantially affect the functional properties of the composition or thermoplastic material include contaminants, impurities, and the like.

As used herein, "comprising" should be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps or components, or groups thereof. Furthermore, each of the terms "by", "including", "comprises", "comprising", "including", "comprises", "including", "included", "including", "involving", and "such as" are used in their open, non-limiting sense and may be used interchangeably. Furthermore, the term "comprising" is intended to include the examples and aspects encompassed by the terms "consisting essentially of … …" and "consisting of … …". Similarly, the term "consisting essentially of … …" is intended to include the example covered by the term "consisting of … …".

When a range is expressed, additional aspects include from the one particular value and/or to the other particular value. For example, where the stated range includes one or both of the extremes, ranges excluding either or both of those included extremes are also included in the disclosure, e.g., the phrase "x to y" includes ranges from 'x' to 'y' as well as ranges greater than 'x' and less than 'y'. Ranges can also be expressed as upper limits, e.g., 'about x, y, z, or less' and should be interpreted to include specific ranges of 'about x', 'about y', and 'about z' as well as ranges of 'less than x', 'less than y', and 'less than z'. Likewise, the phrase 'about x, y, z or greater' should be construed to include specific ranges of 'about x', 'about y', and 'about z' as well as ranges of 'greater than x', 'greater than y', and 'greater than z'. Further, the phrase "about 'x' to 'y'", where 'x' and 'y' are numerical values, includes "about 'x' to about 'y'".

It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For purposes of this specification, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and sub-ranges (e.g., about 0.5% to about 1.1%, about 5% to about 2.4%, about 0.5% to about 3.2%, and about 0.5% to about 4.4%, as well as other possible sub-ranges) within the indicated range.

As used herein, the terms "about (about)", "about (approximate)", "at (at) or about" and "substantially" mean that the amount or value in question may be an exact value or a value that provides an equivalent result or effect to that recited in the claims or taught herein. That is, it is to be understood that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art so that an equivalent result or effect is obtained. In some cases, values that provide equivalent results or effects cannot be reasonably determined. In such cases, it will generally be understood that, as used herein, "about" and "at or about" mean a variation of the indicated nominal value of ± 10%, unless otherwise indicated or inferred. Generally, an amount, size, formulation, parameter, or other quantity or characteristic is "about", or "at or about", whether or not explicitly stated to be so. It is understood that where "about," "approximately," or "at or about" is used before a quantitative value, a parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

As used herein, in the context of a composition, the phrase "substantially the same" means that the composition has from about 80% to 100% of the same ingredients as the recited reference composition. For example, a first composition is substantially identical to a second composition if it comprises at least 99% or at least 98% or at least 97% or at least 96% or at least 95% or at least 94% or at least 93% or at least 92% or at least 91% or at least 90% or at least 89% or at least 88% or at least 87% or at least 86% or at least 85% or at least 84% or at least 83% or at least 82% or at least 81% or at least 80% of the same ingredients as the second composition.

As used herein, the term "optional" or "optionally" means that the subsequently described feature may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

In this specification and the claims which follow, reference will be made to a number of terms which shall be defined to have certain meanings unless a contrary intention is apparent.

The present disclosure provides compositions, components, and articles described as recyclable. As used herein, "recyclable" refers to the ability of an article or component thereof to be reprocessed and entered into a recycling stream without compromising the suitability of the composition comprising the recycled material for further use in later manufacturing applications and/or processing.

The present disclosure provides methods of recycling articles and parts to produce recycled thermoplastic compositions, and also provides methods of producing articles and parts using recycled thermoplastic compositions. Although the term recycle may be used to describe many different acts of reusing or reusing something, as used herein, the term "recycle" refers to physical reprocessing of thermoplastic materials (e.g., by grinding, cutting, shredding, melting, re-extruding, etc.) to form recycled thermoplastic compositions. As used herein, "recycled" material (e.g., recycled composition) refers to material that has been recovered from previous use and processed into a suitable form for further use in a later manufacturing application and/or process.

In one aspect, the present disclosure relates to structurally colored components and articles. A structurally colored part or article includes at least a first side comprising a thermoplastic material and having an optical element disposed thereon. The optical element disposed on the first side imparts a structural color to the component or article. When the structurally colored part or article is recycled, the resulting recycled thermoplastic composition, including the optical element or fragment thereof, as described herein, and the part or article formed from the recycled thermoplastic composition, no longer exhibit a visible structural color.

Structurally colored articles may include post-consumer goods or packaging, as well as factory trim (factory trim) and waste to manufacture or assemble such goods or packaging. By way of example, a structurally colored part may include a container, an article of apparel, an article of footwear, an article of athletic or recreational equipment, an article of entertainment, an outdoor entertainment article, an educational article, a home decoration or ornament, an article of electronic equipment, an article of construction, or any part thereof, or any material produced or assembled therefrom.

The article of manufacture may comprise a content, such as a bag, bottle, liquid receptacle, package, backpack, suitcase, or the like. The article of manufacture may comprise sporting or recreational equipment, including sporting equipment, protective equipment, locomotive equipment, fishing equipment, hunting equipment, camping equipment, or the like. The sporting object or item of play equipment may comprise, for example, a bat, racket, stick, club, golf club, paddle, striking device, ball, hockey, golf bag, baseball glove, football glove, soccer ball restriction structure, mat, helmet, shield, visor, bicycle, motorcycle, skateboard, car, truck, boat, surfboard, ski, snowboard, sail, parachute, or the like. The items for entertainment may include toys, game machines, or the like. The article of apparel may include a shirt, jersey, pants, shorts, gloves, socks, hat bands, caps, jackets, undergarments, eye shields, clocks, jewelry, or the like. The home decoration or adornment may include a decorative article for furniture, bedding, a tablecloth, a towel, a curtain, a banner, or the like.

In particular embodiments, the article may be an article of footwear. The article of footwear may be designed for a variety of uses, such as athletic use, military use, work-related use, recreational use, or recreational use. Primarily, the article of footwear is intended for outdoor use on unpaved surfaces (partially or wholly), such as on ground surfaces including one or more of grass, turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether as athletic performance surfaces or as general outdoor surfaces. However, the article of footwear may also be desirable for indoor applications, such as, for example, indoor sports that include a dirt playing surface (e.g., indoor baseball fields with dirt infields).

The article of footwear may be designed for indoor or outdoor athletic activities, such as international football (football)/soccer (soccer), golf, american football, rugby, baseball, running, track and field, cycling (e.g., road cycling and mountain cycling), and similar athletic activities. The article of footwear may optionally include traction elements (e.g., lugs, cleats, studs and cleats, and tread patterns) to provide traction on soft and smooth surfaces, wherein the article of the present disclosure may be used or applied between or among traction elements, and optionally on the sides of the traction elements but on the surface of the traction elements that contacts the ground or surface. Cleats, spikes, and nails are commonly included in footwear designed for sports such as international/soccer, golf, american football, rugby, baseball, and the like, which are often performed on unpaved surfaces. Lugs and/or enhanced tread patterns are typically included in footwear, including boots designed for use in harsh outdoor conditions, such as cross-country running, hiking, and military use.

The article may be an article of apparel (i.e., a garment). The article of apparel may be an article of apparel designed for athletic or leisure activities. The article of apparel may be an article of apparel designed to provide protection from elements (e.g., wind and/or rain) or from impact.

The article may be an item of sports equipment. The article of athletic equipment may be designed for indoor or outdoor athletic activities, such as international/soccer, golf, american football, rugby, baseball, running, track and field, cycling (e.g., road and mountain biking), and the like.

Fig. 1A-1M illustrate footwear, apparel, athletic equipment, content, electronic equipment, and visual protection that include structures (e.g., inorganic optical elements) of the present disclosure. The structure including the inorganic optical element is represented by the hashed regions 12A '/12M ' -12A "/12M '. The location of the structure is provided merely to indicate one possible area where the structure may be located. Further, two locations are illustrated in some figures and one location is illustrated in other figures, but this is for illustration purposes only, as the article may comprise one or more structures, where size and location may be determined based on the article. The structure located on each article may represent a number, letter, symbol, design, logo, graphical indicia, icon, trademark, or the like.

Fig. 1n (a) and 1n (b) illustrate perspective and side views of an article of footwear 100 that includes a sole structure 104 and an upper 102. Structures including inorganic optical elements are denoted by 122a and 122 b. Sole structure 104 is secured to upper 102 and sole structure 104 extends between the foot and the ground when article of footwear 100 is worn. The primary elements of sole structure 104 are a midsole 114 and an outsole 112. Midsole 114 is secured to a lower area of upper 102 and may be formed from a polymer foam or another suitable material. In further configurations, midsole 114 may incorporate fluid-filled chambers, plates, moderators, and/or other elements that further attenuate forces, enhance stability, or influence the motions of the foot. Outsole 112 is secured to a lower surface of midsole 114 and may be formed of, for example, a wear-resistant rubber material that is textured to impart traction. Upper 102 may be formed from various elements (e.g., laces, tongues, collars) that combine to provide a structure for securely and comfortably receiving a foot. Although the configuration of upper 102 may vary significantly, the various elements generally define a void (void) within upper 102 for receiving and securing the foot relative to sole structure 104. The surface of the void within upper 102 is shaped to receive the foot and may extend over instep and toe areas of the foot, along medial and lateral sides of the foot, under the foot, and around a heel area of the foot. Upper 102 may be manufactured from one or more materials, such as textiles, polymer foam, leather, synthetic leather, and the like, that are stitched or bonded together. Although this configuration of sole structure 104 and upper 102 provides an example of a sole structure that may be used in conjunction with an upper, a variety of other conventional or nonconventional configurations of sole structure 104 and/or upper 102 may also be utilized. Accordingly, the configuration and features of sole structure 104 and/or upper 102 may vary significantly.

Fig. 1o (a) and 1o (b) illustrate perspective and side views of an article of footwear 130 that includes a sole structure 134 and an upper 132. Structures comprising inorganic optical elements are denoted by 136a and 136b/136 b'. Sole structure 134 is secured to upper 132 and sole structure 134 extends between the foot and the ground when article of footwear 130 is worn. Upper 132 may be formed from various elements (e.g., laces, a tongue, a collar) that, in combination, provide structure for securely and comfortably receiving a foot. Although the configuration of upper 132 may vary significantly, the various elements generally define a void within upper 132 for receiving and securing a foot relative to sole structure 134. The surface of the void within upper 132 is shaped to receive the foot and may extend over instep and toe areas of the foot, along medial and lateral sides of the foot, under the foot, and around a heel area of the foot. Upper 132 may be manufactured from one or more materials that are stitched or bonded together, such as textiles including natural and synthetic leather, molded polymer components, polymer foams, and the like.

The primary elements of sole structure 134 are a forefoot component 142, a heel component 144, and an outsole 146. Each of forefoot component 142 and heel component 144 is secured directly or indirectly to a lower area of upper 132 and is formed from a polymer material that encloses a fluid, which may be a gas, a liquid, or a gel. For example, during walking and running, forefoot component 142 and heel component 144 compress between the foot and the ground, thereby attenuating ground reaction forces. That is, forefoot component 142 and heel component 144 are inflated and may be pressurized with a fluid to cushion the foot. Outsole 146 is secured to lower regions of forefoot component 142 and heel component 144, and may be formed of a wear-resistant rubber material that is textured to impart traction. Forefoot component 142 may be fabricated from one or more polymers (e.g., one or more layers of polymer film) that form more than one chamber that includes a fluid, such as a gas. More than one chamber may be independent or fluidly interconnected. Similarly, heel component 144 may be manufactured from one or more polymers (e.g., one or more layers of polymer film) that form more than one chamber that includes a fluid such as a gas and that may also be separate or fluidly interconnected. In some configurations, sole structure 134 may include a foam layer that extends between upper 132 and one or both of forefoot component 142 and heel component 144, or foam elements may be located within indentations (indentations) in lower regions of forefoot component 142 and heel component 144, for example. In other configurations, sole structure 132 may incorporate plates, moderators, lasting elements, or motion control members, for example, to further attenuate forces, enhance stability, or influence the motion of the foot. Although the depicted configurations of sole structure 134 and upper 132 provide examples of sole structures that may be used in conjunction with an upper, a variety of other conventional or nonconventional configurations of sole structure 134 and/or upper 132 may also be utilized. Accordingly, the configuration and features of sole structure 134 and/or upper 132 may vary significantly.

Fig. 1o (c) is an a-a cross-sectional view depicting upper 132 and heel component 144. Optical element 136b may be disposed on an outer wall of heel component 144, or alternatively or optionally, optical element 136 b' may be disposed on an inner wall of heel component 144.

Fig. 1p (a) and 1p (b) illustrate perspective and side views of an article of footwear 160 that includes traction elements 168. Structures including inorganic optical elements are denoted by 172a and 172 b. Article of footwear 160 includes an upper 162 and a sole structure 164, with upper 162 secured to sole structure 164. Sole structure 164 may include one or more of a toe plate 166a, a middle plate 166b, and a heel plate 166 c. The plate may include one or more traction elements 168, or traction elements may be applied directly to the ground-facing surface of the article of footwear. As shown in fig. 1p (a) and 1p (b), traction elements 168 are cleats, but may include lugs, cleats, studs and nails, and tread patterns to provide traction on soft and smooth surfaces. In general, cleats, spikes, and nails are typically included in footwear designed for sports such as international/soccer, golf, american football, rugby, baseball, and the like, while lugs and/or enhanced tread patterns are typically included in footwear (not shown) including boots designed for use in harsh outdoor conditions such as cross-country running, hiking, and military use. Sole structure 164 is secured to upper 162 and sole structure 164 extends between the foot and the ground when article of footwear 160 is worn. Upper 162 may be formed from various elements (e.g., laces, a tongue, a collar) that, in combination, provide structure for securely and comfortably receiving a foot. Although the configuration of upper 162 may vary significantly, the various elements generally define a void within upper 162 for receiving and securing a foot relative to sole structure 164. The surface of the void within upper 162 is shaped to receive the foot and extends over the instep and toe areas of the foot, along the medial and lateral sides of the foot, under the foot, and around the heel area of the foot. Upper 162 may be manufactured from one or more materials that are stitched or bonded together, such as textiles including natural and synthetic leather, molded polymer components, polymer foams, and the like. In other aspects not depicted, sole structure 164 may incorporate foam, one or more fluid-filled chambers, plates, moderators, or other elements that further attenuate forces, enhance stability, or influence the motions of the foot. Although the depicted configurations of sole structure 164 and upper 162 provide examples of sole structures that may be used in connection with an upper, a variety of other conventional or nonconventional configurations of sole structure 164 and/or upper 162 may also be utilized. Accordingly, the configuration and features of sole structure 164 and/or upper 162 may vary significantly.

In a particular embodiment, the structurally colored component is a sheet or film or the like, and the optical element is disposed on at least one surface of the sheet or film.

According to various embodiments, structurally colored articles and components exhibit a structural color, i.e., a visible color produced at least in part by an optical effect imparted by the optical element (e.g., by scattering, refraction, reflection, interference, and/or diffraction of light at visible wavelengths). The structural color may comprise one of a number of colors. The "color" of an item as perceived by an observer may be different from the actual color of the item, since the color perceived by an observer is determined by: the optical element may absorb, refract, interfere with, or otherwise alter the light reflected by the article due to the actual color of the article due to its presence; the ability of an observer to detect the wavelength of light reflected by the item; the wavelength of the light used to illuminate the item, and other factors such as the color of the environment of the item and the type of incident light (e.g., sunlight, fluorescent light, and the like). As a result, the color of the object as perceived by the viewer may differ from the actual color of the article.

Conventionally, colour is imparted to man-made objects by applying coloured pigments or dyes to the object. More recently, methods have been developed to impart "structural color" to man-made objects. Structural color is the color produced at least in part by a microstructured surface (microstructured surface) that interferes with visible light of a contact surface. Unlike colors caused by absorption or emission of visible light by coloring substances, structural colors are colors caused by physical phenomena including scattering, refraction, reflection, interference, and/or diffraction of light. For example, optical phenomena that impart color to structures may include multilayer interference, thin film interference, refraction, dispersion, light scattering, mie scattering, diffraction, and diffraction gratings. In aspects described herein, the structural color imparted to the article may be visible to an observer having 20/20 visual acuity and normal color vision at a distance of about 1 meter from the article. In addition to "color," the structural color may be iridescent or metallic.

As described herein, the structural color is at least partially produced by the optical element, as opposed to the color produced by the pigment and/or dye alone. The color of the structurally colored article may be due solely to the structural color (i.e., the article, the colored portion of the article, or the colored outer layer of the article may be substantially free of pigments and/or dyes). The structural color may also be used in combination with pigments and/or dyes, for example, to change all or a portion of the structural color.

"hue" is generally used to describe a property of a color that is distinguishable based on the dominant wavelength of visible light, and is generally described using terms such as magenta, red, orange, yellow, green, cyan, blue, indigo, violet, etc., or may be described as being related to (e.g., similar or dissimilar to) one of these colors. The hue of a color is generally considered to be independent of the intensity or brightness of the color. For example, in the munsell color system, the properties of a color include hue, darkness (brightness), and chroma (color purity). A particular hue is typically associated with a particular range of wavelengths in the visible spectrum: wavelengths in the range of about 700 to 635 nanometers are associated with red, a range of about 635 to 590 nanometers is associated with orange, a range of about 590 to 560 nanometers is associated with yellow, a range of about 560 to 520 nanometers is associated with green, a range of about 520 to 490 nanometers is associated with cyan, a range of about 490 to 450 nanometers is associated with blue, and a range of about 450 to 400 nanometers is associated with violet.

The color (including hue) of the article as perceived by an observer may be different from the actual color of the article. The color perceived by an observer depends not only on the physical properties of the article, but also on the environment of the article, and the characteristics of the perceived eyes and brain. For example, since the color perceived by an observer is determined by the actual color of the item (e.g., the color of light exiting the surface of the item), the ability of the observer to detect the wavelengths of light reflected or emitted by the item, the wavelengths of light used to illuminate the item, and other factors such as the color of the environment of the item and the type of incident light (e.g., sunlight, fluorescent light, and the like). As a result, the color of the object perceived by the viewer may differ from the actual color of the article.

When used in the context of structural color, an individual can characterize the hue of a structurally colored article (i.e., an article that has been structurally colored by incorporating an optical element into the article) based on the wavelength of light that the structurally colored portion of the article absorbs and reflects (e.g., linearly and non-linearly). While the optical element may impart the first structural color, the presence of the optional textured surface and/or primer layer may change the structural color. Other factors such as coatings or transparent elements may further alter the perceived color of the structure. The hues of the structurally colored article may comprise any one of the hues described herein as well as any other hue or combination of hues. Structural colors may be referred to as "mono-hues" (i.e., hues that remain substantially the same regardless of angle of observation and/or illumination) or "multi-hues" (i.e., hues that vary according to angle of observation and/or illumination). The multi-hue structure color may be iridescent (i.e., the hue gradually changes within two or more hues as the angle of observation or illumination changes). The hue of iridescent polychrome structured colors can gradually change over all hues in the visible spectrum (e.g., like a "rainbow") as the angle of observation or illumination changes. The hue of an iridescent polychrome structural color may gradually change over a limited number of hues in the visible spectrum as the angle of observation or illumination changes, in other words, one or more hues in the visible spectrum (e.g., red, orange, yellow, etc.) are not observable in the structural color as the angle of observation or illumination changes. For monochrome structured colors, there may be only one hue or substantially one hue in the visible spectrum. The hues of the multi-hue structure colors may change more abruptly between a limited number of hues (e.g., between 2-8 hues, or between 2-4 hues, or between 2 hues) as the angle of observation or illumination changes.

The structural color may be a multi-hue structural color in which two or more hues are imparted by the structural color.

The structural color can be an iridescent multi-hue structural color in which the hue of the structural color varies over a wide variety of hues (e.g., 4, 5, 6, 7, 8, or more hues) when viewed at a single viewing angle, or when viewed from two or more different viewing angles that are at least 15 degrees apart from one another.

The structural color can be a limited iridescent polychrome structural color in which the hues of the structural color vary or significantly vary (e.g., about 90 percent, about 95 percent, or about 99 percent) over a limited number of hues (e.g., 2 hues or 3 hues) when viewed from two or more different viewing angles that are at least 15 degrees apart from each other.

The structural color can be a mono-hue, angle-independent structural color, wherein the hue, and lightness, or hue, lightness, and chroma, of the structural color are independent of the viewing angle or substantially (e.g., about 90 percent, about 95 percent, or about 99 percent) independent of the viewing angle. For example, the single-hue, angle-independent structural colors may exhibit the same hue or substantially the same hue (e.g., single-hue structural colors) when viewed from at least 3 different angles that are at least 15 degrees apart from each other.

Similarly, other properties of the structural color, such as the brightness of the color, the saturation of the color, and the purity of the color, among others, may be substantially the same regardless of the angle of observation or illumination, or may vary depending on the angle of observation or illumination. The structural color may have a matte appearance, a glossy appearance, or a metallic appearance, or a combination thereof.

As discussed above, the color (including hue) of the structurally colored article may vary depending on the angle at which the structurally colored article is viewed or illuminated. One or more hues of the article may be determined by viewing the article or illuminating the article at a variety of angles using constant lighting conditions. As used herein, an "angle" of illumination or observation is an angle measured from an axis or plane normal to the surface. The viewing angle or illumination angle may be set between about 0 degrees and 180 degrees. The viewing or illumination angles may be set at 0, 15, 30, 45, 60, and-15 degrees, and the color may be measured using a colorimeter or spectrophotometer (e.g., Konica Minolta) that focuses on a specific area of the item to measure the color. The viewing angle or illumination angle may be set to 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, 90 degrees, 105 degrees, 120 degrees, 135 degrees, 150 degrees, 165 degrees, 180 degrees, 195 degrees, 210 degrees, 225 degrees, 240 degrees, 255 degrees, 270 degrees, 285 degrees, 300 degrees, 315 degrees, 330 degrees, and 345 degrees, and the color may be measured using a colorimeter or spectrophotometer. In the specific example of a multi-hue article colored using only structural colors, the hue measured for the article when measured at 0, 15, 30, 45, 60, and-15 degrees consists of: "blue" at three of these measurement angles, "cyan" at two of these measurement angles, and "violet" at one of these measurement angles.

In other embodiments, the color (including hue, darkness and/or chroma) of the structurally colored article does not substantially change, if at all, depending on the angle at which the article is viewed or illuminated. In cases such as this, the structural color may be an angle-independent structural color in that the observed hue, and darkness, or hue, darkness, and chroma, are substantially independent of the angle of observation or independent of the angle of observation.

Various methodologies exist for defining a color coordinate system. One example is the L x a b color space, where L x is the luminance value for a given lighting condition, and a and b are the values of the color opponent dimension based on CIE coordinates (CIE 1976 color space or CIELAB). In embodiments, a structurally colored article having a structural color may be considered to have a "single" color when the change in the measured color of the article at three or more measured viewing or illumination angles selected from the group consisting of 0, 15, 30, 45, 60, and-15 measured viewing or illumination angles is within about 10% or within about 5% of the total number of a or b coordinates of the L a b numerical range (CIE 1976 color space). In certain embodiments, a color is considered a different color when the measured and assigned values 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 in the L a b system. The structurally colored article can have a variation in the total number of a-coordinates or b-coordinates of the L a b range of values (CIE 1976 color space) of less than about 40 percent, or less than about 30 percent, or less than about 20 percent, or less than about 10 percent at three or more measured viewing or illumination angles.

The color change between two measurements in CIELAB space can be determined mathematically. For example, the first measurement has the coordinate L₁*、a₁A and b₁And the second measurement has the coordinate L₂*、a₂A and b₂*. The total difference between these two measurements over the CIELAB value range can be expressed as Δ E ×_abIt is calculated as follows: delta E_ab＝[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^1/2. In general, if two colors have a Δ E less than or equal to 1_abThe difference in color is not perceptible to the human eye and if two colors have a Δ E > 100_abThen the color is considered the opponent color, and a Δ E of about 2-3_abIs considered to be a threshold for perceptible color differences. In certain embodiments, Δ E is between three or more measured viewing or illumination angles selected from the measured viewing or illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and-15 degrees_abLess than 60, or less than 50, or less than 40, or less than 30, structurally colored articles with structural colors may be considered to have a "single" color. The structurally colored article may have a Δ Ε of less than about 100, or less than about 80, or less than about 60 between two or more measured viewing or illumination angles _ab。

Another example of a color value range is the CIELCH color space, where L is the luminance value, C is the chrominance value, and h ° represents the hue expressed in angular measurements for a given lighting condition. In embodiments, a structurally colored article having a structural color may be considered to have a "single" color when the difference in the h ° angular coordinate of the article measured color in the CIELCH color space at three or more measured viewing or illumination angles selected from 0, 15, 30, 45, 60, and-15 degrees is less than 10 degrees or less than 5 degrees. In certain embodiments, a color is considered a different color when the measured and assigned values vary by at least 45 degrees from the h ° measured in the CIELCH system. The structurally colored article may have a variation in the h ° measurement of the CIELCH system of less than about 60 degrees, or less than about 50 degrees, or less than about 40 degrees, or less than about 30 degrees, or less than about 20 degrees, or less than about 10 degrees at three or more measured viewing or illumination angles.

Another system for characterizing color includes the "PANTONE" matching system (PANTONE LLC, Carlstadt, new jersey, usa), which provides a visual color standard system that provides an accurate method for selecting, specifying, diffusing, and matching colors through any medium. In an example, a structurally colored article having a structural color can be considered to have a "single" color when the color measured on the article at three or more measured viewing or illumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and-15 degrees is within a certain number of adjacent standard values, for example within 20 adjacent PANTONE standard values.

Now that the structural colors have been described, additional details regarding the optical elements are provided. As described herein, a structurally colored article, component, or structure includes an optical element. The optical element includes at least one optical layer. The optical element may be or include a single layer reflector, a single layer filter, a multilayer reflector, or a multilayer filter, or a combination thereof. The optical element may be used to modify light impinging thereon such that a structural color is imparted to the article. The optical element may include at least one optical layer and optionally one or more additional layers (e.g., protective layers, textured layers, primer layers, polymeric layers, and the like).

A method of manufacturing a structurally colored article may include disposing (e.g., attaching, bonding, fastening, joining, affixing, connecting, bonding) an optical element onto an article (e.g., an article of footwear, an article of apparel, an article of athletic equipment, etc.). The article includes a component, and the component has a surface on which an optical element can be disposed. As described herein, the surface of the article may be made of a material such as a thermoplastic material or a thermoset material. For example, the article has a surface comprising a thermoplastic material (i.e., a first thermoplastic material), such as an outward-facing surface of the component or an inward-facing surface of the component (e.g., an outward-facing surface or an inward-facing surface of the bladder). For example, the optical element may be arranged onto the thermoplastic material.

In one aspect, the temperature of at least a portion of the first side of an article comprising a thermoplastic material is elevated to be at or above the creep relaxation temperature (T) of the thermoplastic material_cr) Vicat softening temperature (T)_vs) Heat distortion temperature (T)_hd) And/or melting temperature (T)_m) For example to soften or melt the thermoplastic material. The temperature may be raised to a temperature at or above the creep relaxation temperature. The temperature may be raised to a temperature at or above the vicat softening temperature. The temperature may be raised to a temperature at or above the heat distortion temperature. The temperature may be raised to a temperature at or above the melting temperature. The optical element is affixed to the thermoplastic material within at least a portion of the first side of the article when the temperature of the at least a portion of the first side of the article is at or above an elevated temperature (e.g., at or above a creep-relaxation temperature, a heat-deformation temperature, a vicat softening temperature, or a melting temperature of the thermoplastic material). After attachment, the temperature of the thermoplastic material is reduced to a temperature below its creep relaxation temperature to at least partially re-solidify the thermoplastic material. The thermoplastic material may be actively cooled (e.g., removing the source of elevated temperature and actively cooling (e.g., flowing a cooler gas adjacent the article, reducing the temperature of the thermoplastic material)) or passively cooled (e.g., removing the source of elevated temperature and allowing the thermoplastic layer to cool itself).

The optical element has a first side (including an outer surface) and a second side (including an opposing outer surface) opposite the first side, wherein either the first side or the second side is adjacent the article. For example, when the optical element is used in conjunction with a component, such as a film or a capsule, having an inward-facing surface and an outward-facing surface, the first side of the optical element may be disposed on the inward-facing surface of the component, such as in the following order: the second side of the optical element/the core of the optical element/the inward facing surface of the first side of the optical element/the outward facing surface of the core/component of the component. Alternatively, the second side of the optical element may be arranged on the inward facing surface of the component, such as in the following order: the first side of the optical element/the core of the optical element/the inward facing surface of the second side of the optical element/the outward facing surface of the core/component of the component wall. In another example, the first side of the optical element may be disposed on an outward facing surface of the component, such as in the following order: an inward facing surface of the component/an outward facing surface of the component/a core of the component/a first side of the optical element/a core of the optical element/a second side of the optical element. Similarly, the second side of the optical element may be arranged on an outward facing surface of the component, such as in the following order: an inward facing surface of the component/an outward facing surface of the component/a core of the component/a second side of the optical element/a core of the optical element/a first side of the optical element. In examples where an optional textured surface, an optional primer layer, or both are present, the textured surface and/or primer layer may be located at the interface between the surface of the component and the side of the optical element.

The optical elements or layers or portions thereof (e.g., optical layers) can be formed using known techniques such as physical vapor deposition, electron beam deposition, atomic layer deposition, molecular beam epitaxy, cathodic arc deposition, pulsed laser deposition, sputter deposition (e.g., radio frequency, direct current, reactive, non-reactive), chemical vapor deposition, plasma enhanced chemical vapor deposition, low pressure chemical vapor deposition, and wet chemical techniques such as layer-by-layer deposition, sol-gel deposition, Langmuir Blodgett, and the like. The temperature of the first side may be adjusted using the technique of forming the optical element and/or a separate system for adjusting the temperature. Additional details are provided herein.

The optical layers of the optical element may include single or multiple layer reflectors. The multilayer reflector may be configured to have a reflectivity for light at a given wavelength (or range of wavelengths), the reflectivity depending at least in part on the material selection, thickness, and number of layers of the multilayer reflector. In other words, one can carefully select the materials, thicknesses, and number of layers of the multilayer reflector, and optionally the interaction of the multilayer reflector with one or more other layers, such that the multilayer reflector can reflect light of a certain wavelength (or range of wavelengths) to produce a desired structural color. The optical layer may include at least two adjacent layers, wherein the adjacent layers have different refractive indices. The difference in refractive index of adjacent layers of the optical layer can be about 0.0001 percent to 50 percent, about 0.1 percent to 40 percent, about 0.1 percent to 30 percent, about 0.1 percent to 20 percent, about 0.1 percent to 10 percent (and other ranges therebetween (e.g., the range can be in 0.0001 percent to 5 percent increments)). The refractive index depends at least in part on the material of the optical layer and may range from 1.3 to 2.6.

The optical layer may include 2 to 20 layers, 2 to 10 layers, 2 to 6 layers, or 2 to 4 layers. Each of the optical layers may have a thickness that is about one-quarter of the wavelength of the light to be reflected to produce the desired structural color. Each of the optical layers may have a thickness of about 10 to 500 nanometers or about 90 to 200 nanometers. The optical layer may have at least two layers, with adjacent layers having different thicknesses, and optionally the same or different refractive indices.

The optical element may comprise a single or multilayer filter. The multilayer filters destructively interfere with light impinging on the structure or article, where the destructive interference of light and optionally interaction with one or more other layers or structures (e.g., single or multilayer reflectors, textured structures) impart color to the structure. In this regard, the layers of the multilayer filter may be designed (e.g., material selection, thickness, number of layers, etc.) such that a single wavelength of light or a particular range of wavelengths of light constitutes a structural color. For example, the wavelength range of light may be limited to within plus or minus 30 percent of a single wavelength, or within plus or minus 20 percent of a single wavelength, or within plus or minus 10 percent of a single wavelength, or within a range of plus or minus 5 percent of a single wavelength. The wavelength range can be wider to produce more iridescent structural colors.

The optical layer may comprise a plurality of layers, wherein each layer independently comprises a material selected from the group consisting of: transition metals, metalloids, lanthanides and actinides and their nitrides, oxynitrides, sulfides, sulfates, selenides and tellurides. The materials may be selected to provide a refractive index that, when optionally combined with other layers of the optical element, achieves the desired result. One or more layers of the optical layer may be made of liquid crystal. Each of the optical layers may be made of liquid crystal. One or more layers of the optical layer may be made of materials such as silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, aluminum oxide, or combinations thereof. Each of the optical layers may be made of a material such as silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, aluminum oxide, or a combination thereof.

The optical elements may be colorless (e.g., no pigment or dye is added to the structure or layers thereof), colored (e.g., pigment and/or dye is added to the structure or layers thereof (e.g., dark or black)), reflective, and/or transparent (e.g., 75 percent or greater percent light transmittance). The surface of the component on which the optical element is disposed can be colorless (e.g., no pigment or dye is added to the material), colored (e.g., pigment and/or dye is added to the material (e.g., dark or black)), reflective, and/or transparent (e.g., 75 percent or greater percent light transmittance).

The optical layers may be formed in a layer-by-layer manner, with each layer having a different index of refraction. Each of the optical layers may be formed using known techniques such as physical vapor deposition, including: chemical vapor deposition, pulsed laser deposition, evaporative deposition, sputter deposition (e.g., radio frequency, direct current, reactive, non-reactive), plasma enhanced chemical vapor deposition, electron beam deposition, atomic layer deposition, molecular beam epitaxy, cathodic arc deposition, low pressure chemical vapor deposition, and wet chemical techniques such as layer-by-layer deposition, sol-gel deposition, Langmuir Blodgett, and the like.

As mentioned above, the optical element may comprise one or more layers in addition to the optical layer. The optical element has a first side (e.g., a side having a surface) and a second side (e.g., a side having a surface), wherein the first side or the second side is adjacent to the surface of the component. One or more other layers of the optical element may be on the first side and/or the second side of the optical element. For example, the optical element may include a protective layer and/or a polymer layer, such as a thermoplastic polymer layer, wherein the protective layer and/or the polymer layer may be on one or both of the first side and the second side of the optical element. In another example, the optical element can include a primer layer as described herein. One or more of the optional other layers may include a textured surface. Alternatively or additionally, one or more optical layers of the optical element may include a textured surface.

A protective layer may be disposed on the first side and/or the second side of the optical layer to protect the optical layer. The protective layer is more durable or more abrasion resistant than the optical layer. The protective layer is optically transparent to visible light. A protective layer may be on the first side of the optical element to protect the optical layer. All or a portion of the protective layer may include a dye or pigment to alter the appearance of the structural color. The protective layer may comprise a combination of silica, glass, metal oxides, or a mixture of polymers. The protective layer may have a thickness of about 3 nanometers to 1 millimeter.

The protective layer may be formed using physical vapor deposition, chemical vapor deposition, pulsed laser deposition, evaporative deposition, sputter deposition (e.g., radio frequency, direct current, 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, Langmuir Blodgett, and the like. Alternatively or additionally, the protective layer may be applied by spraying, dipping, brushing, spin coating, doctor blading, and the like.

The polymer layer may be disposed on the first side and/or the second side of the optical element. Such as, for example, when the article does not include a thermoplastic material to which the optical element is adhered, the polymer layer may be used to dispose the optical element onto the article. The polymeric layer may comprise a polymeric adhesive material, such as a hot melt adhesive. The polymer layer may be a thermoplastic material and may include one or more layers. The thermoplastic material may be any of the thermoplastic materials described herein. The polymer layer may be applied using a variety of methods such as spin coating, dip coating, doctor blade coating, and the like. The polymer layer may have a thickness of about 3 nanometers to 1 millimeter.

As described above, one or more embodiments of the present disclosure provide articles that incorporate optical elements (e.g., single or multilayer structures) on the sides of the components of the article to impart structural color. The optical element may be arranged onto the thermoplastic material of the side of the article, and the side of the article may comprise a textile, including a textile comprising a thermoplastic material.

In aspects, the component or optical element can optionally include a textured surface. Having described the optical elements, additional details of the optional textured surface will now be described. As described herein, an optical element can include at least one optical layer and optionally a textured surface. The textured surface may be a surface of a textured structure or textured layer. The textured surface may be provided as part of the optical element. For example, the optical element may include a textured layer or a textured structure that includes a textured surface. The textured surface may be formed on the first side or the second side of the optical element. For example, the side of the optical layer may be formed or modified to provide a textured surface, or a textured layer or structure may be attached to the first or second side of the optical element. The textured surface may be provided as a part of the component to which the optical element is arranged. For example, the optical element may be arranged onto a surface of the component, wherein the surface of the component is a textured surface, or the surface of the component comprises a textured structure or a textured layer attached to the surface.

The textured surface (or textured structure or textured layer including a textured surface) may be provided as a feature on or part of another medium such as a transfer medium and imparted to a side or layer of the optical element or to a surface of the component. For example, a mirror image or relief form (relief form) of the textured surface may be disposed on the side of the transfer medium, and the transfer medium contacts the side of the optical element or the surface of the component in a manner that imparts the textured surface to the optical element or article. While various embodiments herein may be described with respect to a textured surface of an optical element, it will be understood that features of the textured surface or textured structure or textured layer may be imparted in any of these ways.

The textured surface may contribute to the structural color produced by the optical element. As described herein, the coloration is imparted to the structure at least in part due to optical effects caused by physical phenomena, such as scattering, diffraction, reflection, interference, or uneven refraction of light rays from the optical element. The textured surface (or its mirror image or relief) may include more than one contour feature and a flat or planar region. More than one profile feature (including the size, shape, orientation, spatial arrangement, etc. of the profile features) included in the textured surface may affect light scattering, diffraction, reflection, interference, and/or refraction produced by the optical element. The flat or planar regions (including the size, shape, orientation, spatial arrangement, etc. of the flat or planar regions) contained in the textured surface may affect light scattering, diffraction, reflection, interference, and/or refraction produced by the optical element. The desired structural color may be designed at least in part by adjusting one or more of the contour features of the textured surface and/or the properties of the flat or planar regions.

The contour features may extend from the sides of the flat region to provide a raised and/or recessed appearance therein. The profile features may include various combinations of protrusions and depressions. For example, a contour feature may include a protrusion having one or more depressions therein, a depression having one or more protrusions therein, a protrusion having one or more additional protrusions thereon, a depression having one or more additional depressions therein, and the like. The flat region need not be completely flat and may include texture, roughness, and the like. The texture of the flat region may not have much, if any, effect on the imparted color of the structure. The texture of the flat areas generally contributes to the imparted structural color. For clarity, the contour features and the flat regions are described with reference to the contour features extending over the flat regions, but when the contour features are depressions in the textured surface, the opposite measure (e.g., size, shape, and the like) may apply.

The textured surface may comprise a thermoplastic material. The profile features and the flat regions may be formed using a thermoplastic material. For example, the textured surface may be formed in the thermoplastic material when the thermoplastic material is heated above its softening temperature, such as by molding, stamping, printing, compressing, cutting, etching, vacuum forming, etc., the thermoplastic material to form contour features and flat areas in the thermoplastic material. The textured surface may be imparted on the side of the thermoplastic material. The textured surface may be formed in a layer of thermoplastic material. The profile features and the flat areas may be made of the same thermoplastic material or different thermoplastic materials. Dimensional measurements for profile features (e.g., length, width, height, diameter, and the like) described herein refer to an average dimensional measurement of the profile feature in 1 square centimeter in an inorganic optical element.

The textured surface typically has a length dimension extending along the x-axis and a width dimension extending along the z-axis and a thickness dimension extending along the y-axis. The textured surface has a substantially planar portion extending in a first plane extending along the x-axis and the z-axis. The contour features may extend outwardly from the first plane so as to extend above or below the plane x. The profile feature may extend generally normal to the first plane or at an angle greater or less than 90 degrees to the first plane.

Dimensional measurements for profile features (e.g., length, width, height, diameter, and the like) described herein refer to an average dimensional measurement of the profile feature in 1 square centimeter in an inorganic optical element.

The dimensions (e.g., length, width, height, diameter, depending on the shape of the profile feature) of each profile feature may be in the nanometer to micrometer range. The textured surface may have profile features and/or flat regions with dimensions of about 10 nanometers to about 500 micrometers. The profile features may have a size in the nanometer range, such as a size from about 10 nanometers to about 1000 nanometers. All dimensions of the profile features (e.g., length, width, height, diameter, depending on geometry) may be in the nanometer range, e.g., from about 10 nanometers to about 1000 nanometers. The textured surface may have more than one profile feature having a dimension of 1 micron or less. In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have dimensions within this range. The profile features may have a width to height dimension ratio and/or a length to height dimension ratio of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1: 10.

The textured surface may have contour features and/or flat regions having dimensions in the micron size range. The textured surface may have profile features and/or flat regions having a size of about 1 micron to about 500 microns. All dimensions of the profile features (e.g., length, width, height, diameter, depending on geometry) may be in the micrometer range, for example, from about 1 micrometer to about 500 micrometers. The textured surface may have more than one profile feature having a dimension from about 1 micron to about 500 microns. In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have dimensions within this range. The height (or depth if recessed) of the profile features may be about 0.1 microns and 50 microns, about 1 micron to 5 microns, or 2 microns to 3 microns. The profile features may have a width to height dimension ratio and/or a length to height dimension ratio of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1: 10.

The textured surface may have more than one profile feature having a mixture of size sizes in the nanometer to micrometer range (e.g., a portion of the profile features on the nanometer scale and a portion of the profile features on the micrometer scale). The textured surface may have more than one profile feature with a blend of size ratios. The textured surface may have profile features with one or more nanoscale protrusions or recesses on the microscale protrusions or recesses.

The profile features can have a height dimension and a width dimension that are within three times of each other (0.33w ≦ h ≦ 3w where w is the width of the profile feature and h is the height of the profile feature), and/or a height dimension and a length dimension that are within three times of each other (0.33I ≦ h ≦ 3I where I is the length of the profile feature and h is the height of the profile feature). The profile features can have a length to width ratio of from about 1:3 to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of the profile features may be substantially the same or different.

In another aspect, the textured surface can have contour features and/or flat regions with at least one dimension in the middle micron range and higher (e.g., greater than 500 microns). The profile feature can have at least one dimension (e.g., a maximum dimension such as length, width, height, diameter, and the like, depending on the geometry or shape of the profile feature) greater than 500 microns, greater than 600 microns, greater than 700 microns, greater than 800 microns, greater than 900 microns, greater than 1000 microns, greater than 2 millimeters, greater than 10 millimeters, or greater. For example, the largest dimension of the profile features may range from about 600 microns to about 2000 microns, or about 650 microns to about 1500 microns, or about 700 microns to about 1000 microns. At least one or more of the dimensions of the profile features (e.g., length, width, height, diameter, depending on geometry) may be in the micrometer range, while one or more other dimensions may be in the nanometer to micrometer range (e.g., less than 500 micrometers, less than 100 micrometers, less than 10 micrometers, or less than 1 micrometer). The textured surface may have more than one profile feature having at least one dimension in the middle micron or larger range (e.g., 500 microns or larger). In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have at least one dimension greater than 500 microns. In particular, at least one of the length and width of the profile feature is greater than 500 microns, or both the length and width of the profile feature are greater than 500 microns. In another example, the diameter of the profile feature is greater than 500 microns. In another example, when the contour feature is an irregular shape, the longest dimension is greater than 500 microns.

In one aspect, the height of the profile features can be greater than 50 microns. In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have a height greater than 50 microns. The height of the profile features can be 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, or about 100 microns to about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 150 microns, about 250 microns, about 500 microns, or greater. For example, the range can include 50 microns to 500 microns, about 60 microns to 250 microns, about 60 microns to about 150 microns, and the like. One or more other dimensions (e.g., length, width, diameter, or the like) may be in the range of nanometers to micrometers (e.g., less than 500 micrometers, less than 100 micrometers, less than 10 micrometers, or less than 1 micrometer). In particular, at least one of the length and width of the profile features is less than 500 microns, or both the length and width of the profile features are less than 500 microns, while the height is greater than 50 microns. One or more other dimensions (e.g., length, width, diameter, or the like) may be in the range of micrometers to millimeters (e.g., greater than 500 micrometers to 10 millimeters).

The dimensions (e.g., length, width, height, diameter, depending on the shape of the profile feature) of each profile feature may be in the nanometer to micrometer range. The textured surface can have contour features and/or flat regions having dimensions of about 10 nanometers to about 500 micrometers or more (e.g., about 1 millimeter, about 2 millimeters, about 5 millimeters, or about 10 millimeters). At least one dimension (e.g., length, width, height, diameter, depending on geometry) of the profile feature may be in the nanometer range (e.g., from about 10 nanometers to about 1000 nanometers), while at least one other dimension (e.g., length, width, height, diameter, depending on geometry) may be in the micrometer range (e.g., 5 micrometers to 500 micrometers or more (e.g., about 1 millimeter to 10 millimeters)). The textured surface can have more than one profile feature having at least one dimension in the nanometer range (e.g., about 10 to 1000 nanometers) and another dimension in the micrometer range (e.g., 5 to 500 micrometers or more). In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have at least one dimension in the nanometer range and at least one dimension in the micrometer range. In particular, at least one of the length and width of the profile features is in the nanometer range, while the other of the length and width of the profile features is in the micrometer range.

In an aspect, the height of the profile feature can be greater than 250 nanometers. In this context, the phrase "more than one profile feature" means that about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more, or about 99 percent or more of the profile features have a height greater than 250 nanometers. The height of the profile features can be 250 nanometers, about 300 nanometers, about 400 nanometers, or about 500 nanometers, to about 300 nanometers, about 400 nanometers, about 500 nanometers, or about 1000 nanometers or more. For example, the range can be 250 nanometers to about 1000 nanometers, about 300 nanometers to 500 nanometers, about 400 nanometers to about 1000 nanometers, and the like. One or more other dimensions (e.g., length, width, diameter, or the like) may be in the range of micrometers to millimeters (e.g., greater than 500 micrometers to 10 millimeters). In particular, at least one of the length and width of the profile features is in the nanometer range (e.g., about 10 to 1000 nanometers), and the other is in the micrometer range (e.g., 5 to 500 micrometers or more), while the height is greater than 250 nanometers.

The profile features may have a spatial arrangement. The spatial arrangement of the profile features may be uniform, such as uniformly spaced or patterned. The spatial arrangement may be random. Adjacent profile features may be spaced about 10 nanometers to 500 nanometers apart, about 100 nanometers to 1000 nanometers apart, about 1 micron to 100 microns apart, or about 5 microns to 100 microns apart. Adjacent profile features may overlap or be adjacent to each other so that little or no flat area is positioned between them. The desired spacing may depend at least in part on the size and/or shape of the profile structure and the desired color effect of the structure.

The profile feature may have a cross-sectional shape (relative to a plane parallel to the first plane). The textured surface may have more than one profile feature with the same or similar cross-sectional shape. The textured surface has more than one profile feature with a blend of different cross-sectional shapes. The cross-sectional shape of the profile feature may include polygonal (e.g., square or triangular or rectangular cross-section), circular, semi-circular, tubular, elliptical, random, high aspect ratio and low aspect ratio, overlapping profile features, and the like.

The profile features (e.g., about 10 nanometers to 500 micrometers) can include an upper planar surface. The profile features (e.g., about 10 nanometers to 500 micrometers) can include an upper concave curved surface. The concave curved surface may extend symmetrically on either side of the highest point. The concave curved surface may extend symmetrically at only 50 percent of the highest point. The profile features (e.g., about 10 nanometers to 500 micrometers) can include an upper convexly curved surface. The curved surface may extend symmetrically on either side of the highest point. The curved surface may extend symmetrically at only 50 percent of the highest point.

The contour features may include protrusions from the textured surface. The contour features may include recesses (hollow regions) formed in the textured surface. The profile feature may have a smoothly curved shape (e.g., a polygonal cross-section with curved corners).

The profile features, whether protrusions or depressions, may be approximately conical or frustoconical (i.e., the protrusions or recesses may have a horizontally or diagonally flattened top) or have approximately part-spherical surfaces (e.g., convex or concave surfaces having a generally uniform radius of curvature, respectively).

The contour feature may have one or more sides or edges extending in a direction forming an angle with a first plane of the textured surface. The angle between the first plane and the edge or rim of the profile feature is about 45 degrees or less, about 30 degrees or less, about 25 degrees or less, or about 20 degrees or less. One or more of the edges or margins may extend in a linear or planar orientation or may be curved such that the angle varies with distance from the first plane. The profile feature may have one or more sides including a step and/or a flat side. The contour feature may have one or more sides (or portions thereof) that may be orthogonal or perpendicular to the first plane of the textured surface, or extend at an angle of about 10 degrees to 89 degrees from the first plane (90 degrees being perpendicular or orthogonal to the first plane). The profile feature may have a side with a stepped configuration, wherein a portion of the side may be parallel to the first plane of the textured surface or have an angle of about 1 degree to 179 degrees (0 degrees being parallel to the first plane).

The textured surface may have contour features with varying shapes (e.g., contour features may vary in shape, height, width, and length among contour features) or have contour features with substantially uniform shapes and/or sizes. The color of the structure created by the textured surface may be determined, at least in part, by the shape, size, spacing, and the like of the contour features.

The profile features can be shaped so as to produce a portion of the surface (e.g., about 25-50 percent or more) that is about perpendicular to incident light when the light is incident perpendicular to the first plane of the textured surface. The profile features can be shaped so as to produce a portion of the surface (e.g., about 25-50 percent or more) that is about perpendicular to incident light when the light is incident at an angle of up to 45 degrees from the first plane of the textured surface.

The spatial orientation of the contour features on the textured surface can be used to generate the structure color or to affect the degree to which the structure color shifts at different viewing angles. The spatial orientation of the profile features on the textured surface may be random, semi-random, or in a set pattern. The defined pattern of profile features is a known arrangement or configuration of profile features in a region (e.g., about 50 square nanometers to about 10 square millimeters (e.g., including any increment between about 50 nanometers and about 10 millimeters), depending on the size of the profile features). A semi-random pattern of profile features is a known arrangement of profile features having some deviation (e.g., 1% to 15% deviation from the set pattern) in an area (e.g., about 50 square nanometers to 10 square millimeters) where random profile features are present but the pattern of profile features is discernable. The random spatial orientation of the topographical features in the regions does not produce a discernable pattern in certain regions (e.g., about 50 square nanometers to 10 square millimeters).

The spatial orientation of the profile features may be periodic (e.g., full or partial) or aperiodic. The periodic spatial orientation of the profile features is a repeating pattern at intervals. The periodicity of the periodic spatial orientation of the profile features may depend on the size of the profile features, but is typically a periodicity from about 50 nanometers to 100 microns. For example, when the dimensions of the profile features are sub-micron, the periodicity of the periodic spatial orientation of the profile features may be in the range of 50 nanometers to 500 nanometers or in the range of 100 nanometers to 1000 nanometers. In another example, when the dimensions of the profile features are on the micron scale, the periodicity of the periodic spatial orientation of the profile features may be in the range of 10 microns to 500 microns or in the range of 10 microns to 1000 microns. A fully periodic pattern of outline features indicates that the entire pattern exhibits periodicity, while a partially periodic indicates that less than the entire pattern exhibits periodicity (e.g., about 70-99 percent of the periodicity is retained). The non-periodic spatial orientation of the profile features is not periodic and does not exhibit periodicity based on the dimensions of the profile features, particularly, in the range of 50 nanometers to 500 nanometers or in the range of 100 nanometers to 1000 nanometers where the dimensions of the profile features are sub-micron, or in the range of 10 micrometers to 500 micrometers or in the range of 10 micrometers to 1000 micrometers where the dimensions of the profile features are in the micrometer range.

In one aspect, the spatial orientation of the contour features on the textured surface can be set to reduce distortion effects, such as distortion effects resulting from interference of one contour feature with another contour feature with respect to the structural color of the article. Since the shape, size, relative orientation of the profile features may vary considerably across the textured surface, the desired spacing and/or relative positioning of particular regions (e.g., within the micron range or about 1 to 10 square microns) having profile features may be determined appropriately. As discussed herein, the shape, size, relative orientation of the profile features affects the profile of the reflective layer and/or component layers, and thus the size (e.g., thickness), refractive index, number of layers in the inorganic optical element (e.g., reflective layer and component layers) are considered when designing the textured side of the textured layer.

The profile features are located in nearly random positions relative to each other over specific areas of the textured surface (e.g., in the micrometer range or about 1 to 10 square micrometers to square centimeters range or about 0.5 square centimeters to 5 square centimeters, and all range increments therein), where the randomness does not defeat the purpose of creating a structural color. In other words, the spacing, shape, size, and relative orientation of the irregularity and contour features; the size (e.g., thickness), refractive index, number, etc. of the layers (e.g., reflective layer, component layers) are uniform in order to achieve structural color.

The contour features are positioned relative to each other in a set manner over a particular area of the textured surface for the purpose of creating a structural color. The relative positions of the outline features do not necessarily follow a pattern, but may follow a pattern consistent with the desired structure color. As mentioned above and herein, various parameters related to the profile features, the flat regions, and the reflective and/or component layers may be used to position the profile features relative to each other in a set manner.

The textured surface may include micro-scale and/or nano-scale profile features that may form a grating (e.g., a diffraction grating), a photonic crystal structure, a selective mirror structure, a crystalline fiber structure, a deformed matrix structure, a spiral wound structure, a surface grating structure, and combinations thereof. The textured surface may include micro-scale and/or nano-scale profile features that form a grating having a periodic or non-periodic design structure to impart color to the structure. The micro-scale and/or nano-scale profile features can have a pattern of peaks and valleys and/or flat areas of the profile features to produce a desired structural color. The grating may be a echelle grating.

The profile features and flat regions of the textured surface in the inorganic optical element can be manifested as topological undulations in each layer (e.g., the reflective layer and/or the constituent layers). For example, referring to fig. 2A, the inorganic optical element 200 includes a textured structure 220 having more than one contour feature 222 and a flat region 224. As described herein, one or more of the contour features 222 may be protrusions from the surface of the textured structure 220, and/or one or more of the contour features may be depressions (not shown) in the surface of the textured structure 220. One or more component layers 240 are disposed on the textured structure 220, and then a reflective layer 230 and one or more component layers 245 are disposed on the previous layers. In some embodiments, the resulting topology of the textured structure 220 and the one or more component layers 240 and 245 and the reflective layer 230 are not the same, but rather the one or more component layers 240 and 245 and the reflective layer 230 may have raised or recessed regions 242, the height of the raised or recessed regions 242 relative to the planar region 244 being raised or recessed and corresponding generally to the location of the contour features 222 of the textured structure 220. One or more of the component layers 240 and 245 and the reflective layer 230 have a planar region 244 that generally corresponds to the location of the planar region 224 of the textured structure 220. Due to the presence of the raised or recessed regions 242 and the planar regions 244, the resulting overall topology of one or more of the component layers 240 and 245 and the reflective layer 230 may be a topology having a wavy or undulating structure. The size, shape, and spacing of the profile features, along with the number of layers that make up the layers, the reflective layers, the thickness of each layer, the refractive index of each layer, and the type of material, can be used to create inorganic optical elements that result in a particular structural color.

While in some embodiments, the textured surface may produce a structural color or may affect the degree to which the structural color shifts at different viewing angles, in other embodiments, the "textured surface" or textured surface may not produce a structural color or may not affect the degree to which the structural color shifts at different viewing angles. Structural colors can be produced by designing inorganic optical elements with or without textured surfaces. As a result, the inorganic optical element may include a textured surface having profile elements with dimensions in the nanometer to millimeter range, but the structural color or the transformation of the structural color is not attributable to the presence or absence of the textured surface. In other words, the inorganic optical element imparts the same structural color regardless of the presence of the textured surface. The design of the textured surface may be configured to not affect the structural color imparted by the inorganic optical element or to not affect the transformation of the structural color imparted by the inorganic optical element. The shape of the profile features, the size of the shape, the spatial orientation of the profile features relative to each other, and the like may be selected such that the textured surface does not affect the structural color attributed to the inorganic optical element.

The structural colors imparted by the first inorganic optical element and the second inorganic optical element can be compared, wherein the only difference between the first inorganic optical element and the second inorganic optical element is that the first inorganic optical element includes a textured surface. Color measurements may be performed on each of the first and second inorganic optical elements at the same relative angle, wherein a comparison of the color measurements may determine what changes, if any, are associated with the presence of the textured surface. For example, at a first viewing angle, the structural color is a first structural color of the first inorganic optical element, and at the first viewing angle, the structural color is a second structural color of the second inorganic optical element. Under given lighting conditions according to the CIE 1976 color space, a first color measurement can be obtained and has the coordinate L₁A and a₁A and b₁While a second color measurement is obtained and has the coordinates L₂A and a₂A and b₂*。

Δ E between the first and second color measurements_abLess than or equal to about 2.2, or less than or equal to about 3, the first structural color associated with the first color measurement and the second structural color associated with the second color measurement are the same or not perceptibly different to an ordinary observer (e.g., the textured surface does not cause or change the structural color by more than 20 percent, 10 percent, or 5 percent). Δ E between the first and second color measurements _abGreater than 3, or optionally greater than about 4 or 5, the first structural color associated with the first color measurement and the second structural color associated with the second color measurement are different or perceptibly different for an ordinary observer (e.g., the textured surface does cause or does change the structural color by more than 20 percent, 10 percent, or 5 percent).

In another approach, when the value L is₁Sum L₂*、a₁A and a₂And b₁A and b₂A first structural color associated with the first color measurement and a second structural color associated with the second color measurement are the same or not perceptibly different to an ordinary observer when the percentage difference between one or more of is less than 20 percent (e.g., the textured surface does not cause or change the structural color by less than 20 percent, 10 percent, or 5 percent). When the value L is₁Sum L₂*、a₁A and a₂And b₁A and b₂A first structural color associated with the first color measurement and a second structural color associated with the second color measurement are different or perceptibly different to an ordinary observer when the percentage difference between one or more of is greater than 20 percent (e.g., the textured surface does not cause or change the structural color by more than 20 percent, 10 percent, or 5 percent).

In another case, the structural color imparted by the first inorganic optical element and the second inorganic optical element can be compared at different angles of incident light on the inorganic optical elements or at different viewing angles, where the first inorganic optical element is a transparent inorganic optical elementThe only difference between the inorganic optical element and the second inorganic optical element is that the first inorganic optical element comprises a textured surface. Color measurements may be performed for each of the first and second inorganic optical elements at different angles (e.g., angles of about-15 degrees and 180 degrees or about-15 degrees and +60 degrees, and which are spaced at least 15 degrees from each other), wherein a comparison of the color measurements may determine what changes, if any, at the different angles are associated with the presence of the textured surface. For example, at a first viewing angle, the structural color is a first structural color of the first inorganic optical element, and at a second viewing angle, the structural color is a second structural color of the second inorganic optical element. Under given lighting conditions according to the CIE 1976 color space, a first color measurement can be obtained and has the coordinate L₁A and a₁A and b₁While a second color measurement is obtained and has the coordinates L ₂A and a₂A and b₂*。

Δ E between the first and second color measurements_abLess than or equal to about 2.2, or less than or equal to about 3, the first structural color associated with the first color measurement and the second structural color associated with the second color measurement are the same or not perceptibly different to an ordinary observer (e.g., the textured surface does not cause or change the structural color based on different angles of incident light on the inorganic optical element or different angles of observation). Δ E between the first and second color measurements_abGreater than 3, or optionally greater than about 4 or 5, the first structural color associated with the first color measurement and the second structural color associated with the second color measurement are different or perceptibly different to an ordinary observer (e.g., the textured surface does cause or does change structural color at different angles of incident light on the inorganic optical element or different angles of observation).

In another approach, when the value L is₁Sum L₂*、a₁A and a₂And b₁A and b₂A percentage difference between one or more ofLess than 20 percent, the first structural color associated with the first color measurement and the second structural color associated with the second color measurement are the same or not perceptibly different to an ordinary observer (e.g., the textured surface does cause or do change the structural color by more than 20 percent, 10 percent, or 5 percent at different angles of incident light on the inorganic optical element or different angles of observation). When the value L is ₁Sum L₂*、a₁A and a₂And b₁A and b₂A first structural color associated with the first color measurement and a second structural color associated with the second color measurement are different or perceptibly different to an ordinary observer when the percentage difference between one or more of is greater than 20 percent (e.g., the textured surface does cause or does change the structural color by more than 20 percent, 10 percent, or 5 percent at different angles of incident light on the inorganic optical element or different angles of observation).

In another embodiment, the structural color may be imparted by an inorganic optical element without a textured surface. The surfaces of the layers of the optical element are substantially flat (or substantially three-dimensionally flat planar surface) or flat (or three-dimensionally flat planar surface) at the micro-scale (e.g., about 1 to 500 microns) and/or nano-scale (e.g., about 50 to 500 nanometers). With respect to being substantially flat or substantially planar, the surface may include some tiny topological features (e.g., nano-scale and/or micro-scale), such as those that may be caused by unintentional defects, unintentional minor undulations, other unintentionally introduced topological features (e.g., extensions above the plane of the layer or depressions below the plane of the layer or within the plane of the layer) caused by the equipment and/or processes used, and the like. The topological features are not similar to the profile features of the textured surface. Further, a substantially flat (or substantially three-dimensionally flat) planar surface or a flat (or three-dimensionally flat) planar surface may include a curvature that increases with the size of the optical element, e.g., about 500 microns or more, about 10 millimeters or more, about 10 centimeters or more, depending on the size of the inorganic optical element, as long as the surface is flat or substantially flat and the surface includes only some minor topological features.

Fig. 2B is a cross-sectional illustration of a substantially flat (or substantially three-dimensionally flat planar surface) or flat (or three-dimensionally flat planar surface) inorganic optical element 300. The inorganic optical element 300 comprises one or more component layers 340 arranged on a planar surface structure 320 that is flat or three-dimensionally flat, and then a reflective layer 330 and one or more component layers 345 are arranged on the preceding layers. The materials that make up the constituent layers and the reflective layer, the number of layers that make up the constituent layers, the reflective layer, the thickness of each layer, the refractive index of each layer, and the like, can produce an inorganic optical element that results in a particular structural color.

In various aspects, the component or optical element can optionally include a primer layer. Having now described the optical elements and textured surface, additional details of the optional primer layer will be provided. The optical element is used to generate a structural color, where the optical element may include (e.g., as part of the optical element) or use a primer layer to generate the structural color. As described herein, the optical element can also include (e.g., as part of the optical element) an optional textured surface, such as a textured layer and/or a textured structure. The combination of the optical element with the optional texture layer and the optional primer layer can form a structural color structure having one of the following designs: texture layer/primer layer/optical element or primer layer/texture layer/optical element. The primer layer may have a thickness of about 3 nanometers to 200 micrometers. The structural color structure may include a combination of a primer layer, an optical element, and (optionally) a textured surface. The selection of variables associated with the primer layer, texture layer, and optical element can be used to control and select the desired color of the structure.

The structural color structure may include a primer layer, a textured surface (optional), and an optical element (e.g., an optical layer), where the optical element is disposed on the textured surface or the primer layer, depending on the design. The combination of the primer layer, the textured surface, and the optical element imparts a structural color to the article, wherein the structural color is different from the primer color, optionally with or without the application of a pigment or dye to the article. The optical element may be arranged on the primer layer and/or the textured surface. The primer layer may include a textured surface as described herein. For example, the primer layer may be formed in such a manner that it has a textured surface.

The primer layer can include a coating layer (e.g., dyes, pigments, and combinations thereof), an ink layer, a regrind layer, an at least partially degraded polymer layer, a metal layer, an oxide layer, or combinations thereof. The primer layer may have a light color or a dark color. The primer layer may have a dark color. For example, the dark color may be selected from: black, shades of black, brown, shades of red, shades of orange, shades of yellow, shades of green, shades of cyan, shades of blue, shades of violet, gray, shades of magenta, shades of indigo, a hue, a shade, or a hue, any of these colors, and combinations thereof. Colors may be defined using a system of L x a b, where the value of L x may be about 70 or less, about 60 or less, about 50 or less, about 40 or less, or about 30 or less, and the a x coordinate values and b x coordinate values may vary over positive and negative value ranges.

The primer layer may be formed using digital printing, inkjet printing, offset printing, pad printing, screen printing, flexographic printing, thermal transfer printing, physical vapor deposition, including: chemical vapor deposition, pulsed laser deposition, evaporation deposition, sputter 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. Alternatively or additionally, the primer layer may be applied by spraying, dipping, brushing, spin coating, doctor blade coating, and the like.

The primer layer can have a percent light transmission 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" can include about 0% (e.g., 0% to 0.01% or 0% to 0.1%), about 1%, about 2.5%, or about 5%.

The primer layer may include a coating composition that forms a thin layer when applied to the structure. The thin layer may be a solid film having a dark color, such as those described above. The coating composition may include known coating compositions that may include one or more of the following components: one or more coating resins (paint resin), one or more polymers, one or more dyes and one or more pigments, as well as water, film forming solvents, drying agents, thickeners, surfactants, anti-skinning agents, plasticizers, mold inhibitors, anti-marring agents (mar-Resistant agent), anti-flooding agents (anti-flooding agent), and combinations thereof.

The primer layer may include a reground and at least partially degraded polymer layer. The reground and at least partially degraded polymer layer may have a dark color, such as those described above.

The primer layer may include a metal layer or an oxide layer. The metal layer or oxide layer may have a dark color, such as those described above. 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 the following: transition metals, metalloids, lanthanides and actinides, as well as nitrides, oxynitrides, sulfides, sulfates, selenides, tellurides, and combinations of these. The metal oxide can 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 and doped versions of each. The metal oxide can be doped with water, inert gases (e.g., argon), reactive gases (e.g., oxygen or nitrogen), metals, small molecules, and combinations thereof.

The primer layer may be a coating on the surface of the article. The coating may be chemically bonded (e.g., covalently bonded, ionically bonded, hydrogen bonded, and the like) to the surface of the article. It has been found that the coating bonds well to surfaces made of polymeric materials. In an example, the surface of the article may be made of a polymeric material, such as polyurethane, including Thermoplastic Polyurethane (TPU), such as those described herein.

The coating may be a crosslinked coating that includes one or more colorants such as solid pigment particles or dyes. The crosslinked coating can be a matrix of crosslinked polymers (e.g., crosslinked polyester polyurethane polymers or copolymers). The colorant may be embedded in the coating, including in the matrix of the crosslinked polymer. The solid pigment particles or dyes may be physically embedded in the cross-linked polymer matrix, may be chemically bonded to the coating or article (e.g., covalently, ionically, hydrogen bonded, and the like to the coating comprising the polymer matrix or to the material forming the surface of the article to which the coating is applied), or a combination of physical and chemical bonding. The crosslinked coating may have a thickness of about 0.01 microns to 1000 microns.

The coating may be the product of crosslinking (or also referred to as "crosslinked product") the polymeric coating composition. The polymer coating composition may comprise one or more colorants (e.g., solid pigment particles or dyes) in a dispersion of the polymer. The dispersion of the polymer may comprise an aqueous dispersion of the polymer (water-borne dispersion), such as an aqueous dispersion of a polyurethane polymer (including a polyester polyurethane copolymer). The aqueous dispersion of the polymer may be crosslinked to embed the colorant. The colorant may be physically entrapped in the crosslinked product, may be chemically bound to the crosslinked product (e.g., covalently, ionically, hydrogen bonded, and the like to the crosslinked copolymer matrix), or may be both physically and chemically bound to the crosslinked product. The product may be formed by crosslinking a polymeric coating composition. The product may have a thickness of about 0.01 microns to 1000 microns.

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

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

The acid dye is a water-soluble anionic dye. A wide variety of acid dyes are available, ranging from dull shades (dull tone) to bright shades (brilliant shade). Chemically, acid dyes include azo compounds, anthraquinone compounds, and triarylmethane compounds. The "color index" (c.i.) published by the Society of Colorists and Colorists (UK) and the American Association of Textile Chemists and Colorists (USA) is a short compilation of the most widespread dyes and pigments used for large-scale coloring purposes, including 12000 products under 2000 c.i. common names. In c.i., each compound is provided with two numbers, which refer to the color classification and the chemical classification. The "common name" refers to an application field and/or a coloring method, and the other number is a "construction number". Examples of acid dyes include acid yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110, 116, 127, 151, 158:1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246, and 250; acid red 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183, 184, 186, 194, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278, 283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419, and 447; acid violet 3, 5, 7, 17, 54, 90 and 92; acid brown 4, 14, 15, 45, 50, 58, 75, 97, 98, 147, 160:1, 161, 165, 191, 235, 239, 248, 282, 283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414, 420, 422, 425, 432, and 434; acid oranges 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, 277:1, 314, 324, 335, and 342; acid green 1, 12, 68:1, 73, 80, 104, 114, and 119; acid black 1, 26, 52, 58, 60, 64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, 235, and combinations of these. The acid dyes may be used alone or in any combination in the ink composition.

Acid dyes and nonionic disperse dyes are commercially available from a number of sources, including Dystar l.p., Charlotte, NC; huntsman Corporation, woodland, TX, USA under the trade names ERIONYL and tecilon; BASF SE under the trade name BASACID, Ludwigshafen, Germany; and Bezema AG, Montlingen, Switzerland under the trade name Bemacid.

The colorant may include a dye and a quaternary (tetraalkyl) ammonium salt, particularly when the dye is an acid dye. The quaternary (tetraalkyl) ammonium salt can be reacted with a dye (e.g., an acid dye) to form a complex dye that can be used in a coating. An "alkyl" group can include C1 to C10 alkyl groups. The quaternary (tetraalkyl) ammonium salt can be selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds. The counter ion of the quaternary ammonium salt should be selected such that the quaternary ammonium salt forms a stable solution with the dye (e.g., an anionic dye). The quaternary ammonium compound may be, for example, a halide (such as chloride, bromide, or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate, chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite, hexafluorophosphite, borate, tetrafluoroborate, cyanide, isocyanide, azide, thiosulfate, thiocyanate, or carboxylate (such as acetate or oxalate). The tetraalkylammonium compound can be or can include tetrabutylammonium halide or tetrahexylammonium halide, in particular tetrabutylammonium bromide or tetrabutylammonium chloride or tetrahexylammonium bromide or tetrahexylammonium chloride. The coating (e.g., coating, polymeric coating composition (before curing)) may include about 1 to 15 weight percent of the quaternary ammonium salt. The molar ratio of acid dye to quaternary ammonium compound can range from about 3:1 to 1:3 or about 1.5:1 to 1: 1.5.

The coating (e.g., the coating, the polymeric coating composition (before curing), the monomers and/or polymers of the matrix of the crosslinked polymer, or the precursor of the coating) may include a crosslinking agent for crosslinking the polymeric component of the coating. The crosslinking agent may be an aqueous crosslinking agent. The cross-linking agent may include one or more of the following: a polycarboxylic acid crosslinking agent, an aldehyde crosslinking agent, a polyisocyanate crosslinking agent, or a combination 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 polyacrylic acid, polymaleic acid, copolymers of acids, copolymers of maleic acid, fumaric acid, or 1,2,3, 4-butanetetracarboxylic acid. The concentration of the crosslinking agent can be about 0.01 to 5 weight percent or 1 to 3 weight percent of the coating.

The coating (e.g., the coating, the polymeric coating composition (before curing), the monomers and/or polymers of the matrix of the crosslinked polymer, or the precursor of the coating) can include a solvent. The solvent may be an organic solvent. The organic solvent may be a water-miscible organic solvent. The coating may contain no water, or may be substantially free of water. For example, the solvent may be or may include acetone, ethanol, 2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethyl ketone, 1-butanol, t-butanol, or any mixture thereof.

Various aspects of the structurally colored articles have been described, providing additional details regarding the recycled thermoplastic compositions produced by the structurally colored articles and components. Various embodiments disclosed herein provide a composition, part, or article comprising a recycled thermoplastic composition. Recycled thermoplastic compositions are the result of recycling articles or parts or compositions that color a structure comprising a thermoplastic material and an optical element. The recycled thermoplastic composition comprises more than one optical element or fragment thereof dispersed in the thermoplastic material.

As a result of recycling, the optical element of the structurally colored article or component is at least partially modified from its pre-recycled state such that it no longer exhibits or imparts an optical effect (e.g., a structural color including "color", iridescent appearance, or metallic appearance), or at least has a reduced ability to exhibit or impart an optical effect to the recycled thermoplastic composition or the component or article formed from the recycled thermoplastic composition. Recycling of structurally colored articles having optical elements includes processing (e.g., grinding, cutting, shredding, etc.) the optical elements to produce a material that includes more than one smaller optical element or segment. A portion of the optical elements and segments (e.g., 1 to 99 weight percent) can be degraded such that they do not impart an optical effect after processing. Alternatively or additionally, another portion of the optical elements and segments (e.g., a small amount, or from 1 to 40 weight percent, or from 1 to 20 weight percent, or less than 10 weight percent) are not degraded and may impart minimal or no optical effect that is visible at a distance of about 1 meter to an observer having 20/20 visual acuity and normal color vision. More than one optical element or segment may include at least a partially complete portion of an optical element, e.g., a smaller segment having one or more layers of optical element structures that are not structurally degraded. More than one optical element or segment may include an incomplete portion of the optical element, e.g., the optical element is melted or otherwise transformed such that one or more layers are no longer distinguishable and/or have different properties than the original optical element disposed on the structurally colored article. However, the collective optical elements or fragments thereof dispersed in the recycled thermoplastic composition degrade or deteriorate to a state where they are insufficient to impart structural color to the recycled thermoplastic composition or an article or part formed from the recycled thermoplastic composition.

The size of more than one optical element or segment may contribute to their ability to impart an optical effect to the composition, structure, or component. For example, beyond a certain size, the optical element segment may be capable of imparting a color or iridescence to the component or structure. The optical element and the segment of the optical element are layered structures having two or more layers stacked in a z-dimension orthogonal to the plane of the layered stack. In addition, the optical elements and segments of the optical elements have a width in the x-dimension, a length in the y-dimension, and a thickness in the z-dimension. In various embodiments, the optical elements or segments are sized in one or more of length, width, and/or thickness such that they do not impart an optical effect. The thickness of the optical elements or fragments of optical elements dispersed in the recycled thermoplastic composition can be less than 30 percent, less than 20 percent, less than 10 percent, less than 5 percent, or less than the thickness of the optical elements on the structurally colored article (prior to recycling). The width and/or length of the segments of optical elements dispersed in the recycled thermoplastic composition can be at least about 50 percent, or 45 percent, or 40 percent, or 35 percent, or 25 percent, or 20 percent, or 15 percent, or 10 percent, or 5 percent or less, respectively, less than the width and/or length of the optical elements on the structurally colored article (prior to recycling). In some embodiments, more than one optical element or segment dispersed in the recycled thermoplastic composition can have an average size, as measured along the largest dimension (in the x, y, or z dimension), of less than 400 nanometers, optionally less than 300 nanometers, or less than 200 nanometers, or less than 100 nanometers.

In various embodiments, the more than one optical element or segment comprises from about 1 percent to about 80 percent segments of the optical element, or from about 10 percent to about 50 percent segments of the optical element, based on the total weight of the more than one optical element or segment.

The amount of optical elements or segments in the recycled thermoplastic composition depends to a large extent on the composition of the article or part being colored by the recycled structure. For example, where the optical elements of the structurally colored article are discrete coatings on a small portion of the surface of a larger article, then the resulting recycled thermoplastic composition will contain only a small number of optical elements or segments. In contrast, where the structurally colored article or part is a film having optical elements over the entire surface, then the resulting recycled thermoplastic composition will contain a greater amount of optical elements or segments. In some embodiments, the recycled thermoplastic composition comprises less than 20 weight percent, or less than 10 weight percent, or less than 5 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of the optical elements or segments, based on the total weight of the recycled thermoplastic composition.

The amount of optical element or segment in the composition or structure can contribute to the ability of the optical element to impart an optical effect to the composition, structure, or component. In some embodiments, the part or article may comprise a composition utilizing a recycled thermoplastic composition, wherein the composition comprises from about 0.01 percent to about 20 percent of the optical elements or segments, or from about 1 percent to about 10 percent of the optical elements or segments, based on the total weight of the composition.

The recycled thermoplastic composition further comprises a thermoplastic material. As a result of the recycling, the thermoplastic material in the recycled thermoplastic composition can be substantially the same as the corresponding thermoplastic material prior to recycling. However, it is possible that the thermoplastic material in the recycled thermoplastic composition may be at least partially modified as a result of one or more recycling processes or steps. For example, the thermoplastic material may be in a different form-e.g., smaller pieces, pellets, or molten form-or may have one or more modified material properties resulting from the recycling process, such as one or more of molecular weight, specific gravity, melt flow index. In various embodiments, the material property of the thermoplastic material in the recycled thermoplastic composition is within about plus or minus 20 percent of the corresponding property of the thermoplastic material prior to recycling.

In some aspects, a structurally colored article or part may comprise a composition comprising one or more colorants, such as pigments or dyes added to the thermoplastic material or to a coating on the article or part. The recycling process described herein will not chemically alter the colorant nor reduce or remove the colorant. As a result of the recycling process, the recycled thermoplastic composition will contain a colorant.

In aspects, the recycled thermoplastic composition is blended with one or more additional materials, such as additional thermoplastic materials. In aspects, the one or more additional thermoplastic materials are the same or substantially the same thermoplastic material as the recycled thermoplastic composition. For example, a recycled thermoplastic composition can be produced by recycling a structurally colored article comprising a thermoplastic polyurethane, and then blending the recycled thermoplastic composition with an additional amount of thermoplastic polyurethane or blend comprising a thermoplastic polyurethane. In other aspects, the one or more additional thermoplastic materials are different materials. For example, a recycled thermoplastic composition may be produced by recycling an article comprising a first thermoplastic material, and the additional thermoplastic material comprises a thermoplastic material different from the first thermoplastic material. In some aspects, the additional thermoplastic material may be virgin material, i.e., material that has not been recycled. In some aspects, the additional thermoplastic material may at least partially comprise recycled thermoplastic material.

In various aspects, a composition comprising a recycled thermoplastic composition can comprise at least 25 weight percent, or at least 50 weight percent, or at least 75 weight percent, or at least 90 weight percent, or at least 95 weight percent of a second thermoplastic material. The second thermoplastic material can be the same (or substantially the same) or different from the thermoplastic material of the recycled thermoplastic composition. For example, the polymer component of the second thermoplastic composition can be the same or substantially the same as the polymer component of the recycled thermoplastic composition, or can be different from the polymer component of the recycled thermoplastic composition.

Optionally, the recycled thermoplastic composition may further comprise one or more additives. Exemplary additives may include pigments, stabilizers, flame retardants, waxes, antioxidants, and the like. Optional additives may be provided, for example, to improve the material properties or to facilitate the processability of the recycled thermoplastic composition. For example, the recycled thermoplastic composition may optionally include a plasticizer to increase flexibility and durability of the final product, and/or to facilitate processing of the material by subsequent processes such as extrusion or molding. The recycled thermoplastic composition may optionally include a processing aid such as a mold release agent or lubricant. One of ordinary skill in the art will recognize that these and other optional additives may be added to the recycled thermoplastic composition to achieve the necessary or desired results.

According to various embodiments, the recycled thermoplastic composition and articles or parts made therefrom have different optical properties than the structurally colored article or part prior to recycling.

In some embodiments, the colored structure or component can be characterized by recycling the optical property differences. The recycling optical property difference is a measure of the change in the optical properties of the structure before and after recycling. In this context, the optical property may include, for example, a visible light transmittance measurement, a visible light reflectance measurement, or a color measurement. A larger difference in recycled optical properties indicates a larger change in optical properties due to recycling. Conversely, a smaller difference in recycled optical properties indicates a smaller change in optical properties due to recycling.

According to the method, a target surface of a structure or component is identified and isolated. The target surface is a surface representing a visible feature or structure, including a color or optical effect exhibited by the structure or feature. For example, if a structure or component is colored with a pigment or dye in a thermoplastic material, the target surface will be identified on the side of the component or structure having a representative amount of the pigment or dye in its thermoplastic material; if the coating is used to color a structure or component, the target surface will have a representative coating across the target surface.

Using the methods described further herein, differences in recycled optical properties of a target surface of a structure or component can be measured. The difference in recycled optical properties of structurally colored parts or articles is greater than that of parts or articles colored with conventional colorants such as dyes or pigments. In parts or articles that are colored with dyes or pigments, the dyes or pigments are carried into the recycled thermoplastic composition by a recycling process. As a result, the optical properties of the first and second structures are not substantially different. In contrast, for parts that are structurally colored with an optical element, the structural color depends on the structure of the optical element, e.g., the presence and relationship of multiple layers of the optical element. Recycling of structures comprising optical elements results in structural degradation of the optical elements, resulting in optical elements or segments thereof having different sizes, structures and layers. As a result, the optical elements or fragments thereof in the recycled thermoplastic composition do not exhibit or impart the same optical effects as they impart on the structurally colored article. Thus, the structurally colored parts or articles have a relatively higher difference in recycled optical properties than conventionally colored parts and articles.

In various embodiments, a structurally colored part or article includes greater than 40 percent, or greater than 45 percent, or greater than 50 percent, or greater than 55 percent, or greater than 60 percent, or greater than 65 percent, or greater than 70 percent, or greater than 75 percent, or greater than 80 percent, or greater than 85 percent, or greater than 90 percent recycled optical property differences.

According to various embodiments, the recycled thermoplastic composition and articles or parts made therefrom have very similar optical properties to similar compositions, articles or parts that do not include optical elements or segments. For example, a first sheet or film comprising a first thermoplastic material and a recycled thermoplastic composition comprising an optical element or fragment thereof can have a first optical property (e.g., visible light transmittance, color measurement, or both) that is within about 10 percent of the same optical property (e.g., visible light transmittance, color measurement, or both, respectively) of a sheet or film comprising only the first thermoplastic material (i.e., in the absence of the optical element or fragment). Because the recycled thermoplastic composition does not significantly alter the optical properties of the first thermoplastic material, it can be more easily combined with the first thermoplastic material without significant visual impact on the resulting composition, part, or article. As a result, a higher percentage of recycled thermoplastic composition may be included in the recycle stream for material and cargo manufacturing.

In various embodiments, a part or article comprising a recycled thermoplastic composition comprising a first thermoplastic material and an optical element or fragment thereof has a minimum visible light transmittance that is within 10 percent (plus or minus), or within 9 percent, or within 8 percent, or within 7 percent, or within 6 percent, or within 5 percent, or within 4 percent, or within 3 percent, or within 2 percent of the visible light transmittance of a part or article comprising the first polymeric material in the absence of the optical element or fragment thereof.

In various embodiments, a part or article comprising a recycled thermoplastic composition comprising a first thermoplastic material and an optical element or fragment thereof has a color measurement within 10 percent (plus or minus) of the color measurement of a part or article comprising the first polymeric material in the absence of the optical element or fragment thereof, or within 9 percent, or within 8 percent, or within 7 percent, or within 6 percent, or within 5 percent, or within 4 percent, or within 3 percent, or within 2 percent. In some embodiments, the first thermoplastic material may be colored, for example with a dye or pigment. Regardless of whether the first thermoplastic material has a colorant or not, the color measurement of the recycled thermoplastic composition comprising the optical element or segment thereof will be similar to the color measurement of the first thermoplastic material without the optical element or segment present.

In various embodiments, the color measurements of two items can be characterized and compared according to the CIE 1976 color space. A first structure compositionally comprising a first thermoplastic material and an optical element or segment thereof has a coordinate L at an observation angle of about-15 degrees to 180 degrees or about-15 degrees and +60 degrees under given illumination conditions₁A and a₁A and b₁A first color measurement and a second structure compositionally comprising a first thermoplastic material, absent an optical element or fragment thereof, has a coordinate L₂A and a₂A and b₂Second color measurement of, wherein Δ E between the first color measurement and the second color measurement_abLess than or equal to about 4, wherein Δ E_ab＝[(L₁*-L₂*)²+(a₁*–a₂*)²+(b₁*-b₂*)²]^1/2Or optionally Δ E_abLess than or equal to about 3, or optionally less than or equal to about 2, or optionally less than or equal to about 1.

Having discussed the recycled thermoplastic composition, we now provide additional details regarding the method of recycling the article or component colored by the structure.

According to various embodiments, the method of recycling includes the step of converting the structurally colored article into a recycled thermoplastic composition. Prior to converting, the structurally colored article includes at least one structure comprising a thermoplastic material and having optical elements disposed on sides of the structure that impart a color to the structure. After conversion, the resulting recycled thermoplastic composition comprises a thermoplastic material and more than one optical element or fragment thereof dispersed in the thermoplastic material. In certain embodiments, the converting step may include any process or combination of processes that can be used to act on the recyclable material to produce a material having a particle size small enough to make the material suitable for use in subsequent polymer processing methods. Exemplary processes include abrading an article or a portion thereof, cutting an article or a portion thereof, or a combination of the foregoing. Exemplary milling or cutting techniques include, but are not limited to, grinding (or regrinding), cutting, shredding, pulverizing, crushing, grinding, flaking, and the like. The particle size produced by processing the article is not limited unless the particle size should be of a sufficient degree or degree suitable for use in polymer processing operations, such as, for example, to achieve suitable softening or melting properties, or for use in a mixer or extrusion process.

In various aspects, the converting may include melting the article or a portion thereof. For example, ground or cut thermoplastic material may be heated to produce an at least partially molten material. In various embodiments, the first thermoplastic material has a first glass transition temperature. In the melting step, the temperature of the ground or cut material may be raised, for example by suitable heating means, to a temperature above the first glass transition temperature to produce an at least partially molten material. The molten material may be further processed, as needed or desired, such as by filtration or the like, to render it suitable for further processing.

According to various embodiments, the method of recycling does not include chemically altering any colorant, nor does it include reducing or removing any colorant. In other words, if the structurally colored article includes any pigments or dyes, these pigments or dyes will be carried by the method of recycling and will be included in the recycled thermoplastic composition, as well as any structure or article that includes the recycled thermoplastic composition.

The method of recycling may optionally include extruding the molten material, or co-extruding the molten material with one or more additional materials. Extrusion may be carried out using any extruder known in the art. In some embodiments, the recycled thermoplastic composition may be extruded (or coextruded) into a film or sheet or web. In some embodiments, the recycled thermoplastic composition may be extruded to form fibers and/or a nonwoven web. In some embodiments, the extruded material may be laminated to one or more additional materials. For example, the recycled thermoplastic composition can be extruded (or coextruded) into a film or sheet or web that is laminated to another web.

The method of recycling may optionally include pelletizing the ground, molten or extruded material. For example, an extruder may extrude molten material into the shape of pellets, or the molten or extruded material may be otherwise formed into pellets having a desired size and shape. The pellets may then be solidified, for example, by lowering the temperature of the extruded material below the glass transition temperature of the pelletized material.

The method of recycling may optionally include blending or mixing the recycled thermoplastic material with one or more additional thermoplastic materials. The blending step may be performed before, during or after one or more of a grinding step or a cutting step, a melting step, an extrusion step and/or a pelletizing step. The blending step may use a static mixer or other device to provide the necessary or desired mixing or blending of the thermoplastic materials.

The method of recycling may further comprise forming another article of a second composition comprising the recycled thermoplastic composition. The second composition may comprise from about 1 weight percent to about 100 weight percent of the recycled thermoplastic composition.

The method of recycling may optionally include decorating or coloring the recycled thermoplastic composition or the part or article formed therefrom. For example, the resulting article may be colored with one or more dyes or pigments, or may be printed with a desired pattern. In some embodiments, optical elements may be disposed on an article formed from the recycled thermoplastic composition to impart a structural color to the article.

Additional details are provided regarding the polymeric materials mentioned herein, for example regarding the thermoplastic polymers and materials described below: articles, components of articles, structures, layers, films, bladders, foams, primer layers, coatings, and the like. The thermoplastic material is described with respect to the structurally colored article prior to recycling as well as recycled thermoplastic compositions and compositions including recycled thermoplastic compositions. The thermoplastic material may comprise as a polymer component a thermoplastic polymer, optionally a thermoplastic elastomer. The thermoplastic polymer may include one or more thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic copolymers thereof, or combinations thereof.

The polymer component of the thermoplastic material may comprise or consist essentially of: thermoplastic polyurethanes, including thermoplastic polyester polyurethane copolymers. The polymer component of the thermoplastic material may comprise or consist essentially of a thermoplastic polyester. The polymer component of the thermoplastic material may comprise or consist essentially of a thermoplastic polyether. The polymer component of the thermoplastic material may comprise or consist essentially of: thermoplastic polyamides, including thermoplastic polyamide copolymers, such as polyether block amide (PEBA) block copolymers. The polymer component of the thermoplastic material may comprise or consist essentially of: thermoplastic polyolefins, including thermoplastic polypropylene, thermoplastic polyethylene, and copolymers of ethylene or polypropylene, such as ethylene-vinyl acetate or ethylene-vinyl alcohol copolymers.

In particular examples, the polymer component of the recycled thermoplastic composition can include or consist essentially of a thermoplastic polyurethane, and the recycled thermoplastic composition can be combined with a thermoplastic material having a polymer component that can include or consist essentially of a mixture of a thermoplastic polyurethane and a thermoplastic ethylene-vinyl alcohol copolymer.

The term "polymer" refers to a compound formed from more than one repeating structural unit called a monomer. Polymers are typically formed by polymerization reactions in which more than one building block becomes covalently bonded together. When the monomer units forming the polymer all have the same chemical structure, the polymer is a homopolymer. When the polymer comprises two or more monomer units having different chemical structures, the polymer is a copolymer. One example of a copolymer type is a terpolymer, which includes three different types of monomer units. The copolymer can include two or more different monomers randomly distributed in the polymer (e.g., a random copolymer). Alternatively, one or more blocks comprising more than one monomer of the first type may be combined with one or more blocks comprising more than one monomer of the second type to form a block copolymer. A single monomeric unit may include one or more different chemical functional groups.

A polymer having a repeating unit comprising two or more types of chemical functional groups may be referred to as having two or more segments. For example, polymers having repeating units of the same chemical structure may be referred to as having repeating segments. A segment is generally described as being relatively hard or soft, based on the chemical structure of the segment, and a polymer generally includes relatively hard and soft segments bonded to each other in a single monomeric unit or in different monomeric units. When the polymer comprises repeating segments, physical interactions or chemical bonds may be present within the segments or between the segments, or both. Examples of segments commonly referred to as hard segments include segments comprising urethane linkages, which can be formed by reacting an isocyanate with a polyol to form a polyurethane. Examples of segments commonly referred to as soft segments include segments comprising alkoxy functionality, such as segments comprising ether functionality or ester functionality, and polyester segments. The segments may be referred to based on the name of the functional groups present in the segment (e.g., polyether segments, polyester segments), as well as the name of the chemical structure that reacts to form the segment (e.g., polyol-derived segments, isocyanate-derived segments). When referring to a segment of a particular functional group or a segment of a particular chemical structure from which the segment is derived, it is understood that the polymer may contain up to 10 mole percent of segments of other functional groups or segments derived from other chemical structures. For example, as used herein, a polyether segment is understood to include up to 10 mole percent of non-polyether segments.

As previously described, the polymer may be a thermoplastic polymer. Generally, thermoplastic polymers soften or melt when heated and return to a solid state when cooled. A thermoplastic polymer transitions from a solid state to a softened state when its temperature is increased to a temperature at or above its softening temperature, and transitions to a liquid state when its temperature is increased to a temperature at or above its melting temperature. When sufficiently cooled, the thermoplastic polymer transitions from a softened or liquid state to a solid state. In this way, the thermoplastic polymer can be softened or melted, molded, cooled, re-softened or re-melted, re-molded, and re-cooled through multiple cycles. By amorphous thermoplastic polymer, the solid state is understood to be the "rubbery" state above the glass transition temperature of the polymer. The thermoplastic polymer may have a melting temperature of from about 90 ℃ to about 190 ℃ when determined according to ASTM D3418-97 as described herein below, and includes all subranges therein in 1 degree increments. The thermoplastic polymer may have a melting temperature of from about 93 ℃ to about 99 ℃ when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer may have a melting temperature of from about 112 ℃ to about 118 ℃ when determined according to ASTM D3418-97 as described herein below.

The glass transition temperature is the temperature at which an amorphous polymer transitions from a relatively brittle "glass" state to a relatively more flexible "rubber" state. The thermoplastic polymer may have a glass transition temperature of from about-20 ℃ to about 30 ℃ when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer may have a glass transition temperature of from about-13 ℃ to about-7 ℃ when determined according to ASTM D3418-97 as described herein below. The thermoplastic polymer may have a glass transition temperature of from about 17 ℃ to about 23 ℃ when determined according to ASTM D3418-97 as described herein below.

When tested according to ASTM D1238-13 as described herein belowThe thermoplastic polymer can have a weight of from about 10 cubic centimeters per 10 minutes (cc/10 min) to about 30 cubic centimeters per 10 minutes (cm) when tested at 160 ℃ using a weight of 2.16 kilograms (kg)³/10 min). The thermoplastic polymer may have a weight of from about 22cm when tested according to ASTM D1238-13 as described herein below at 160 ℃ using a weight of 2.16kg³A/10 min to about 28cm³Melt flow index at 10 min.

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

The Thermoplastic polymer may have a modulus of about 5 megapascals (MPa) to about 100MPa when measured on thermoformed substrates according to the ASTM D412-98 standard test method for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic elastomer-tensile (Vulcanized Rubbers and Thermoplastic Elastomers-tensile), with the modifications described herein below. The thermoplastic polymer may have a modulus of from about 20MPa to about 80MPa when determined on a thermoformed substrate according to ASTM D412-98 standard test methods for vulcanized rubber and thermoplastic elastomer-tensile, with the modifications described herein below.

The polymer may be a thermosetting polymer. As used herein, "thermoset polymer" is understood to refer to a polymer that cannot be heated and melted because its melting temperature is at or above its decomposition temperature. "thermoset" refers to a material comprising at least one thermoset polymer. Thermoset polymers and/or thermoset materials can be prepared from precursors (e.g., uncured or partially cured polymers or materials) using thermal energy and/or actinic radiation (e.g., ultraviolet radiation, visible radiation, high energy radiation, infrared radiation) to form partially cured or fully cured polymers or materials that no longer remain fully thermoplastic. In some cases, the cured or partially cured polymer or material may retain thermoelastic properties because the polymer or material may be partially softened and molded at elevated temperatures and/or pressures, but it is not possible to melt the polymer or material. For example, curing may be promoted by the use of high pressure and/or catalysts. In many instances, the curing process is irreversible because it results in a crosslinking reaction and/or a polymerization reaction of the precursor. The uncured or partially cured polymer or material may be malleable or liquid prior to curing. In some cases, uncured or partially cured polymers or materials may be molded into their final shape or used as adhesives. After hardening, the thermosetting polymer or thermosetting material cannot be remelted for reshaping. The textured surface may be formed by partially or fully curing an uncured precursor material to lock the textured surface.

Polyurethane

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

One or more of the polyurethanes may be produced by polymerizing one or more isocyanates with one or more polyols to produce polymer chains having urethane linkages (-n (co) O-) as shown in formula 1 below, wherein the isocyanates each preferably include two or more isocyanate (-NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups per molecule (although monofunctional isocyanates may also be optionally included, for example as chain terminating units).

Each R₁Group and R₂The groups are independently aliphatic or aromatic. Optionally, each R₂Can be relatively hydrophilic groups, including groups having one or more hydroxyl groups.

Additionally, the isocyanate may also be chain extended with one or more chain extenders to bridge two or more isocyanates, increasing the length of the hard segment. This can result in a polyurethane polymer chain as shown in formula 2 below, where R is₃Including chain extenders. As for each R₁And R₃In the same way, each R₃Independently an aliphatic functionality or an aromatic functionality.

Each R in formula 1 and formula 2₁The groups may independently include straight or branched chain groups having from 3 to 30 carbon atoms, based on the particular isocyanate used, and may be aliphatic, aromatic, or include a combination of aliphatic and aromatic moieties. The term "aliphatic" refers to a saturated or unsaturated organic molecule or portion of a molecule that does not include a ring conjugated ring system (cycloconjugated ring system) having delocalized pi electrons. In contrast, the term "aromatic" refers to an organic molecule or portion of a molecule having a ring system with a ring conjugate of delocalized pi electrons that exhibits greater stability than a hypothetical ring system with localized pi electrons.

Each R is based on the total weight of the polymer-forming reactant compounds or monomers₁The groups may be present at about 5 percent to about 85 percent by weight, from about 5 percent to about 70 percent by weight, orPresent in an amount from about 10 percent to about 50 percent by weight.

In aliphatic embodiments (from aliphatic isocyanates), each R₁The groups may include straight chain aliphatic groups, branched chain aliphatic groups, cycloaliphatic groups, or combinations thereof. For example, each R₁The groups may include straight or branched chain alkylene groups having from 3 to 20 carbon atoms (e.g., alkylene groups having from 4 to 15 carbon atoms, or alkylene groups having from 6 to 10 carbon atoms), one or more cycloalkylene groups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof. As used herein, the term "alkene" or "alkylene" refers to a divalent hydrocarbon. When associated with the term C_nWhen used in combination, it means that the alkene or alkylene group has "n" carbon atoms. E.g. C_1-6Alkylene refers to an alkylene group having, for example, 1, 2, 3, 4, 5, or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing polyurethane polymer chains include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Butylene Diisocyanate (BDI), diisocyanatocyclohexylmethane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanatomethylcyclohexane, diisocyanatomethyltricyclodecane, Norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4' -dicyclohexylmethane diisocyanate (H12MDI), diisocyanatododecane, lysine diisocyanate, and combinations thereof.

The isocyanate-derived segment may comprise a segment derived from an aliphatic diisocyanate. The majority of the isocyanate-derived segments may include segments derived from aliphatic diisocyanates. At least 90% of the isocyanate-derived segments are derived from an aliphatic diisocyanate. The isocyanate-derived segment may consist essentially of a segment derived from an aliphatic diisocyanate. The aliphatic diisocyanate-derived segments can be substantially (e.g., about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more) derived from linear aliphatic diisocyanates. At least 80% of the aliphatic diisocyanate derived segments may be derived from aliphatic diisocyanates that do not contain side chains. The segment derived from an aliphatic diisocyanate may include a straight chain aliphatic diisocyanate having from 2 to 10 carbon atoms.

When the isocyanate-derived segment is derived from an aromatic isocyanate, each R₁The groups may comprise one or more aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylene, indanyl, indenyl, anthracenyl and fluorenyl. Unless otherwise specified, the aromatic group can be an unsubstituted aromatic group or a substituted aromatic group, and can also include heteroaromatic groups. "heteroaromatic" refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system wherein one to four ring atoms are selected from oxygen, nitrogen, or sulfur and the remaining ring atoms are carbon, and wherein the ring system is attached to the remainder of the molecule through any ring atom. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl and benzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing polyurethane polymer chains include Toluene Diisocyanate (TDI), TDI adduct with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), Xylene Diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), Hydrogenated Xylene Diisocyanate (HXDI), naphthalene 1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 4' -dibenzyl diisocyanate (DBDI), 4-chloro-1, 3-phenylene diisocyanate, and combinations thereof. The polymer chain may be substantially free of aromatic groups.

The polyurethane polymer chain may be made from materials including HMDI, TDI, MDI, H₁₂Aliphatic compounds and combinations thereof. For example, polyurethanesThe ester may comprise one or more polyurethane polymer chains derived from diisocyanates including HMDI, TDI, MDI, H₁₂Aliphatic compounds and combinations thereof.

In accordance with the present disclosure, at least partially crosslinked or crosslinkable polyurethane chains may be used. By reacting polyfunctional isocyanates to form polyurethanes, crosslinked or crosslinkable polyurethane chains can be produced. Examples of suitable triisocyanates for producing polyurethane chains include TDI, HDI and IPDI adducts with Trimethylolpropane (TMP), uretdione (i.e., dimerized isocyanate), polymeric MDI, and combinations thereof.

R in formula 2₃The groups may include straight or branched chain groups having from 2 to 10 carbon atoms based on the particular chain extender polyol used, and may be, for example, aliphatic, aromatic, or ether or polyether. Examples of suitable chain extender polyols for producing polyurethanes include ethylene glycol, lower oligomers of ethylene glycol (e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol), 1, 2-propanediol, 1, 3-propanediol, lower oligomers of propylene glycol (e.g., dipropylene glycol, tripropylene glycol, and tetrapropylene glycol), 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, 2-ethyl-1, 6-hexanediol, 1-methyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, dihydroxyalkylated aromatic compounds (e.g., bis (2-hydroxyethyl) ethers of hydroquinone and resorcinol, xylene-a, bis (2-hydroxyethyl) ether of a-diol, xylene-a, a-diol), and combinations thereof.

R in formula 1 and formula 2₂The groups may include polyether groups, polyester groups, polycarbonate groups, aliphatic groups, or aromatic groups. Each R is based on the total weight of the reactant monomers₂The groups may be present in an amount of about 5 percent to about 85 percent by weight, from about 5 percent to about 70 percent by weight, or from about 10 percent to about 50 percent by weight.

At least one R of polyurethane₂The groups include polyether segments (i.e., segments having one or more ether groups). Suitable polyether groups include, but are not limited to, polyepoxidesEthane (PEO), polypropylene oxide (PPO), Polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof. The term "alkyl" as used herein refers to straight and branched chain saturated hydrocarbon groups containing from one to thirty carbon atoms, for example from one to twenty carbon atoms or from one to ten carbon atoms. When associated with the term C_nWhen used in combination, it means that the alkyl group has "n" carbon atoms. E.g. C₄Alkyl refers to an alkyl group having 4 carbon atoms. C_1-7Alkyl refers to an alkyl group having a number of carbon atoms that encompasses the entire range (i.e., 1 to 7 carbon atoms) as well as all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7 carbon atoms). Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), tert-butyl (1, 1-dimethylethyl), 3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise specified, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group.

In some examples of the polyurethane, at least one R₂The groups include polyester groups. The polyester groups can be derived from the polyesterification of one or more dihydric alcohols (e.g., ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methylpentanediol, 1, 5-diethylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid, suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid, and citraconic acid, and combinations thereof). The polyester groups may also be derived from polycarbonate prepolymers such as poly (hexamethylene carbonate) diol, poly (trimethylene carbonate) diol, poly (tetramethylene carbonate) diol, and poly (nonamethylene carbonate) diol. Suitable polyesters may include, for example, polyethylene adipate (PEA), poly (1, 4-butylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly (hexamethylene adipates)Propyl carbonate), poly (tetramethylene carbonate), poly (nonamethylene carbonate), and combinations thereof.

At least one R₂The groups may include polycarbonate groups. The polycarbonate groups may be derived from the reaction of one or more dihydric alcohols (e.g., ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methylpentanediol, 1, 5-diethylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with ethylene carbonate.

The aliphatic group may be linear, and may include, for example, an alkylene chain having from 1 to 20 carbon atoms or an alkenylene chain having from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, vinylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term "alkene" or "alkylene" refers to a divalent hydrocarbon. The term "alkenylene" refers to a divalent hydrocarbon molecule or portion of a molecule having at least one double bond.

The aliphatic and aromatic groups may be substituted with one or more relatively hydrophilic and/or charged pendant groups. The hydrophilic pendant group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) hydroxyl groups. The pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) amino groups. In some cases, the hydrophilic pendent group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) carboxylate groups. For example, the aliphatic group may include one or more polyacrylic acid groups. In some cases, the hydrophilic pendent group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) sulfonate groups. In some cases, the hydrophilic pendent group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) phosphate groups. In some examples, the hydrophilic pendant groups include one or more ammonium groups (e.g., tertiary and/or quaternary ammonium). In other examples, the hydrophilic pendant group includes one or more zwitterionic groups (e.g., betaines, such as poly (carboxybetaine) (pCB) and ammonium phosphonate groups, such as phosphatidyl choline groups).

R₂The groups may include charged groups capable of binding counterions to ionically crosslink the polymer and form an ionomer. For example, R₂Are aliphatic or aromatic groups having pendant amino groups, pendant carboxylate groups, pendant sulfonate groups, pendant phosphate groups, pendant ammonium groups, or pendant zwitterionic groups, or a combination thereof.

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

The hydrophilic side groups can be polyether groups (e.g., polyethylene oxide (PEO) groups, polyethylene glycol (PEG) groups), polyvinylpyrrolidone groups, polyacrylic acid groups, or combinations thereof.

The pendant hydrophilic groups can be bonded to aliphatic or aromatic groups through a linking group. The linking group can be any bifunctional small molecule capable of linking the hydrophilic pendant group to an aliphatic or aromatic group (e.g., a bifunctional small molecule having from 1 to 20 carbon atoms). For example, the linking group can include a diisocyanate group as previously described herein that forms a urethane linkage when connected to the hydrophilic side group as well as to the aliphatic or aromatic group. The linking group may be 4,4' -diphenylmethane diisocyanate (MDI), as shown below.

The hydrophilic side groups may be polyethylene oxide groups and the linking groups may be MDI, as shown below.

The pendant hydrophilic groups can be functionalized to enable them to be bonded to aliphatic or aromatic groups, optionally through a linking group. For example, when the hydrophilic pendant group comprises an olefinic group, the olefinic group can undergo Michael addition with a thiol-containing bifunctional molecule (i.e., a molecule having a second reactive group such as a hydroxyl group or an amino group) to produce a hydrophilic group that can react with the polymer backbone, optionally through a linker, using the second reactive group. For example, when the hydrophilic side group is a polyvinylpyrrolidone group, it can react with a thiol group on mercaptoethanol to produce a hydroxyl-functionalized polyvinylpyrrolidone, as shown below.

At least one R in the polyurethane₂The groups may include polytetramethylene oxide ether groups. At least one R in the polyurethane₂The groups may include aliphatic polyol groups functionalized with polyethylene oxide groups or polyvinylpyrrolidone groups, such as the polyols described in european patent No. 2462908, which is hereby incorporated by reference. For example, R ₂The groups may be derived from the reaction product of a polyol (e.g. pentaerythritol or 2,2, 3-trihydroxypropanol) with an MDI derived methoxypolyethylene glycol (to obtain a compound as shown in formula 6 or formula 7) or with an MDI derived polyvinylpyrrolidone (to obtain a compound as shown in formula 8 or formula 9) which had been previously reacted with mercaptoethanol as shown below.

At least one R in the polyurethane₂May be a polysiloxane. In these cases, R₂The groups may be derived from siloxane monomers of formula 10, such as the siloxane monomers disclosed in U.S. patent No. 5,969,076, which is hereby incorporated by reference:

wherein: a is 1 to 10 or greater (e.g., 1, 2,3, 4, 5, 6, 7, 8, 9, or 10); each R₄Independently hydrogen, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms, an aryl group, or a polyether; and each R₅Independently an alkylene group having from 1 to 10 carbon atoms, a polyether or a polyurethane.

Each R₄The groups may independently be H, an alkyl group having from 1 to 10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aryl group having from 1 to 6 carbon atoms, a polyethylene group, a polypropylene group, or a polybutylene group. Each R ₄The groups may be independently selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, propenyl, phenyl and polyethylene groups.

Each R₅The groups may independently include alkylene groups having from 1 to 10 carbon atoms (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene groups). Each R₅The groups may be polyether groups (e.g. polyethylene groups, polypropylene groups orA polybutene group). Each R₅The groups may be polyurethane groups.

Optionally, the polyurethane may comprise an at least partially crosslinked polymer network comprising polymer chains that are derivatives of the polyurethane. The level of crosslinking can be such that the polyurethane retains thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane can melt and resolidify under the processing conditions described herein). The crosslinked polyurethane may be a thermoset polymer. As shown in formulas 11 and 12 below, the crosslinked polymer network may be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polymercapto compounds (polysufhydryl compounds), or combinations thereof:

Wherein the variables are as described above. Additionally, the isocyanate may also be chain extended with one or more polyamino or polythiol chain extenders to bridge two or more isocyanates, such as described previously for the polyurethane of formula 2.

The polyurethane chain may be physically cross-linked to another polyurethane chain by, for example, nonpolar interactions or polar interactions between the urethane (urethane) or urethane (carbamate) groups (hard segments) of the polymer. R in formula 1₁A group and R in formula 2₁Group and R₃The groups form part of a polymer commonly referred to as a "hard segment", and R₂The groups form part of a polymer commonly referred to as a "soft segment". The soft segment is covalently bonded to the hard segment. The polyurethane having physically crosslinked hard and soft segments can be a hydrophilic polyurethane (i.e., a polyurethane that includes a thermoplastic polyurethane that includes hydrophilic groups as disclosed herein).

The polyurethane may be a thermoplastic polyurethane comprising MDI, PTMO and 1, 4-butanediol, as described in U.S. patent No. 4,523,005. Commercially available polyurethanes suitable for use in the present invention include, but are not limited to, polyurethanes sold under the trade name "SANCURE" (e.g., "SANCURE" series of polymers such as "SANCURE" 20025F) or "TECHNILIC" (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60) (Lubrizol, Countryside, IL, USA), "PELLETHANE" 2355-85ATP and 2355-95AE (Dow Chemical Company of Midland, MI, USA), "ESTANE" (e.g., ALR G500 or 58213; Lubrizol, Countryside, IL, USA).

One or more of the polyurethanes, such as those used in primers as coatings (e.g., water-dispersible polyurethanes), can be produced by polymerizing one or more isocyanates with one or more polyols to produce copolymer chains having urethane linkages (-N (C ═ O) O-) and one or more water-dispersibility enhancing moieties, where the polymer chains comprise one or more water-dispersibility enhancing moieties (e.g., monomers in the polymer chains). Water-dispersible polyurethanes may also be referred to as "aqueous polyurethane polymer dispersions". The water dispersibility-enhancing moiety can be added to the chain of formula 1 or formula 2 (e.g., within the chain and/or as a side chain onto the chain). The inclusion of a water-dispersibility enhancing moiety enables the formation of aqueous polyurethane dispersions. The term "aqueous" herein means a continuous phase of a dispersion or formulation having from about 50 to 100 weight percent water, from about 60 to 100 weight percent water, from about 70 to 100 weight percent water, or about 100 weight percent water. The term "aqueous dispersion" refers to a dispersion of components (e.g., polymers, crosslinkers, and the like) in water without a cosolvent. Co-solvents may be used in the aqueous dispersion, and the co-solvent may be an organic solvent. Additional details regarding the polymers, polyurethanes, isocyanates, and polyols are provided below.

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

The water dispersibility-enhancing moiety can be a moiety comprising a carboxyl group. The carboxyl group-containing water dispersibility enhancing moiety can be prepared from a compound having the general formula (HO) _xQ(COOH)_yWherein Q may be a linear or branched divalent hydrocarbon group containing 1 to 12 carbon atoms, and x and y may each independently be 1 to 3. Illustrative examples include dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixtures thereof.

The water dispersibility enhancing moiety can comprise a reactive polymer polyol component containing anionic side groups that can be polymerized into the backbone to impart water dispersibility characteristics to the polyurethane. Anionic functional polymer polyols may include anionic polyester polyols, anionic polyether polyols, and anionic polycarbonate polyols, with additional details provided in U.S. patent No. 5,334,690.

The water dispersibility-enhancing moiety can comprise a pendant hydrophilic monomer. For example, water dispersibility-enhancing moieties comprising pendant hydrophilic monomers can include alkylene oxide polymers and copolymers wherein the alkylene oxide groups have from 2 to 10 carbon atoms, as shown in U.S. Pat. No. 6,897,281. Additional types of water dispersibility-enhancing moieties can include thioglycolic acid, 2, 6-dihydroxybenzoic acid, sulfoisophthalic acid (sulfoisophtalic acid), polyethylene glycol, and the like, and mixtures thereof. Additional details regarding water dispersibility enhancing moieties can be found in U.S. patent 7,476,705.

Polyamide

The polymer may comprise a polyamide such as a thermoplastic polyamide or a thermoset polyamide. The polyamide may be an elastomeric polyamide, including an elastomeric thermoplastic polyamide or an elastomeric thermoset polyamide. The polyamide may be a polyamide homopolymer having repeating polyamide segments of the same chemical structure. Alternatively, the polyamide may comprise a plurality of polyamide segments having different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments having different chemical structures may be arranged randomly or may be arranged as repeating blocks.

The polyamide may be a copolyamide (i.e., a copolymer comprising polyamide segments and non-polyamide segments). The polyamide segments of the copolyamide may comprise or consist of: polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the copolyamide may be arranged randomly or may be arranged as repeating segments. The polyamide segments may comprise or consist of: polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segments and polyamide 12 segments. In examples where the polyamide segments of the copolyamide comprise polyamide 6 segments and polyamide 12 segments, the segments may be randomly arranged. The non-polyamide segments of the copolyamide may comprise or consist of: a polyether segment, a polyester segment, or both a polyether segment and a polyester segment. The copolyamide may be a copolyamide or may be a random copolyamide. The copolyamide may be formed by polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a copolymer comprising polyamide segments). Optionally, the second prepolymer may be a hydrophilic prepolymer.

The polyamide may be a block copolymer comprising a polyamide. For example, the block copolymer may have repeating hard segments and repeating soft segments. The hard segments may include polyamide segments and the soft segments may include non-polyamide segments. The polyamide-containing block copolymer may be an elastomeric copolyamide comprising or consisting of a polyamide-containing block copolymer having repeating hard segments and repeating soft segments. In block copolymers comprising block copolymers having repeating hard and soft segments, physical crosslinks may be present within the segments or between the segments, or both within and between the segments.

The polyamide itself or the polyamide segments of the polyamide-containing block copolymer may be derived from the condensation of polyamide prepolymers such as lactams, amino acids and/or diamino compounds with dicarboxylic acids or activated forms thereof. The resulting polyamide segment contains an amide linkage (- (CO) NH-). The term "amino acid" refers to a molecule having at least one amino group and at least one carboxyl group. Each polyamide segment in the polyamide may be the same or different.

The polyamide segment of the polyamide or polyamide-containing block copolymer may be derived from the polycondensation of a lactam and/or an amino acid, and may comprise an amide segment having a structure shown in formula 13 below, wherein R is₆The groups represent polyamide moieties derived from lactams or amino acids.

R₆The group may be derived from a lactam. R₆The group may be derived from a lactam group having from 3 to 20 carbon atoms, or a lactam group having from 4 to 15 carbon atoms, or a lactam group having from 6 to 12 carbon atoms. R₆The groups may be derived from caprolactam or laurolactam. R₆The groups may be derived from one or more amino acids. R₆The groups may be derived from amino acid groups having from 4 to 25 carbon atoms, or amino acid groups having from 5 to 20 carbon atoms, or amino acid groups having from 8 to 15 carbon atoms. R₆The group may be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, to increase the relative degree of hydrophilicity of the polyamide-containing block copolymer, formula 13 can include polyamide-polyether block copolymer segments, as shown below:

wherein m is 3 to 20 and n is 1 to 8. Optionally, m is 4-15 or 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12) and n is 1, 2, or 3. For example, m may be 11 or 12, and n may be 1 or 3. The polyamide segment of the polyamide or polyamide-containing block copolymer may be derived from the condensation of a diamino compound with a dicarboxylic acid or an activated form thereof, and may comprise an amide segment having a structure shown in formula 15 below, wherein R is ₇The radicals represent polyamide moieties derived from diamino compounds, and R₈The radicals represent moieties derived from dicarboxylic acid compounds:

R₇the group may be derived from a diamino compound comprising an aliphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbon atoms, or from 6 to 9 carbon atoms. The diamino compound may contain aromatic groups such as phenyl, naphthyl, xylyl, and tolyl. R₇Suitable diamino compounds from which groups may be derived include, but are not limited to, Hexamethylenediamine (HMD), tetramethylenediamine, Trimethylhexamethylenediamine (TMD), m-xylylenediamine (MXD), and 1, 5-pentanediamine. R₈The group may be derived from a dicarboxylic acid or an activated form thereof, including aliphatic groups having from 4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10 carbon atoms. R₈The dicarboxylic acids from which they may be derived, or their activated forms, include aromatic groups such as phenyl, naphthyl, xylyl and tolyl groups. R₈Suitable carboxylic acids or activated forms thereof from which they may be derived include adipic acid, sebacic acid, terephthalic acid and isophthalic acid. The polyamide chain may be substantially No aromatic groups.

Each polyamide segment of the polyamide (including the polyamide-containing block copolymer) may be independently derived from a polyamide prepolymer selected from the group consisting of 12-aminolauric acid, caprolactam, hexamethylenediamine, and adipic acid.

The polyamide may comprise or consist essentially of poly (ether-block-amide). The poly (ether-block-amide) may be formed from the polycondensation of a carboxylic acid terminated polyamide prepolymer and a hydroxyl terminated polyether prepolymer to form a poly (ether-block-amide), as shown in formula 16:

the poly (ether block amide) polymer may be prepared by polycondensation of polyamide blocks containing reactive ends with polyether blocks containing reactive ends. Examples include: 1) polyamide blocks containing diamine chain ends and polyoxyalkylene blocks containing carboxylic acid chain ends; 2) polyamide blocks containing dicarboxylic chain ends and polyoxyalkylene blocks containing diamine chain ends obtained by cyanoethylation and hydrogenation of an aliphatically dihydroxylated alpha-omega polyoxyalkylene known as a polyetherdiol; 3) the product obtained in this particular case is a polyetheresteramide, comprising polyamide blocks having dicarboxylic chain ends and a polyetherdiol. The polyamide blocks of the poly (ether-block-amide) may be derived from lactams, amino acids, and/or diamino compounds and dicarboxylic acids, as previously described. The polyether blocks may be derived from one or more polyethers selected from the group consisting of: polyethylene oxide (PEO), polypropylene oxide (PPO), Polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof.

Poly (ether block amide) polymers may include those comprising polyamide blocks containing dicarboxylic acid chain ends derived from the condensation of alpha, omega-aminocarboxylic acids, lactams, or dicarboxylic acids with diamines in the presence of a chain-limiting dicarboxylic acid. In this type of poly (ether block amide) polymer, an α, ω -aminocarboxylic acid such as aminoundecanoic acid; lactams such as caprolactam or lauryl lactam may be used; dicarboxylic acids such as adipic acid, sebacic acid, or dodecanedioic acid; and diamines such as hexamethylenediamine; or a combination of any of the foregoing. The copolymer may comprise polyamide blocks comprising polyamide 12 or polyamide 6.

The poly (ether block amide) polymers may include those comprising polyamide blocks derived from the condensation of one or more alpha, omega-aminocarboxylic acids and/or one or more lactams having from 6 to 12 carbon atoms in the presence of dicarboxylic acids having from 4 to 12 carbon atoms, and are of low quality, i.e. they have a number average molecular weight of from 400 to 1000. In this type of poly (ether block amide) polymer, an α, ω -aminocarboxylic acid such as aminoundecanoic acid or aminododecanoic acid; dicarboxylic acids such as adipic acid, sebacic acid, isophthalic acid, succinic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, sodium or lithium salts of sulfoisophthalic acid, dimer fatty acids (these dimer fatty acids have a dimer content of at least 98 weight percent and are preferably hydrogenated) and dodecanedioic acid HOOC- (CH) ₂)₁₀-COOH; and lactams such as caprolactam and lauryl lactam; or a combination of any of the foregoing. The copolymer may comprise polyamide blocks obtained by condensation of lauryl lactam in the presence of adipic or dodecanedioic acid and having a number-average molecular weight of at least 750, the copolymer having a melting temperature of from about 127 ℃ to about 130 ℃. The various constituents of the polyamide blocks and their proportions can be chosen so as to obtain a melting point lower than 150 ℃ or from about 90 ℃ to about 135 ℃.

The poly (ether block amide) polymers may include those polymers comprising polyamide blocks derived from the condensation of at least one alpha, omega-aminocarboxylic acid (or lactam), at least one diamine, and at least one dicarboxylic acid. In this type of copolymer, the alpha, omega-aminocarboxylic acid, the lactam and the dicarboxylic acid may be chosen from those described above, and diamines, such as aliphatic diamines containing from 6 to 12 atoms, and which may be acyclic and/or saturated cyclic, such as but not limited to hexamethylenediamine, piperazine, 1-aminoethylpiperazine, diaminopropylpiperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1, 5-diaminohexane, 2, 4-trimethyl-1, 6-diaminohexane, diamine polyols, Isophoronediamine (IPD), methylpentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM) and bis (3-methyl-4-aminocyclohexyl) methane (BMACM).

The polyamide may be a thermoplastic polyamide and the components of the polyamide blocks and their proportions may be selected so as to obtain a melting temperature of less than 150 ℃, such as a melting point of from about 90 ℃ to about 135 ℃. The various components of the thermoplastic polyamide blocks and their proportions may be selected so as to obtain a melting point of less than 150 ℃, such as from about 90 ℃ to about 135 ℃.

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

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

The copolymer comprising polyamide blocks and polyether blocks can be prepared by any means for attaching polyamide blocks and polyether blocks. In practice, basically two processes are used, one being a two-step process and the other being a one-step process.

In a two-step process, polyamide blocks having dicarboxylic chain ends are first prepared and then, in a second step, these polyamide blocks are linked to polyether blocks. The polyamide blocks having dicarboxylic chain ends are derived from the condensation of polyamide precursors in the presence of a chain terminator dicarboxylic acid. If the polyamide precursor is only a lactam or an alpha, omega-aminocarboxylic acid, a dicarboxylic acid is added. If the precursor already contains a dicarboxylic acid, this is used in excess with respect to the stoichiometry of the diamine. The reaction typically takes place at from about 180 ℃ to about 300 ℃, such as from about 200 ℃ to about 290 ℃, and the pressure in the reactor may be set from about 5 bar to about 30 bar and maintained for about 2 to 3 hours. The pressure in the reactor is slowly reduced to atmospheric pressure and then the excess water is distilled off, for example for one or two hours.

After the polyamide with carboxylic acid end groups has been prepared, the polyether, polyol and catalyst are then added. The total amount of polyether may be divided into one or more parts and added in one or more parts, as may the catalyst. The polyether is added first and the reaction of the OH end groups of the polyether and the polyol with the COOH end groups of the polyamide begins, wherein ester bonds are formed and water is eliminated. Removing as much water as possible from the reaction mixture by distillationAnd then introducing a catalyst in order to complete the connection of the polyamide blocks to the polyether blocks. This second step is carried out with stirring, preferably under vacuum of at least 50 mbar (5000 pascals), at a temperature such that the reactants and the copolymer obtained are in the molten state. For example, the temperature may be from about 100 ℃ to about 400 ℃, such as from about 200 ℃ to about 250 ℃. The reaction is monitored by measuring the torque exerted by the polymer melt on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the torque or target power. A catalyst is defined as any product which promotes the attachment of the polyamide blocks to the polyether blocks by esterification. The catalyst may be a derivative of a metal (M) selected from the group formed by titanium, zirconium and hafnium. The derivatives may be of the formula M (OR) ₄Wherein M represents titanium, zirconium or hafnium, and R, which may be the same or different, represents a linear or branched alkyl group having from 1 to 24 carbon atoms.

The catalyst may comprise salts of the metal (M), in particular salts of (M) with organic acids, and complex salts of the oxide of (M) and/or the hydroxide of (M) with organic acids. The organic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, or crotonic acid. The organic acid may be acetic acid or propionic acid. M may be zirconium and such salts are known as zirconyl salts (zirconyl salt), for example, the commercially available product sold under the name zirconyl acetate (zirconyl acetate).

The weight ratio of the catalyst may vary from about 0.01 percent to about 5 percent of the weight of the mixture of the dicarboxylic acid polyamide and the polyether diol and polyol. The weight ratio of the catalyst may vary from about 0.05 percent to about 2 percent of the weight of the mixture of the dicarboxylic acid polyamide and the polyether diol and polyol.

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

Suitable ratios of polyamide blocks to polyether blocks can be found in a single poly (ether block amide), or a blend of two or more poly (ether block amides) of different compositions can be used with a suitable average composition. It may be useful to blend block copolymers having high levels of polyamide groups with block copolymers having higher levels of polyether blocks to produce blends having an average polyether block level of about 20 weight percent to about 40 weight percent, or about 30 weight percent to about 35 weight percent of the total blend of poly (amide-block-ether) copolymers. The copolymer may comprise a blend of two different poly (ether-block-amides) comprising at least one block copolymer having a polyether block level of less than 35 weight percent and a second poly (ether-block-amide) having a polyether block of at least 45 weight percent.

Exemplary commercially available copolymers include, but are not limited to, those available under the following trademarks: "VESTAMID" (Evonik Industries, Essen, Germany); "PLATAMID" (Arkema, Colombes, France), for example, product code H2694; "PEBAX" (Arkema), such as product codes "PEBAX MH 1657" and "PEBAX MV 1074"; "PEBAX RNEW" (Arkema); "GRILAMID" (EMS-Chemie AG, Domat-Ems, Switzerland); or there may be other similar materials produced by other suppliers.

Polyamides can be physically crosslinked by, for example, nonpolar or polar interactions between the polyamide groups of the polymer. In the example where the polyamide is a copolyamide, the copolyamide may be physically crosslinked by interaction between the polyamide groups and optionally by interaction between the copolymer groups. When the copolyamide is physically crosslinked by interaction between the polyamide groups, the polyamide segments may form part of a polymer called hard segments and the copolymer segments may form part of a polymer called soft segments. For example, when the copolyamide is a poly (ether-block-amide), the polyamide segments form the hard segments of the polymer and the polyether segments form the soft segments of the polymer. Thus, in some examples, the polymer may include a physically cross-linked polymer network having one or more polymer chains with amide linkages.

The polyamide segment of the copolyamide may comprise polyamide-11 or polyamide-12 and the polyether segment may be a segment selected from the group consisting of: polyethylene oxide segments, polypropylene oxide segments, and polytetramethylene oxide segments, and combinations thereof.

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

Polyester

The polymer may comprise a polyester. The polyester may comprise a thermoplastic polyester or a thermoset polyester. Further, the polyester may be an elastomeric polyester, including thermoplastic polyesters or thermoset elastomeric polyesters. Polyesters may be formed by the reaction of one or more carboxylic acids or ester-forming derivatives thereof (ester-forming derivatives) with one or more divalent or polyvalent aliphatic, cycloaliphatic, aromatic or araliphatic alcohols or bisphenols. The polyester may be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester may comprise a plurality of polyester segments having different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments having different chemical structures may be arranged randomly or may be arranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare the polyester include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitro-terephthalic acid, 4 '-diphenyl ether dicarboxylic acid, 4' -diphenyl sulfide dicarboxylic acid, 4 '-diphenyl sulfone-dicarboxylic acid, 4' -diphenylalkylene dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, and cyclohexane-1, 3-dicarboxylic acid. Exemplary diols or phenols suitable for use in preparing the polyester include, but are not limited to, ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 2-propanediol, 2-dimethyl-1, 3-propanediol, 2, 4-trimethylhexanediol, p-xylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, and bisphenol A.

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

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

For example, the polyester may be a block copolyester having repeating blocks of polymer units of the same chemical structure that are relatively hard (hard segments) and repeating blocks of the same chemical structure that are relatively soft (soft segments). In block copolyesters comprising block copolyesters having repeating hard and soft segments, physical crosslinking can occur in blocks or between blocks, or both in and between blocks. The polymer may comprise or consist essentially of an elastomeric copolyester having hard segments of repeating blocks and soft segments of repeating blocks.

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

The polyester may be a block copolymer comprising segments of one or more of the following: polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyhexamethylene terephthalate, poly-1, 4-dimethylcyclohexane terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), Polyarylate (PAR), polybutylene naphthalate (PBN) and liquid crystalline polyesters. For example, suitable polyesters as block copolymers may be PET/PEI copolymers, polybutylene terephthalate/tetraethylene glycol copolymers, polyoxyalkylene diimide diacid/polybutylene terephthalate copolymers, or blends or mixtures of any of the foregoing.

The polyester may be a biodegradable resin, for example a copolyester in which a poly (alpha-hydroxy acid) such as polyglycolic acid or polylactic acid is contained as a main repeating unit.

The disclosed polyesters can be prepared by a variety of polycondensation processes known to the skilled artisan, such as a solvent polymerization process or a melt polymerization process.

Polyolefins

The polymer may comprise or consist essentially of a polyolefin. The polyolefin may be a thermoplastic polyolefin or a thermoset polyolefin. Further, the polyolefin may be an elastic polyolefin, including thermoplastic elastic polyolefins or thermoset elastic polyolefins. Exemplary polyolefins may include polyethylene, polypropylene, and olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and an alpha-olefin having from 4 to about 8 carbon atoms). The polyolefin may be a polymer comprising: polyethylene, ethylene-alpha-olefin copolymers, ethylene-propylene rubber (EPDM), polybutylene, polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymers and olefin elastomers such as dynamically cross-linked polymers (dynamic cross-linked polymers) obtained from polypropylene (PP) and ethylene-propylene rubber (EPDM), as well as blends or mixtures of the foregoing. Additional exemplary polyolefins include polymers of cyclic olefins such as cyclopentene or norbornene.

It is to be understood that polyethylenes that may be optionally crosslinked include a variety of polyethylenes, including Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), (VLDPE) and (ULDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), and blends or mixtures of any of the foregoing polyethylenes. The polyethylene can also be a polyethylene copolymer derived from monomers of mono-and di-olefins copolymerized with: vinyl, acrylic, methacrylic, ethyl acrylate, vinyl alcohol, and/or vinyl acetate. The polyolefin copolymer comprising vinyl acetate-derived units can be a high vinyl acetate content copolymer, such as greater than about 50 weight percent of a vinyl acetate-derived composition.

The polyolefin may be formed via free radical polymerization, cationic polymerization, and/or anionic polymerization by methods well known to those skilled in the art (e.g., using peroxide initiators, heat, and/or light). The disclosed polyolefins may be prepared by free radical polymerization at elevated pressure and at elevated temperature. Alternatively, the polyolefin may be prepared by catalytic polymerization using a catalyst that typically contains one or more metals from the group IVb, Vb, VIb or VIII metals. The catalyst typically has one or more than one ligand, typically an oxide, halide, alcoholate, ester, ether, amine, alkyl, alkenyl, and/or aryl that can be para-coordinated or ortho-coordinated, complexed with a group IVb, Vb, VIb, or VIII metal. The metal complexes may be in free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. The metal catalyst may be soluble or insoluble in the polymerization medium. The catalyst may be used alone for polymerization, or an additional activator may be used, typically a group Ia, group IIa and/or group IIIa metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide or metal alkyl siloxane. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups.

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

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

Suitable dynamically crosslinked polymers can be obtained by crosslinking the rubber component as the soft segment while physically dispersing the hard segment such as PP and the soft segment such as EPDM using a kneading machine such as a Banbury mixer (Banbury mixer) and a twin-screw extruder.

The polyolefin may be a mixture of polyolefins, such as a mixture of two or more polyolefins disclosed herein above. For example, a suitable polyolefin blend may be a blend of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP/HDPE, PP/LDPE) or a blend of different types of polyethylene (e.g. LDPE/HDPE).

The polyolefin may be a copolymer of a suitable monoolefin monomer or a copolymer of a suitable monoolefin monomer and a vinyl monomer. Exemplary polyolefin copolymers include ethylene/propylene copolymers, Linear Low Density Polyethylene (LLDPE), and blends thereof with Low Density Polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers, and blends thereof with carbon monoxide or ethylene/acrylic acid copolymers, and salts thereof (ionomers), as well as ethylene with propylene and copolymers such as hexadiene, and the like, A diene terpolymer of dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers (alternating or random polyalkylene/carbon monooxide copolymers) and mixtures thereof with other polymers, for example polyamides.

The polyolefin may be a polypropylene homopolymer, a polypropylene copolymer, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a polyethylene block copolymer, a Low Density Polyethylene (LDPE), a Linear Low Density Polyethylene (LLDPE), a medium density polyethylene, a High Density Polyethylene (HDPE), or a blend or mixture of one or more of the foregoing polymers.

The polyolefin may be polypropylene. As used herein, the term "polypropylene" is intended to encompass any polymer composition comprising propylene monomers, either alone or in admixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers such as ethylene, butylene, and the like. Such terms also encompass any of the different configurations and arrangements of constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, ribbons, stitches, and the like of drawn polymer (draw polymer). The polypropylene may have any standard melt flow (passing the test); however, standard fiber grade polypropylene resins have a melt flow index range between about 1 and 1000.

The polyolefin may be polyethylene. As used herein, the term "polyethylene" is intended to encompass any polymer composition comprising ethylene monomers, either alone or in admixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers such as propylene, butylene, and the like. Such terms also encompass any of the different configurations and arrangements of constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, ribbons, stitches, and the like of drawn polymer. The polyethylene may have any standard melt flow (pass the test); however, standard fiber grade polyethylene resins have a melt flow index range between about 1 and 1000.

The thermoplastic material and/or thermoset material may also include one or more processing aids. The processing aid may be a non-polymeric material. These processing aids may be independently selected from the group including, but not limited to: curing agents, initiators, plasticizers, mold release agents, lubricants, antioxidants, flame retardants, dyes, pigments, reinforcing and non-reinforcing fillers, fiber reinforcing agents and light stabilizers.

In certain embodiments, the structurally colored component may be used in conjunction with a bladder, as further described herein. When a structural design (e.g., an optical element) is disposed onto the balloon, the balloon may be unfilled, partially inflated, or fully inflated. The bladder is a bladder capable of containing a volume of fluid. The unfilled bladder is a fluid-fillable bladder, and the filled bladder has been at least partially inflated with a fluid at a pressure equal to or greater than atmospheric pressure. When disposed on or incorporated into an article of footwear, apparel, or athletic equipment, the bladder is typically a fluid-filled bladder at that time. The fluid is a gas or a liquid. The gas may comprise air, nitrogen (N)₂) Or other suitable gas.

The bladder may have a gas permeability to nitrogen, for example, wherein a bladder wall of a given thickness has a gas permeability to nitrogen that is at least about ten times lower than the gas permeability to nitrogen of a butyl rubber layer having a thickness substantially the same as the thickness of the bladder described herein. The bladder may have a first bladder wall having a first bladder wall thickness (e.g., about 0.1 mils to about 40 mils). The bladder may have a first bladder wall that may have less than about 15cm for an average wall thickness of 20 mils for nitrogen gas ³/m²Atm.day, less than about 10cm³/m²Atm.day, less than about 5cm³/m²Atm.day, less than about 1cm³/m²Atm. day (e.g., from about 0.001 cm)³/m²Atm.day to about 1cm³/m²Atm.day, about 0.01cm³/m²Atm.day to about 1cm³/m²Atm.day or about 0.1cm³/m²Atm.day to about 1cm³/m²Atm · day) Gas Transmission Rate (GTR). The bladder may have a first bladder wall having a first bladder wall thickness, wherein the first bladder wall has 15cm for nitrogen for an average wall thickness of 20 mils³/m²Atm · day or less.

In one aspect, the capsule has a capsule wall having an interior-facing side and an exterior-facing (or exterior) -facing side, wherein the interior-facing (or interior) -facing side defines at least a portion of an interior region of the capsule. A multilayer optical film (or optical element) having a first side and an opposing second side may be disposed on the exterior-facing side of the capsule, the interior-facing side of the capsule, or both. The exterior-facing side of the capsule, the interior-facing side of the capsule, or both, may include more than one topology (or contour feature) extending from the exterior-facing side of the capsule wall, the interior-facing side of the capsule, or both, wherein the first side or the second side of the multilayer optical film is disposed on and covers the exterior-facing side of the capsule wall, is disposed on and covers the interior-facing side of the capsule wall, or both, and wherein the multilayer optical film imparts a color to the capsule wall structure.

In particular aspects, the bladder may include a top wall operatively secured to the footwear upper, a bottom wall opposite the top wall, and one or more sidewalls extending between the top wall and the bottom wall of the inflated bladder. The top wall, the bottom wall, and the one or more side walls collectively define an interior region of the inflated bladder, and wherein the one or more side walls each include an outwardly facing side. A multilayer optical film having a first side and an opposing second side may be disposed on the exterior-facing side of the bladder, the interior-facing side of the bladder, or both. The exterior-facing side of the capsule, the interior-facing side of the capsule, or both, may include more than one topology extending from the exterior-facing side of the capsule wall, the interior-facing side of the capsule, or both, wherein the first side or the second side of the multilayer optical film is disposed on and covers the exterior-facing side of the capsule wall, is disposed on and covers the interior-facing side of the capsule wall, or both, and wherein the multilayer optical film imparts a color to the capsule wall structure.

A well-established method for measuring the relative permeability, permeability and diffusion of an inflated bladder is ASTM D-1434-82-V. See, for example, U.S. patent No. 6,127,026, which is incorporated by reference as if fully set forth herein. According to ASTM D-1434-82-V, the transmission, permeability and diffusion are measured by the following formulae:

Transmittance of light

(amount of gas)/[ (area) x (time) x (differential pressure)]Transmittance (GTR)/(differential pressure) cm³/m²Atm.day (i.e. 24 hours)

Permeability rate of penetration

[ (amount of gas) x (film thickness)][ (area) x (time) x (differential pressure)]Permeability [ (GTR) x (film thickness)](differential pressure) [ (cm)³) (mil)]/m²Atm.day (i.e. 24 hours)

Diffusion at one atmosphere

(amount of gas)/[ (area) x (time)]＝GTR＝cm³/m²Days (i.e. 24 hours).

The capsule may comprise a capsule wall comprising a film comprising at least one polymer layer or at least two or more polymer layers. Each polymer layer may have a thickness of about 0.1 mil to 40 mils.

The polymeric layer may be formed from a polymeric material, such as a thermoplastic material as described above and herein, and may be a thermoplastic layer on which a primer layer may be disposed, on which optical elements may be disposed, on which a textured layer may be disposed, which may be used to form textured layers and the like. The thermoplastic material may comprise an elastomeric material, such as a thermoplastic elastomer. The thermoplastic material may include Thermoplastic Polyurethane (TPU), such as those described above and herein. The thermoplastic material may include a polyester-based TPU, a polyether-based TPU, a polycaprolactone-based TPU, a polycarbonate-based TPU, a polysiloxane-based TPU, or a combination thereof. Non-limiting examples of thermoplastic materials that may be used include: "PELLETHANE" 2355-85ATP and 2355-95AE (Dow Chemical Company of Midland, MI., USA), "ELASTOLLAN" (BASF Corporation, Wyandotte, MI, USA), and "ESTANE" (Lubrizol, Brecksville, OH, USA), all of which are ester-based or ether-based. Additional thermoplastic materials may include those described in the following U.S. patent nos.: 5,713,141; 5,952,065; 6,082,025; 6,127,026; 6,013,340; 6,203,868; and 6,321,465, which are incorporated herein by reference.

The polymer layer may be formed from one or more of the following: ethylene vinyl alcohol copolymers (EVOH), poly (vinyl chloride), polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride), polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g., acrylonitrile-methyl acrylate copolymers), polyurethane engineering plastics, polymethylpentene resins, ethylene-carbon monoxide copolymers, liquid crystal polymers, polyethylene terephthalate, polyetherimides, polyacrylimides, and other polymeric materials known to have relatively low gas transmission rates. Also suitable are blends and alloys of these materials and blends and alloys with the TPU described herein, and blends and alloys optionally including a combination of polyimide and crystalline polymer. For example, blends of polyimides and liquid crystalline polymers, blends of polyamides and polyethylene terephthalate, and blends of polyamides with styrenics are suitable.

Specific examples of the polymeric material of the polymeric layer may include acrylonitrile copolymers such as "BAREX" resins available from Ineos (Rolle, Switzerland); polyurethane engineering plastics such as "ispast" ETPU available from Lubrizol (Brecksville, OH, USA); ethylene vinyl alcohol copolymers sold under the trade name "EVAL" by Kuraray (Houston, TX, USA), under the trade name "SOARNOL" by Nippon Gohsei (Hull, England), and under the trade name "SELAR OH" by DuPont (Wilmington, DE, USA); polyvinylidene chloride available from s.c. johnson (Racine, WI, USA) under the trade name "SARAN" and from Solvay (Brussels, belgium) under the trade name "IXAN"; liquid crystal polymers such as "VECTRA" from Celanese (Irving, TX, USA) and "XYDAR" from Solvay; "MDX 6" nylon, as well as amorphous nylons such as "NOVAMID" X21 from Koninklijke DSM N.V (Heerlen, the Netherlands), "SELAR PA" from DuPont; polyetherimides sold under the trade name "ULTEM" by SABIC (Riyadh, saudi arabia); poly (vinyl alcohol) s; and polymethylpentene resins available from Mitsui Chemicals (tokyo, japan) under the trade name "TPX".

Each polymer layer of the film may be formed from a thermoplastic material, which may include a combination of thermoplastic polymers. The thermoplastic material may optionally include colorants, fillers, processing aids, free radical scavengers, ultraviolet light absorbers, and the like, in addition to the one or more thermoplastic polymers. Each polymer layer of the film may be made of a different thermoplastic material, including different types of thermoplastic polymers.

The bladder may be made by applying heat, pressure and/or vacuum to the film. In this regard, primer layers, optical elements, textured layers, and the like may be disposed before, during, and/or after these steps, formed by these steps, or the like. The bladder (e.g., one or more polymer layers) may be formed using one or more polymer materials and using one or more processing techniques including, for example, extrusion, blow molding, injection molding, vacuum molding, rotational molding, transfer molding, pressure forming, heat sealing, casting, low pressure casting, spin casting, reaction injection molding, Radio Frequency (RF) welding, and the like. The bladder may be made by co-extrusion, followed by heat sealing or welding to create an inflatable bladder, which may optionally include one or more valves (e.g., one-way valves) that allow the bladder to be filled with a fluid (e.g., gas).

Before the embodiments are explained, it is to be understood that this disclosure is not limited to particular aspects described, and as such may, of course, vary. Other systems, methods, features and advantages of the foam compositions and components thereof will be or become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. The skilled person will recognise many variations and adaptations of the aspects described herein. Such modifications and adaptations are intended to be included within the teachings of this disclosure and are intended to be covered by the claims herein.

Test method

1. Sampling procedure

The predetermined sampling procedure may be: a part sampling procedure when a part is present as part of an article; a membrane sampling procedure when the part is part of a membrane or a layered membrane; pure material sampling procedure when the part is a material not available in the form of a membrane. Each of these sampling procedures is described in more detail below.

(A) Part sampling procedure

The procedure may be used to obtain a sample of a structure or component as incorporated into an article of manufacture, such as, for example, a bag or bottle or an article of footwear or the like, so that an optical property of a target surface of the structure or component (e.g., a surface of the article having one or more optical effects to be characterized) may be determined. The sample comprising the structure is obtained when the structure or part is formed or cut from the part, such as by using a blade. The process is performed by: identifying a target surface of a structure or component; separating a portion of the structure or component comprising the target surface from the article; and if necessary, removing any material from the target surface that may interfere with the determination of the optical properties. For example, the target surface may be peeled, polished, scratched, or otherwise cleaned to remove any upper adhesives, yarns, fibers, foam, and the like that may potentially interfere with optical property determinations.

The resulting part sample includes the target surface of the structure or part as it will be visible in the article. Thus, any test using a component sampling program can simulate how a structure or component will be visible as part of an article.

In this procedure, a sample is taken at a location along the structure or component that desirably provides a substantially uniform composition and has the necessary or desired surface area (e.g., a surface area large enough to determine the optical properties of the target surface). For example, if the target surface is intended to include a multilayer film with an optical element coating, then the sample is taken along a portion of the structure or component having both the multilayer film and the optical element coating throughout the sample.

(B) Membrane sampling procedure

This procedure can be used to obtain samples of the optical element when the optical element is extruded or coextruded or laminated onto the surface of a film or sheet. In this case, the thermoplastic composition and optionally the optical element are extruded or coextruded or laminated into a web or sheet having a substantially constant material thickness (within +/-10% of the average material thickness) and cooled to solidify the resulting web or sheet. A sample of the structure or component including the desired layers and coatings is then cut from the resulting web or sheet, having the necessary or desired surface area (e.g., a surface area large enough to determine the optical properties of the target surface).

(C) Pure material sampling procedure

This procedure can be used to obtain samples of the materials of the present disclosure. In this case, the material is provided in pure form, such as flakes, granules, powder, pellets, and the like. If the source of the material is not available in pure form, the material may be cut, scraped, or ground from the article or from a sheet or web to separate the material.

2. Visible light transmittance and visible light reflectance

The measurement of visible light transmittance and visible light reflectance was performed using a Shimadzu UV-2600 spectrometer (Shimadzu Corporation, japan). Prior to measurement, the spectrometer was calibrated using a standard. The angle of incidence for all measurements was zero.

Visible light transmittance is a measure of the amount of visible light (or light energy) transmitted through a sample material when visible light in the spectral range of 400 nm to 700 nm passes through the material. The results for all light transmissions in the range of 400 nm to 700 nm were collected and recorded. For each sample, the minimum value of visible light transmittance for this range was determined.

Visible light reflectance is a measure of the visible light (or light energy) reflected by a sample material when visible light in the spectral range of 400 nm to 700 nm passes through the material. The results for all reflectivities in the range of 400 nm to 700 nm were collected and recorded. For each sample, the minimum of the visible reflectance for this range was determined.

3. Difference in recycled optical Properties

The recycling optical property difference is a measure of the change in the optical properties of the structure before and after recycling. According to the method, a target surface of a structure or component is identified and isolated. The target surface is a surface representing a visible portion of a part or structure, including the color or optical effect exhibited by the structure or part. For example, if the structure or component is colored with a pigment or dye in a thermoplastic material, the target surface will be identified on the side of the component or structure having a representative amount of the pigment or dye in its thermoplastic material; if the coating is used to color a structure or component, the target surface will have a representative coating across the target surface.

A sample having a target surface measuring 1 cm by 1 cm is then extracted from the structure or component using one of the sampling procedures described in more detail herein. If differences in recycled optical properties of a composition (such as a thermoplastic composition or a recycled thermoplastic composition) are being measured, the composition is extracted using a pure material sampling procedure and melted and solidified to form a substrate having substantially uniform sides with a target surface area measured 1 centimeter by 1 centimeter.

A first optical property of a target surface of a sample is determined. The optical property may be visible light reflectance, visible light transmittance, or a color measurement. For example, the optical property may be a minimum or average visible light reflectance as measured in the visible light range having a wavelength from 400 to 700 nanometers. In another example, the optical property may be a minimum or average visible light transmittance measured in terms of a visible light range having a wavelength from 400 nanometers to 700 nanometers. The measured value is recorded as a first optical property value.

After determining the first optical property of the target surface of the sample, the sample is then recycled to form a recycled thermoplastic composition. The method for recycling the sample may include any means of processing (grinding, cutting, shredding, etc., as described herein) the sample into more than one piece. The method for recycling the sample does not include any means of chemically modifying or otherwise reducing, separating, or removing any colorant from the sample or recycled thermoplastic composition. The method for recycling a sample may further comprise increasing the temperature of the recycled thermoplastic composition to soften or melt the recycled thermoplastic composition. The resulting recycled thermoplastic composition comprises a solid or molten composition that comprises the same material in composition as the sample.

A second sample is formed from the recycled thermoplastic composition. The recycled thermoplastic composition is softened or melted and solidified to form a substrate having substantially uniform sides with a surface area measuring 1 centimeter by 1 centimeter. A second optical property of the target surface of the second sample is determined. The optical property measurements are performed using the same test method as for the corresponding first optical property. The measured value is recorded as a second optical property value.

The difference in the recycled optical properties of the samples was calculated using the following formula:

examples

1. Light transmittance of recycled structurally colored films

In this example, the film is made of a thermoplastic polyurethane substrate (base material) on which is deposited an optical element that imparts a blue structural color to the film. The film is ground to form a recycled thermoplastic composition. The recycled thermoplastic composition was combined with the original thermoplastic polyurethane (colorless) to provide three sample compositions comprising 5 percent, 10 percent, and 15 percent by weight of the recycled thermoplastic composition. A control sample composition comprising a thermoplastic polyurethane (colorless) without any recycled thermoplastic composition was prepared for comparison. The three sample compositions and the control composition were extruded to provide extruded film samples. Fig. 3 shows four sample films. The light transmittance of each film sample was evaluated qualitatively, and it was observed that the light transmittance of the film with the recycled thermoplastic composition was similar to that of the control.

It should be emphasized that the above-described aspects of the present disclosure are merely possible examples of implementations, and are merely set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described aspects of the disclosure without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For purposes of this specification, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also the individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. In one aspect, the term "about" can include conventional rounding according to the numerical significance of the numerical value. In addition, the phrase "about 'x' to 'y'" includes "about 'x' to about 'y'".

When recited in the claims, the term "providing," such as "providing an item" and similar terms, is not intended to require any particular delivery or receipt of the provided item. Rather, for the purposes of clarity and readability, the term "provided" is used merely to recite an item that will be referred to in the elements that follow the claim.

Many variations and modifications may be made to the above-described aspects. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.