阅读说明：本技术 用于使物品热成型的系统和方法 (System and method for thermoforming articles ) 是由 吉欧凡尼·亚达米 山姆·埃米斯 斯儿吉欧·卡瓦里尔 胡孟俊 约翰·赫德 詹姆士·摩立那克斯 于 2016-11-10 设计创作，主要内容包括：本申请涉及一种用于使物品热成型的系统和方法。方法可以包含利用负压产生系统将物品密封在成型材料中,从而将成型材料压缩到物品的外表面上。方法还可以包含将密封的物品暴露于高温,接着暴露于低温,同时维持成型材料对物品的外表面的压缩力。除了向物品的外表面施加额外的压缩力之外,还可以在进行加热和/或冷却步骤时向密封的物品施加正压,这有助于在热成型过程中从物品中去除气泡。(The present application relates to a system and method for thermoforming an article. The method may include sealing the article in the modeling material using the negative pressure generating system, thereby compressing the modeling material onto the outer surface of the article. The method may further comprise exposing the sealed article to an elevated temperature followed by a lower temperature while maintaining a compressive force of the molding material against an outer surface of the article. In addition to applying additional compressive force to the outer surface of the article, positive pressure may be applied to the sealed article as the heating and/or cooling step is performed, which aids in the removal of air bubbles from the article during thermoforming.)

1. A system for thermoforming an article, the system comprising:

a heating station;

a cooling station;

a bracket;

a negative pressure generating system, which is used for generating negative pressure,

wherein the negative pressure generating system is to at least partially seal the article within a molding material by exposing the article to a pressure below atmospheric pressure,

wherein the negative pressure generating system and the heating station cooperatively function to expose the article to: thermal energy, said sub-atmospheric pressure while said article is at least partially sealed within said modeling material;

wherein the negative pressure generating system and the cooling station cooperatively function to expose the article to a temperature that is lower than a temperature to which the article is subjected in the heating station when the article is at least partially sealed within the modeling material and exposed to the sub-atmospheric pressure; and is

Wherein the carriage and the negative pressure generating system cooperatively function to move the article between the heating station and the cooling station while being at least partially sealed within the modeling material.

2. The system for thermoforming an article according to claim 1, wherein the molding material exhibits a melting temperature T above 135 ℃_mDecomposition temperature T_dOr both.

3. The system for thermoforming an article of claim 1, wherein the heating station comprises one or more thermal elements.

4. The system for thermoforming an article of claim 3, wherein the one or more thermal elements each comprise a source of infrared radiation.

5. A system for thermoforming an article as recited in claim 3, wherein the heating station further comprises an air pressurization device to pressurize air in an interior portion of the heating station.

6. A system for thermoforming an article according to claim 1, wherein the article is an upper of a shoe, and wherein the molding material is sized to seal the entire upper within the molding material.

7. A system for thermoforming an article as claimed in claim 1, wherein the bracket is connected with the negative pressure generating system and the bracket is to connect with the article when the article is at least partially sealed within the molding material.

8. A system for thermoforming an article according to claim 7, wherein the carriage is to connect with the heating station when at least a portion of the article is located in an interior portion of the heating station.

9. A system for thermoforming an article as recited in claim 1, wherein the cooling station includes a positive pressure source and is to maintain a pressure above atmospheric pressure while the article is at least partially sealed within the modeling material and exposed to the pressure below atmospheric pressure.

10. A system for thermoforming an article according to claim 9, wherein the article comprises an upper of a shoe, the upper including an outsole portion, the heating station including one or more thermal elements, and wherein the outsole portion protrudes beyond at least a portion of the one or more thermal elements when the upper is located in an interior portion of the heating station.

11. A method for thermoforming an article, the method comprising: receiving an article; compressing the molding material onto the outer surface of the article with a negative pressure generating system by reducing the pressure between the outer surface of the article and the molding material to a pressure below atmospheric pressure, thereby forming a sealed article; exposing the sealed article to thermal energy in a heating station while: maintaining a pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure; and after exposing the sealed article to thermal energy, moving the sealed article from the heating station to a cooling station using a carriage and the negative pressure generating system while maintaining the pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure.

12. Use according to claim 11Method for thermoforming an article, wherein the molding material exhibits a melting temperature T higher than 135 ℃_mDecomposition temperature T_dOr both.

13. The method for thermoforming an article of claim 11, wherein at least a portion of the article is covered in a protective sleeve.

14. The method for thermoforming an article according to claim 11, wherein the article comprises an upper of a shoe, the upper including an outsole portion, and wherein the method further comprises placing the upper on a last such that outsole portion covers a bottom portion of the last.

15. The method for thermoforming an article as recited in claim 11, wherein the heating station includes a closure structure having an interior portion defined by opposing first and second end faces and at least one sidewall, and wherein the first end face is to receive at least a portion of the sealed article, and wherein the closure structure is capable of maintaining a pressure above atmospheric pressure.

16. The method for thermoforming an article according to claim 15, wherein the article comprises an upper of a shoe, the upper including an outsole portion, the heating station including one or more thermal elements, and wherein the method further comprises locating the upper in the interior portion of the heating station such that the outsole portion protrudes beyond the one or more thermal elements.

17. A method for thermoforming an article as claimed in claim 11, after locating the sealed article in the cooling station, increasing the pressure between the outer surface of the article and the modeling material to a pressure above atmospheric pressure such that the modeling material is no longer compressed onto the outer surface of the article.

18. The method for thermoforming an article as recited in claim 11, further comprising transferring the sealed article from the heating station to the cooling station using a carriage while maintaining the pressure between the exterior surface of the article and the molding material at the sub-atmospheric pressure.

19. A method for thermoforming an article according to claim 18, wherein the carriage is connected to a negative pressure generating system, and wherein the carriage, the negative pressure generating system and the heating station cooperate to expose the sealed article to a temperature of 135 ℃ or below 135 ℃ in an interior portion of the heating station while maintaining the pressure between the exterior surface of the article and the forming material at the sub-atmospheric pressure and while pressurizing at least a portion of the heating station containing the sealed article to a pressure above atmospheric pressure.

20. The method for thermoforming an article as recited in claim 19, wherein the carriage, the negative pressure generating system, and the cooling station cooperate to simultaneously expose the sealed article to: a temperature of 25 ℃ or less than 25 ℃ in an interior portion of the cooling station while maintaining the pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure; and a positive pressure above atmospheric pressure.

Technical Field

The present disclosure is directed to articles of wear, such as articles of apparel and/or articles of footwear. In particular, the present disclosure is directed to articles of wear comprising one or more fabrics comprising a low processing temperature polymer composition and a high processing temperature polymer composition. The present disclosure is also directed to methods of making an article of wear using a fabric comprising a low processing temperature polymer composition and a high processing temperature polymer composition.

Background

Traditionally, certain articles of wear, such as articles of footwear, are made by cutting individual pieces of material and combining them together. The individual pieces may be combined by stitching and/or using an adhesive. However, the cutting and combining process of multiple material sheets is wasteful, labor intensive, and error prone, with such errors leading to increased waste and increased manufacturing time and energy.

Disclosure of Invention

The present invention is directed to a system for thermoforming an article.

The present invention is directed to a method for thermoforming an article.

According to an embodiment of the invention, a system for thermoforming an article comprises: a heating station to obtain and maintain a pressure above atmospheric pressure; a cooling station; a negative pressure generating system comprising a molding material, a sealing member, and a negative pressure generating device, wherein the negative pressure generating system is to at least partially seal the article within the molding material by exposing the article to a pressure below atmospheric pressure, wherein the negative pressure generating system and the heating station cooperate to simultaneously expose the article to: thermal energy, the sub-atmospheric pressure when the article is at least partially sealed within the modeling material, and the super-atmospheric pressure; and wherein the negative pressure generating system and the cooling station cooperate to expose the article to a temperature that is lower than that to which the article is subjected in the heating station when the article is at least partially sealed within the modeling material and exposed to the pressure that is lower than atmospheric pressure.

In a system for thermoforming an article according to an embodiment of the invention, the molding material exhibits a melting temperature T above about 135 ℃_mDecomposition temperature T_dOr thisAnd both.

In a system for thermoforming an article according to an embodiment of the present invention, the heating station includes one or more thermal elements. The one or more thermal elements each comprise a source of infrared radiation. The heating station also includes an air pressurization device to pressurize air in an interior portion of the heating station.

In a system for thermoforming an article according to an embodiment of the invention, the article is an upper of a shoe, and wherein the molding material is sized to seal the entire upper within the molding material.

In a system for thermoforming an article according to an embodiment of the present invention, the system further includes a bracket coupled to the negative pressure generating system, wherein the bracket is configured to couple to the article when the article is at least partially sealed within the molding material. The carriage is configured to couple with the heating station when at least a portion of the article is located in the interior portion of the heating station.

In a system for thermoforming an article according to an embodiment of the invention, the cooling station includes a positive pressure source and is to maintain a pressure above atmospheric pressure while the article is at least partially sealed within the modeling material and exposed to the pressure below atmospheric pressure. The article includes an upper of a shoe, the upper including an outsole portion, and wherein the outsole portion protrudes beyond at least a portion of the one or more thermal elements when the upper is located in the interior portion of the heating station.

According to an embodiment of the invention, a method for thermoforming an article comprises: receiving an article; compressing a molding material onto an outer surface of the article by reducing a pressure between the outer surface of the article and the molding material to a pressure below atmospheric pressure, thereby forming a sealed article; exposing the sealed article to thermal energy in a heating station while: maintaining a pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure and pressurizing at least a portion of the heating station containing the sealed article to a pressure above atmospheric pressure; and after exposing the sealed article to thermal energy, locating the sealed article in a cooling station while maintaining the pressure between the outer surface of the article and the modeling material at the sub-atmospheric pressure.

In a method for thermoforming an article according to an embodiment of the invention, the molding material exhibits a melting temperature T above about 135 ℃_mDecomposition temperature T_dOr both.

In a method for thermoforming an article according to an embodiment of the invention, at least a portion of the article is covered in a protective sleeve.

In a method for thermoforming an article according to an embodiment of the invention, the article includes an upper of a shoe, the upper including an outsole portion, and wherein the method further includes placing the upper on a last such that the outsole portion covers a bottom portion of the last.

In a method for thermoforming an article according to an embodiment of the present invention, the heating station includes a closure structure having an interior portion defined by a first end face and an opposing second end face and at least one sidewall, and wherein the first end face is to receive at least a portion of the sealed article, and wherein the closure structure is capable of maintaining the above-atmospheric pressure. The article comprises an upper of a shoe, the upper including an outsole portion, and wherein the method further comprises locating the upper in the interior portion of the heating station such that the outsole portion protrudes beyond the one or more thermal elements.

In a method for thermoforming an article according to an embodiment of the invention, after the sealed article is located in the cooling station, the pressure between the outer surface of the article and the modeling material is increased to a pressure above atmospheric pressure such that the modeling material is no longer compressed onto the outer surface of the article.

A method for thermoforming an article according to an embodiment of the present invention further includes transferring the sealed article from the heating station to the cooling station using a carriage while maintaining a pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure.

In a method for thermoforming an article according to an embodiment of the present invention, the carriage is connected with a negative pressure generating system, and wherein the carriage, the negative pressure generating system, and the heating station cooperate to expose the sealed article to a temperature of about 135 ℃ or less than about 135 ℃ in an interior portion of the heating station while maintaining a pressure between the exterior surface of the article and the molding material at the sub-atmospheric pressure and while pressurizing at least the portion of the heating station containing the sealed article to the above-atmospheric pressure. The carriage, the negative pressure generating system, and the cooling station cooperate to simultaneously expose the sealed article to: a temperature of about 25 ℃ or less than about 25 ℃ in an interior portion of the cooling station while maintaining the pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure; and a positive pressure above atmospheric pressure.

Drawings

In the various figures of the drawings, certain aspects are illustrated by way of example and not by way of limitation.

Fig. 1A is a top and side perspective view of an article of footwear according to aspects of the invention, primarily illustrating the location of three different textile regions.

FIG. 1B is a bottom and side perspective view of the article of footwear of FIG. 1A, according to aspects of the invention.

FIG. 1C is a top and side perspective view of an alternative aspect of the article of footwear of FIG. 1A, showing primarily the location of three different textile regions, in accordance with aspects of the invention.

Fig. 2A is a side view of an article of apparel, primarily illustrating an elbow patch, according to aspects of the present invention.

Fig. 2B is a close-up view of an elbow patch of the article of apparel of fig. 2A, showing primarily three different fabric regions, in accordance with aspects of the present invention.

Fig. 3 is a plan view of a schematic depiction of a fabric having three types of fabric regions, in accordance with aspects of the present invention.

Fig. 4A-4E depict exemplary cross-sections of different types of fabric regions of the fabric of fig. 3, according to aspects of the present invention.

Fig. 5A-5J depict exemplary braided structures that may be present in different portions of the exemplary cross-sections depicted in fig. 4A-4E, according to aspects of the present invention.

Fig. 6 is a schematic diagram of two interconnected courses of stitches having different types of yarns and depicting a staggered interface, in accordance with aspects of the present invention.

Fig. 7A is a schematic diagram of three interconnected courses, wherein a middle course is formed from a different yarn than an outer course, in accordance with aspects of the present invention.

Fig. 7B is a schematic view of the interconnected courses of fig. 7A after exposure to a thermoforming process, and showing the middle course converted to a non-yarn material after thermoforming, but not the two outer courses, in accordance with aspects of the present invention.

Fig. 8 is a schematic illustration of a cross-section of the non-yarn material of fig. 7B, and showing a portion of a yarn from one of the outer courses encapsulated in the non-yarn material, in accordance with aspects of the present invention.

Fig. 9A is a schematic diagram of a cross-section of a portion of the interconnected courses of fig. 7A, illustrating one coil in the middle course and one coil in the upper course, in accordance with aspects of the present invention.

Fig. 9B is a cross-section of fig. 9A, but is a schematic view after the interconnected courses of fig. 7A are exposed to a thermoforming process, showing how the yarn loops in the middle course are deformed but maintaining the general yarn structure, in accordance with aspects of the present invention.

FIG. 10A is a schematic diagram of three interconnected courses of one type of yarn in float stitch (float stitch) and tuck stitch (tack stitch) with an anchoring yarn, in accordance with aspects of the present invention.

Fig. 10B is a schematic illustration of the interconnected courses of fig. 10A, and demonstrates that after thermoforming, one type of yarn forming the interconnected courses is converted to non-yarn material while the anchoring yarn is still present as a yarn, in accordance with aspects of the present invention.

Fig. 10C is a schematic illustration of a cross-section of the non-yarn material of fig. 10B, showing the anchoring yarn encapsulated in the non-yarn material, in accordance with aspects of the present invention.

Fig. 11A is a schematic illustration of a portion of one of the fabric regions of the fabric of fig. 3, and illustrating regions of different types of fibers, in accordance with aspects of the present invention.

Fig. 11B is a schematic view of the portion of fig. 11A after exposure to a thermoforming process, and illustrates how one of the several types of fibers is converted into a non-fibrous material and fibers of the other material are embedded within the non-fibrous material, in accordance with aspects of the present invention.

FIG. 11C is a cross-section of the non-fibrous material of FIG. 11B, showing two other fibers encapsulated in the non-fibrous material, in accordance with aspects of the present invention.

Fig. 12 is a schematic, side view of an article of footwear including a textile material, and illustrating a chassis (chassis), heel counter (heel counter), and sockliner (sock liner) for incorporation into the article of footwear, in accordance with aspects of the present invention.

Fig. 13 is a cross-section of the article of footwear of fig. 12, with the chassis, heel counter, and footbed located on the interior of the article of footwear, in accordance with aspects of the present invention.

Fig. 14 is a schematic, side view of an article of footwear incorporating a textile material, illustrating the addition of ground-engaging studs to a ground-engaging outsole region of the article of footwear, in accordance with aspects of the invention.

FIG. 15 is a top and side perspective view illustrating an upper for an article of footwear being placed on a last, in accordance with aspects of the present invention.

Fig. 16 is a top and side perspective view of the upper on the last from fig. 15, showing the upper wrapped around at least a bottom portion of the last, in accordance with aspects of the present invention.

FIG. 17 is a cross-section of the upper on the last from FIG. 16 along cut line 17-17, showing the last in contact with an interior surface of the upper, in accordance with aspects of the present invention.

Fig. 18 is a top and side perspective view of the upper on the last from fig. 16, showing a protective sheath (protective skin) wrapping around the upper, in accordance with aspects of the present invention.

Fig. 19 is a cross-section of the sock-covered upper from fig. 18 along cut line 19-19, showing the sock contacting the exterior surface of the upper, in accordance with aspects of the present invention.

Fig. 20A is a side view of the shoe upper on the last from fig. 16, showing a vacuum bag inside which the shoe upper is placed, in accordance with aspects of the present invention.

Fig. 20B is a side view of the shoe upper within the vacuum bag of fig. 20A, showing the vacuum bag compressing against an exterior surface of the shoe upper, in accordance with aspects of the present invention.

FIG. 21 is a schematic diagram of a thermoforming system having a heating zone and a cooling zone, in accordance with aspects of the present invention.

FIG. 22 is a schematic diagram of a thermoforming system having a heating station, a cooling station, and a negative pressure generating system, in accordance with aspects of the present invention.

FIG. 23 is a schematic diagram of another thermoforming system having a heating station, a cooling station, and a negative pressure generating system, in accordance with aspects of the present invention.

FIG. 24 is a perspective view of a heating station of the thermoforming system of FIG. 22, illustrating a plurality of thermal elements, a positive pressure source, and a fan, in accordance with aspects of the present technique.

FIG. 25 is a top view of the heating station of FIG. 24, in accordance with aspects of the present invention.

FIG. 26 is a perspective view of a sealing member and a molding material of the negative pressure generating system associated with the thermoforming system of FIG. 22, in accordance with aspects of the present technique.

FIG. 27 is a flow diagram of an exemplary method for thermoforming an article, according to aspects of the present invention.

Detailed Description

Conventional thermoforming processes may include heating a thermoplastic material to melt the thermoplastic material, followed by cooling the article to solidify the melted thermoplastic material to form a thermoformed article. In some methods, it may be difficult to thermoform an article comprising one or more thermoplastic polymers into a three-dimensional shape, such as an article of wear. For example, some methods may require that the article be formed around an object, such as a shoe upper, located on a last. In such a method, it may be advantageous to provide external pressure to the article during the thermoforming process in order to better form the article around the target. However, conventional thermoforming techniques do not provide the full and uniform pressure required to effectively thermoform an upper over an entire article, such as a footwear upper positioned on a last, while the upper is positioned on the last.

The thermoforming systems and methods described herein can mitigate one or more of the above problems. In various aspects, the thermoforming systems described herein are capable of providing a consistent and uniform pressure across an article when exposed to a heating step and/or a cooling step. In these aspects, this consistent and uniform pressure across the article may be achieved, at least in part, by using a negative pressure generating system capable of sealing the article to be thermoformed within the molding material, compressing the molding material onto the outer surface of the article. In addition, the thermoforming system can also provide positive pressure to the article as it undergoes the heating step and/or the cooling step, which helps form the article (e.g., the upper on the last) around the object, enhances bonding, and helps remove air bubbles from the article.

The present disclosure also includes specific materials and methods of forming articles for use in the thermoforming processes described herein. For example, the present disclosure also describes an article of wear comprising a fabric comprising fibers, yarns, or both formed from a first thermoplastic polymer composition (e.g., a yarn composition or a fiber composition) comprising one or more first thermoplastic polymers. First thermoplastic polymer comprising one or more first polymersThe composition is referred to herein as a low processing temperature polymer composition. The fabrics of the present disclosure also comprise fibers, yarns, or both comprising a second thermoplastic polymer composition comprising one or more second polymers. A second thermoplastic polymer composition comprising one or more second polymers is referred to herein as a high processing temperature polymer composition. As used herein, "low processing temperature polymer composition" and "high processing temperature polymer composition" are relative terms, wherein the low processing temperature polymer composition exhibits a creep relaxation temperature (T) greater than the high processing temperature polymer composition_crHeat deflection temperature (T)_hdVicat softening temperature T_vsOr melting temperature T_mLow melting temperature T of one or more of_m. These parameters are described in further detail below. It is to be understood that other characteristics and parameters may differ between the low processing temperature polymer composition and the high processing temperature polymer composition, as discussed in detail below.

In certain aspects, thermoforming a fabric described herein can cause the low processing temperature polymer composition to melt or deform (and subsequently solidify), thereby changing the structure of the low processing temperature polymer composition, while the high processing temperature polymer composition does not melt and/or deform, thereby maintaining its structure, such as its structure as a yarn or fiber. In these aspects, this thermoforming process can result in a more rigid structural component (e.g., an outsole portion of a shoe) integrally connected with a less rigid portion of the fabric, such as an upper portion of a shoe, having fibers (e.g., fibers in the form of yarns) comprising the high processing temperature polymer composition.

Accordingly, in one aspect, a system for thermoforming an article is provided. The system includes a heating station, a cooling station, and a negative pressure generating system to obtain and maintain a pressure above atmospheric pressure. The negative pressure generating system includes a molding material, a sealing member, and a negative pressure generating device. The negative pressure generating system is to at least partially seal the article within the molding material by exposing the article to a pressure below atmospheric pressure. The negative pressure generating system and the heating station cooperate to simultaneously expose the articles to: heat energy; a sub-atmospheric pressure while the article is at least partially sealed within the molding material; and pressures above atmospheric pressure. The negative pressure generating system and the cooling station cooperate to expose the article to a temperature that is lower than that experienced in the heating station when the article is at least partially sealed within the modeling material and to a pressure that is lower than atmospheric pressure.

In another aspect, a method for thermoforming an article is provided. The method includes receiving an article and compressing a modeling material onto an outer surface of the article by reducing a pressure between the outer surface of the article and the modeling material to a pressure below atmospheric pressure, thereby forming a sealed article. The method further comprises exposing the sealed article to thermal energy in a heating station while: maintaining a pressure between the outer surface of the article and the molding material at a pressure below atmospheric pressure; and pressurizing at least a portion of the heating station containing the sealed articles to a pressure above atmospheric pressure. The method further comprises after exposing the sealed article to thermal energy, positioning the sealed article in a cooling station while maintaining a pressure between the outer surface of the article and the modeling material at a pressure below atmospheric pressure.

As discussed above, the fibers, yarns, and fabrics described herein may comprise the selective incorporation of a low processing temperature polymer composition and/or the selective incorporation of a high processing temperature polymer composition. In various aspects, such low processing temperature polymer compositions can be present in the form of fibers comprising the low processing temperature polymer composition. In some aspects, the fibers comprising the low processing temperature polymer composition are substantially free of the high processing temperature polymer composition. In other aspects, the fibers comprising the low processing temperature polymer composition consist essentially of the low processing temperature polymer composition. In accordance with the present disclosure, these fibers may be used to form yarns, which in turn may be used to form fabrics, including braided, woven, or wound fabrics. These fibers may also be used to form a non-woven textile according to the present disclosure.

Similarly, the high processing temperature polymer composition described above can be present in the form of fibers comprising the high processing temperature polymer composition. In some aspects, the fibers comprising the high processing temperature polymer composition are substantially free of the low processing temperature polymer composition. In other aspects, the fibers comprising the high processing temperature polymer composition consist essentially of the high processing temperature polymer composition. In accordance with the present disclosure, these fibers may be used to form yarns, which in turn may be used to form fabrics, including braided, woven, or wound fabrics. These fibers may also be used to form nonwoven fabrics according to the present disclosure.

In some aspects, fibers and/or yarns comprising the low processing temperature polymer composition may additionally comprise a high processing temperature polymer composition. For example, the fibers can be bicomponent fibers having the low processing temperature polymer composition present on at least a portion of the outer surface of the fibers. For example, the low processing temperature composition and the high processing temperature composition may have a side-by-side structure (side-by-side structure) or may have a core-and-sheath structure (core-and-sheath structure) in which the low processing temperature composition is present in the sheath. In certain aspects, the low processing temperature polymer composition, the high processing temperature polymer composition, or both may further comprise one or more conventional additives found in yarns or fibers comprising polymeric materials. Although the above may describe only the characteristics and parameters of the yarn or yarn composition, it is to be understood that such characteristics and parameters also apply to the fiber or fiber composition, unless otherwise mentioned.

In certain aspects, one or more of the yarns may be a monofilament yarn or a multifilament yarn. In certain aspects, the yarn may be a spun yarn. In various aspects, one or more of the yarns may be formed using conventional techniques, including but not limited to melt spinning, solution spinning, or electrospinning.

In certain aspects, the fibers described herein can be different size fibers, including fibers that are not suitable for spinning into commercial yarns. The yarns described herein include yarns that are suitable for use in commercial knitting machines as well as yarns that are not individually suitable for use in commercial knitting machines.

In certain aspects, the yarns and/or fibers described herein may be used to provide specific functionality. For example, in certain aspects, yarns comprising the low processing temperature polymer composition may be thermoformed to form films having water-resistant or water-resistant properties. In these aspects, the film may be provided on the outer surface of the article by using yarns and or fibers comprising a low processing temperature polymeric material on the outside of the fabric, including the woven structure forming the fabric.

As discussed above, in certain aspects, one or more of the yarns and/or fibers may be dyed, for example, for aesthetic purposes. In various aspects, the yarn and/or fiber may be dyed using conventional dyeing techniques, such as package dyeing (package dyeing) or solution dyeing (solution dyeing). Generally, package dyeing is a process performed on already formed yarn and/or fiber, while dope dyeing is a process in which fiber is dyed before forming the fiber into yarn. In certain aspects, yarns or fibers comprising the high processing temperature polymer composition may be dyed. In certain aspects, yarns or fibers comprising the low processing temperature polymer composition may not be dyed and may be formed from a polymer composition that is substantially free of pigments or dyes, which may result in transparent or near transparent regions comprising the low processing temperature composition (e.g., non-yarn or non-fiber material after thermoforming).

In certain aspects, yarns comprising the low processing temperature polymeric compositions can exhibit a tenacity of about 1 gram/denier to about 5 grams/denier. In one or more aspects, the yarn comprising the low processing temperature polymeric composition can exhibit a tenacity of from about 1.5 g/denier to about 4.5 g/denier. In one aspect, a yarn comprising the low processing temperature polymeric composition can exhibit a tenacity of from about 2 grams/denier to about 4.5 grams/denier. "toughness" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

In various aspects, the yarn comprising the low processing temperature polymer composition can exhibit an elongation of about 10% to about 130%. In one or more aspects, the yarn comprising the low processing temperature polymer composition can exhibit an elongation of about 20% to about 130%. In one aspect, a yarn comprising the low processing temperature polymer composition can exhibit an elongation of about 40% to about 130%. The term "elongation" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

As discussed above, in certain aspects, it may be desirable to utilize yarns suitable for use on commercial weaving equipment. Free-standing shrinkage of the yarn at 50 ℃ is a property that can be predicted for a yarn suitable for use on a commercial knitting machine. In certain aspects, a yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 60% when heated from 20 ℃ to 50 ℃. In one or more aspects, the yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 30% when heated from 20 ℃ to 50 ℃. In one aspect, a yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 20% when heated from 20 ℃ to 50 ℃. The term "independent shrinkage" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

In one or more aspects, the independent shrinkage of the yarn at 70 ℃ can be used to indicate the ability of the yarn to not undergo any substantial change in its physical structure when exposed to certain environmental conditions. In certain aspects, a yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 60% when heated from 20 ℃ to 70 ℃. In one or more aspects, the yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 30% when heated from 20 ℃ to 70 ℃. In one aspect, a yarn comprising the low processing temperature polymer composition is capable of exhibiting an independent shrinkage of about 0% to about 20% when heated from 20 ℃ to 70 ℃.

In one or more aspects, the yarn comprising the low processing temperature polymer composition can exhibit a modulus of about 1Mpa to about 500 Mpa. In certain aspects, the yarn comprising the low processing temperature polymeric composition can exhibit a modulus of about 5Mpa to about 150 Mpa. In one aspect, the yarn comprising the low processing temperature polymeric composition can exhibit a modulus of about 20Mpa to about 130 Mpa. In another aspect, a yarn comprising the low processing temperature polymer composition can exhibit a modulus of from about 30MPa to about 120 MPa. In another aspect, the yarn comprising the low processing temperature polymeric composition can exhibit a modulus of about 40MPa to about 110 MPa. The term "modulus" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

In one or more aspects, the low processing temperature polymeric composition is capable of exhibiting a modulus of about 1Mpa to about 500Mpa when present in sheet form. In certain aspects, the low processing temperature polymeric composition in the form of a sheet is capable of exhibiting a modulus of from about 5Mpa to about 150 Mpa. In one aspect, the low processing temperature polymeric composition in the form of a sheet is capable of exhibiting a modulus of from about 20Mpa to about 130 Mpa. In another aspect, the low processing temperature polymeric composition in the form of a sheet is capable of exhibiting a modulus of from about 30MPa to about 120 MPa. In another aspect, the low processing temperature polymeric composition in the form of a sheet is capable of exhibiting a modulus of from about 40MPa to about 110 MPa.

In one or more aspects, when a yarn comprising the low processing temperature polymer composition reaches a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mThe resulting thermoformed material (e.g., non-yarn material) is capable of exhibiting a modulus of about 1Mpa to about 500Mpa when tested at about 20 ℃ and a pressure of 1 ATM. In various aspects, when a yarn comprising the low processing temperature polymer composition reaches a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mThe resulting thermoformed material (e.g., non-yarn material) is capable of exhibiting a modulus of about 5Mpa to about 150Mpa when tested at about 20 ℃ and a pressure of 1 ATM. In one or more aspects, includeThe yarn of the processing temperature polymer composition reaches a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mThe resulting thermoformed material (e.g., non-yarn material) is capable of exhibiting a modulus of about 20Mpa to about 130Mpa when tested at about 20 ℃ and a pressure of 1 ATM. In one or more aspects, the yarn comprising the low processing temperature polymer composition reaches a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mThe resulting thermoformed material (e.g., non-yarn material) is capable of exhibiting a modulus of about 30Mpa to about 120Mpa when tested at about 20 ℃ and a pressure of 1 ATM. In one or more aspects, the yarn comprising the low processing temperature polymer composition reaches a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mThe resulting thermoformed material (e.g., non-yarn material) is capable of exhibiting a modulus of about 40Mpa to about 110Mpa when tested at about 20 ℃ and a pressure of 1 ATM.

In various aspects, when a yarn comprising the low processing temperature polymer composition is present in a fabric and has reached a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mWhen tested at a temperature of about 20 ℃ and a pressure of 1ATM, the resulting thermoformed material (or non-yarn material) exhibited a cold cross flex (cold cross flex) of about 5000 cycles to about 500,000 cycles. In one or more aspects, when the yarn comprising the low processing temperature polymer composition is present in the fabric and has reached a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mWhen tested at a temperature of about 20 ℃ and a pressure of 1ATM, the resulting thermoformed material (or non-yarn material) exhibits a clos of about 10,000 cycles to about 300,000 cyclesAnd (4) bending. In certain aspects, when the yarn comprising the low processing temperature polymer composition is present in a fabric and has reached a temperature above the melting temperature T of the low processing temperature polymer composition_mAnd then reaches a temperature below the melting temperature T of the low processing temperature polymer composition_mWhen tested at a temperature of about 20 ℃ and a pressure of 1ATM, the resulting thermoformed material (or non-yarn material) exhibits a cold ross bend of at least about 150,000 cycles. The term "cryoflex" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

In certain aspects, as discussed in detail below, the anchoring yarns may be used to help restrict the flow of a molten material, such as a low processing temperature polymer composition, during the thermoforming process, and/or to impart some flexibility to the thermoformed material. In these aspects, the anchoring yarn may exhibit an elongation that is less than the elongation of a low processing temperature polymer composition, such as a yarn comprising a low processing temperature polymer composition or a non-yarn material produced by thermoforming of such a yarn. For example, in various aspects, the anchor yarn may exhibit an elongation that is at least about 10% less than the elongation of the yarn comprising the low processing temperature polymer composition or the non-yarn material produced by thermoforming the yarn comprising the low processing temperature polymer composition. In one aspect, the anchor yarn may exhibit an elongation that is at least about 25% less than the elongation of the yarn comprising the low processing temperature polymer composition or the non-yarn material produced by thermoforming the yarn comprising the low processing temperature polymer composition. In another aspect, the anchor yarn may exhibit an elongation that is at least about 50% less than the elongation of the yarn comprising the low processing temperature polymer composition or the non-yarn material produced by thermoforming the yarn comprising the low processing temperature polymer composition. In another aspect, the anchor yarn may exhibit an elongation that is at least about 75% less than the elongation of the yarn comprising the low processing temperature polymer composition or the non-yarn material produced by thermoforming the yarn comprising the low processing temperature polymer composition. Exemplary anchoring yarns include polyamide yarns, polyolefin yarns, and polyester yarns, including yarns having a tenacity of from about 5 g/denier to about 10 g/denier.

The anchor yarns may be formed from a high processing temperature polymer composition that includes one or more polymers. The one or more polymers of the high processing temperature polymer composition of the anchoring yarn may be a thermoplastic polymer. In certain aspects, the one or more polymers of the high processing temperature polymer composition of the anchor yarn may be the same as the one or more polymers of the high processing temperature polymer composition of the second yarn used in forming the fabric comprising the anchor yarn. In other aspects, the one or more polymers of the high processing temperature polymer composition of the anchor yarn are different from the one or more polymers of the high processing temperature polymer composition of the second yarn used in forming the fabric comprising the anchor yarn.

As discussed above, in certain aspects, the low processing temperature polymer composition and the high processing temperature polymer composition have different properties. In various aspects, these different characteristics enable the low processing temperature polymer composition to melt and flow during the thermoforming process, and subsequently cool and solidify into a structure different from the structure prior to the thermoforming process (e.g., thermoformed from yarn to non-yarn material) when the thermoforming process is conducted at a temperature below the creep-relaxation temperature, heat-distortion temperature, or vicat softening temperature of the high processing temperature polymer composition, while the high processing temperature polymer composition does not deform or melt during such process and is capable of maintaining its structure (e.g., as yarn). In these aspects, the non-yarn material formed during the thermoforming process from the low processing temperature composition can be integrally connected with an unaltered structure (e.g., yarn or fiber) to provide a three-dimensional structure and/or other properties specific to a particular point on the article of wear.

Low processing temperature polymer compositions

As discussed above, in certain aspects, the low processing temperature polymer composition includes one or more first thermoplastic polymers and is capable of exhibiting a lower heat change than the high processing temperature polymer compositionShape temperature T_hdVicat softening temperature T_vsCreep relaxation temperature T_crOr melting temperature T_mA melting temperature T of at least one of_m(or melting point). In the same or alternative aspects, the low processing temperature polymer composition is capable of exhibiting a melting temperature T_mThermal deformation temperature T_hdVicat softening temperature T_vsAnd creep relaxation temperature T_crIs below the heat distortion temperature T of the high processing temperature polymer composition_hdVicat softening temperature T_vsCreep relaxation temperature T_crOr melting temperature T_mOne or more of the above. "creep relaxation temperature T" as used herein_cr"," Vicat softening temperature T_vs"," Heat distortion temperature T_hdAnd melting temperature T_m"refers to the corresponding test methods described below in the characterization and characterization procedure section.

In certain aspects, the low processing temperature polymer composition can exhibit a melting temperature T of about 135 ℃ or less than about 135 ℃_m(or melting point). In one aspect, the low processing temperature polymer composition is capable of exhibiting a melting temperature T of about 125 ℃ or less than about 125 ℃_m. In another aspect, the low processing temperature polymer composition is capable of exhibiting a melting temperature T of about 120 ℃ or less than about 120 ℃_m. In certain aspects, the low processing temperature polymer composition is capable of exhibiting a melting temperature T of about 80 ℃ to about 135 ℃_m. In various aspects, the low processing temperature polymer composition is capable of exhibiting a melting temperature T of about 90 ℃ to about 120 ℃_m. In one aspect, the low processing temperature polymer composition is capable of exhibiting a melting temperature T of about 100 ℃ to about 120 ℃_m。

In one or more aspects, the low processing temperature polymer composition can exhibit a glass transition temperature T of about 50 ℃ or less than about 50 ℃_g. In one aspect, the low processing temperature polymer composition is capable of exhibiting a glass transition temperature T of about 25 ℃ or less than about 25 ℃_g. In another aspect, the low processing temperature polymer composition is capable of exhibiting a glass transition of about 0 ℃ or less than about 0 ℃Variable temperature T_g. In various aspects, the low processing temperature polymer composition is capable of exhibiting a glass transition temperature T of about-55 ℃ to about 55 ℃_g. In one aspect, the low processing temperature polymer composition is capable of exhibiting a glass transition temperature T of about-50 ℃ to about 0 ℃_g. In certain aspects, the low processing temperature polymer composition is capable of exhibiting a glass transition temperature T of about-30 ℃ to about-5 ℃_g. The term "glass transition temperature T" as used herein_g"refers to the corresponding test methods described below in the characterization and characterization procedure section.

In various aspects, the low processing temperature polymer composition is capable of exhibiting a melt flow index (melt flow index) of about 0.1 grams/10 minutes (min) to about 60 grams/10 min using a 2.16 kilogram test weight. In certain aspects, the low processing temperature polymer composition is capable of exhibiting a melt flow index of from about 2 g/10 min to about 50 g/10 min using a 2.16 kilogram test weight. In another aspect, the low processing temperature polymer composition is capable of exhibiting a melt flow index of from about 5 g/10 min to about 40 g/10 min using a 2.16 kg test weight. In certain aspects, the low processing temperature polymer composition is capable of exhibiting a melt flow index of about 25 g/10 min using a 2.16 kg test weight. The term "melt flow index" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

In one or more aspects, the low processing temperature polymer composition can exhibit an enthalpy of fusion of about 8J/g to about 45J/g. In certain aspects, the low processing temperature polymer composition is capable of exhibiting a melting enthalpy of about 10J/g to about 30J/g. In one aspect, the low processing temperature polymer composition is capable of exhibiting a melting enthalpy of about 15J/g to about 25J/g. The term "enthalpy of fusion" as used herein refers to the corresponding test method described below in the characterization and characterization procedure section.

As previously described, the low processing temperature polymer composition includes one or more thermoplastic polymers. In various aspects, the thermoplastic polymer may comprise one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins. In aspects, the thermoplastic polymer may comprise one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and combinations thereof.

In one or more aspects, the thermoplastic polymer can comprise one or more polyesters. In these aspects, the polyester can comprise polyethylene terephthalate (PET). In certain aspects, the thermoplastic polymer may comprise one or more polyamides. In these aspects, the polyamide may comprise poly (hexamethylene adipamide) (nylon 6,6), polycaprolactam (nylon 6), polydodecalactam (nylon 12), and combinations thereof. In aspects, the thermoplastic polymer may comprise one or more polyurethanes.

In various aspects, the thermoplastic polymer can comprise one or more copolymers. In certain aspects, the thermoplastic polymer may comprise one or more copolymers selected from the group consisting of copolyesters, copolyethers, copolyamides, copolycarbamates, and combinations thereof. In one or more aspects, the thermoplastic polymer can comprise one or more copolyesters. In certain aspects, the thermoplastic polymer can comprise one or more copolyethers. In various aspects, the thermoplastic polymer may comprise one or more copolyamides. In certain aspects, the thermoplastic polymer may comprise one or more copolyurethanes. In one aspect, the thermoplastic polymer may comprise one or more polyether block amide (PEBA) copolymers. Exemplary thermoplastic polymers are described in detail below.

Exemplary thermoplastic polymers

In various aspects, exemplary thermoplastic polymers include homopolymers and copolymers. In certain aspects, the thermoplastic polymer can be a random copolymer. In one aspect, the thermoplastic polymer can be a block copolymer. For example, the thermoplastic polymer may be a block copolymer having repeating blocks of relatively hard polymer units (segments) (hard segments) of the same chemical structure and repeating blocks of relatively soft polymer segments (soft segments). In various aspects, in block copolymers, including block copolymers having repeating hard and soft segments, there can be physical cross-linking within the blocks or between the blocks or within and between the blocks. Specific examples of the hard segment include an isocyanate segment and a polyamide segment. Specific examples of the soft segment include polyether segments and polyester segments. As used herein, a polymer segment may be referred to as a particular type of polymer segment, such as an isocyanate segment, a polyamide segment, a polyether segment, a polyester segment, and the like. It is understood that the chemical structure of the segment is derived from the described chemical structure. For example, the isocyanate segment is a polymeric unit comprising an isocyanate functional group. When referring to blocks of polymer segments of a particular chemical structure, the blocks may contain up to 10 mol% of segments of other chemical structures. For example, as used herein, a polyether segment is understood to comprise up to 10 mol% of non-polyether segments.

In various aspects, the thermoplastic polymer may comprise one or more of a thermoplastic polyurethane, a thermoplastic polyamide, a thermoplastic polyester, and a thermoplastic polyolefin. It is to be understood that other thermoplastic polymer materials not specifically described below are also contemplated for use in the low processing temperature polymer composition and/or the high processing temperature polymer composition.

In certain aspects, the thermoplastic polymer may be a thermoplastic polyurethane. In various aspects, the thermoplastic polyurethane may be a thermoplastic block polyurethane copolymer. In these aspects, the thermoplastic block polyurethane copolymer may be a block copolymer having a hard segment block and a soft segment block. In various aspects, the hard segment may include or consist of an isocyanate segment. In the same or alternative aspects, the soft segment can include or consist of: a polyether segment, or a polyester segment, or a combination of a polyether segment and a polyester segment. In a particular aspect, the thermoplastic material may comprise or consist essentially of: an elastomeric thermoplastic polyurethane having hard segment repeating blocks and soft segment repeating blocks.

In various aspects, one or more of the thermoplastic polyurethanes may be produced by: one or more isocyanates, each preferably containing two or more isocyanate groups (— NCO) per molecule, such as 2,3 or 4 isocyanate groups per molecule (although monofunctional isocyanates may also optionally be included, for example as chain terminating units), are polymerized with one or more polyols to produce copolymer chains having urethane linkages (— n (co) O-) as shown in formula 1 below.

In these examples, each R₁And R₂Independently an aliphatic or aromatic segment. Alternatively, each R₂May be a hydrophilic segment.

Any of the functional groups or compounds described herein may be substituted or unsubstituted, unless otherwise specified. A "substituted" group or compound, such as alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate, means that the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate group has at least one hydrogen group substituted with a non-hydrogen group (i.e., substituent). Examples of non-hydrogen radicals (or substituents) include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl, heteroaryl, heterocycloalkyl, hydroxy, oxy (or oxo), alkoxy, ester, thioester, acyl, carboxy, cyano, nitro, amino, amide, sulfur, and halo. When the substituted alkyl group contains more than one non-hydrogen group, the substituents may be bound to the same carbon or to two or more different carbon atoms.

Additionally, the isocyanates may also be chain extended by bridging two or more isocyanates with one or more chain extenders. This may result in a polyurethane copolymer chain as shown in formula 2 below, where R is₃Comprising a chain extender. As for each R₁And R₂In the same way, each R₃Independently an aliphatic or aromatic segment.

Each segment R in formula 1 and formula 2, based on the particular isocyanate used₁Or the first segment may independently comprise a straight or branched chain C_3-30And may be aliphatic, aromatic, or contain a combination of aliphatic and aromatic moieties. The term "aliphatic" refers to saturated or unsaturated organic molecules that do not contain a ring-conjugated ring system with delocalized pi electrons. In contrast, the term "aromatic" refers to a ring conjugated ring system with delocalized pi electrons that exhibits greater stability than ring systems that are hypothesized to have localized pi electrons.

Each segment R based on the total weight of reactant monomers₁May be present in an amount of 5 to 85 wt.%, 5 to 70 wt.%, or 10 to 50 wt.%.

In the aliphatic example (from aliphatic isocyanates), each segment R₁May contain straight chain aliphatic groups, branched aliphatic groups, cycloaliphatic groups, or combinations thereof. For example, each segment R₁May contain straight or branched C_3-20Alkylene segment (e.g. C)_4-15Alkylene or C_6-10Alkylene), one or more C_3-8Cycloalkylene segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof.

Examples of aliphatic diisocyanates suitable for making the polyurethane copolymer chain include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Butylene Diisocyanate (BDI), diisocyanatocyclohexylmethane (HMDI), 2,4-trimethylhexamethylene diisocyanate (2,2,4-trimethylhexamethylene diisocyanate, TMDI), diisocyanatomethylcyclohexane (NDI), diisocyanatomethyltricyclomethyltricyclomethyldecane (bisisocyanatomethyl isocyanurate), norbornane diisocyanate (norbomane diisocyanate, NDI), cyclohexane diisocyanate (isocyclohexane, 4 '-diisocyanate), 4' -dicyclohexylmethane (4 '-diisocyanate), 4' -diisocyanate (MDI), and combinations thereof.

In the aromatic example (from aromatic isocyanates), each segment R₁May contain one or more aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylene, indanyl, indenyl, anthracenyl and fluorenyl groups. Unless otherwise indicated, the aromatic group may be an unsubstituted aromatic group or a substituted aromatic group, and may further comprise a heteroaromatic group. "heteroaromatic" refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system in which one to four ring atoms are selected from oxygen, nitrogen, or sulfur and the remaining ring atoms are carbon, and in which the ring system is attached to the rest of the molecule through any one of the ring atoms. 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 aromatic diisocyanates suitable for making the polyurethane copolymer chain include Toluene Diisocyanate (TDI), TDI adduct with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), Xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), Hydrogenated Xylene Diisocyanate (HXDI), naphthalene 1,5-diisocyanate (naphthalene 1,5-diisocyanate, NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (para-phenylene diisocyanate, PPDI), 3' -dimethyldiphenyl-4,4' -diisocyanate (3, 4' -dimethyl diisocyanate, 4' -diphenylmethane diisocyanate), 4' -dimethyldiphenyl-4,4' -diisocyanate (dd4, 4' -dimethyldiphenylmethane diisocyanate, 4' -dibenzyl diisocyanate, DBDI), 4-chloro-1, 3-phenylene diisocyanate, and combinations thereof. In some embodiments, the copolymer chains are substantially free of aromatic groups.

In particular aspects, the polyurethane copolymer chain is made from a polymer comprising HMDI, TDI, MDI, H₁₂Aliphatic groups, and combinations thereof.

In certain aspects, crosslinked (e.g., partially crosslinked polyurethane copolymers that retain thermoplastic properties) or possibly crosslinked polyurethane chains may be used in accordance with the present disclosure. It is possible to use polyfunctional isocyanates to produce crosslinked or crosslinkable polyurethane copolymer chains. Examples of triisocyanates suitable for making the polyurethane copolymer chain include TDI, HDI, and IPDI adducts with Trimethylolpropane (TMP), uretdiones (i.e., dimeric isocyanates), polymeric MDI, and combinations thereof.

The segment R in formula 2 is based on the particular chain extender polyol used₃May contain straight or branched C₂-C₁₀A segment, and may be, for example, aliphatic, aromatic, or polyether. Examples of chain extender polyols suitable for making polyurethane copolymer chains 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, bis (e.g., 2-hydroxyethyl) ethers of dihydroxyalkylated aromatic compounds hydroquinone and resorcinol, bis (e.g., 2-hydroxyethyl) ether, Xylene-a, a-diol, bis (2-hydroxyethyl) ethers of xylene-a, a-diol, and combinations thereof.

Segment R in formula 1 and formula 2₂May comprise polyether groups, polyester groups, polycarbonate groups, aliphatic groups or aromatic groups. Each segment R based on the total weight of reactant monomers₂May be present in an amount of 5 to 85 wt.%, 5 to 70 wt.%, or 10 to 50 wt.%.

Alternatively, in some examples, the thermoplastic polyurethanes of the present disclosure may be thermoplastic polyurethanes having a relatively large degree of hydrophilicity. For example, the thermoplastic polyurethane may be a thermoplastic polyurethane in which the segment R in formula 1 and formula 2₂Comprising polyether groups, polyester groups, polycarbonate groups, aliphatic or aromatic groups, wherein the aliphatic or aromatic groups are substituted with one or more pendant groups having a relatively greater degree of hydrophilicity (i.e., groups that are "hydrophilic" relatively greater). The "hydrophilic" relatively large group may be selected from the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone (PVP)), amino, carboxylic acid ester, sulfonic acid ester, phosphate ester, ammonium (e.g., tertiary and quaternary ammonium), zwitterion (e.g., betaine, such as poly (carboxybetaine), pCB), and ammonium phosphonate, such as phosphatidylcholine), and combinations thereof. In such examples, R₂Such relatively hydrophilic groups or segments of (a) may form part of the polyurethane backbone or may be grafted onto the polyurethane backbone as a pendant group. In some examples, the pendant hydrophilic groups or segments can be bonded to the aliphatic or aromatic groups through a linking group. Each segment R based on the total weight of reactant monomers₂May be present in an amount of 5 to 85 wt.%, 5 to 70 wt.%, or 10 to 50 wt.%.

In some examples, at least one R of the thermoplastic polyurethane₂The segment comprises a polyether segment (i.e., a segment having one or more ether groups). Suitable polyethers include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), Polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof. The term "alkyl" as used herein refers to straight chain sums containing from one to thirty carbon atoms, e.g., from one to twenty carbon atoms or from one to ten carbon atomsA branched saturated hydrocarbon group. Term C_nMeaning that the alkyl group has "n" carbon atoms. For example, C₄Alkyl refers to an alkyl group having 4 carbon atoms. C_1-7Alkyl refers to alkyl groups having a full range of carbon numbers (i.e., 1 to 7 carbon atoms) and all subgroups (e.g., 1 to 6, 2 to 7, 1 to 5, 3 to 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 indicated, alkyl groups may be unsubstituted alkyl groups or substituted alkyl groups.

In some embodiments of the thermoplastic polyurethane, at least one R₂The segment comprises a polyester segment. The polyester segments can be derived from the polyesterification of 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) to one or more diols (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). Polyesters may also be derived from polycarbonate prepolymers such as poly (hexamethylene carbonate) glycol, poly (propylene carbonate) glycol, poly (tetramethylene carbonate) glycol, and poly (nonylmethylene carbonate) glycol. Suitable polyesters may include, for example, polyethylene adipates (PEAs), poly (1, 4-butylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), polycaprolactone, poly (hexamethylene carbonate), poly (propylene carbonate), poly (tetramethylene carbonate), poly (nonane methylene carbonate), and combinations thereof.

In different thermoplastic polyurethanes, at least one R₂The segment comprises a polycarbonate segment. Poly(s) are polymerizedThe carbonate segment can be derived from the reaction of one or more diols (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.

In various examples of thermoplastic polyurethanes, at least one R₂A segment may comprise aliphatic groups substituted with one or more groups having a relatively greater degree of hydrophilicity, i.e., groups that are "hydrophilic" relative to each other. The one or more relatively hydrophilic groups may be selected from the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone), amino, carboxylic acid ester, sulfonate, phosphate ester, ammonium (e.g., tertiary and quaternary), zwitterions (e.g., betaines such as poly (carboxybetaines) (pCB); and ammonium phosphonates such as phosphatidylcholine), and combinations thereof. In some examples, aliphatic groups are straight chain and may contain, for example, C_1-20Alkylene chain or C_1-20Alkenylene chains (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 "alkylene" refers to a divalent hydrocarbon. Term C_nMeaning that the alkylene group has "n" carbon atoms. For example, C_1-6Alkylene means alkylene having, for example, 1,2, 3, 4,5 or 6 carbon atoms. The term "alkenylene" refers to a divalent hydrocarbon having at least one double bond.

In some cases, at least one R₂The segment comprises an aromatic group substituted with one or more relatively hydrophilic groups. The one or more hydrophilic groups may be selected from the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone), amino, carboxylic acid ester, sulfonic acid ester, phosphoric acid ester, ammonium (e.g., tertiary ammonium and quaternary ammonium), bisSexual ions (e.g., betaines, such as poly (carboxybetaine) (pCB), and ammonium phosphonates, such as phosphatidylcholine), and combinations thereof. Suitable aromatic groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylene, indanyl, indenyl, anthracenyl, fluorenylpyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl benzothiazolyl, and combinations thereof.

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

In some aspects, R₂The segment may comprise charged groups capable of binding with counter ions, ionically crosslinking the thermoplastic polymer and forming an ionomer. In these aspects, for example, R₂Having pendant amino, carboxylate, sulfonate, phosphorus groupsAn aliphatic or aromatic group of an acid ester, an ammonium or zwitterionic group, or a combination thereof.

In various instances, when a pendant hydrophilic group is present, the pendant "hydrophilic" group is at least one polyether group, such as two polyether groups. In other cases, the pendant hydrophilic group is at least one polyester. In various instances, the pendant hydrophilic groups are polylactone groups (e.g., polyvinylpyrrolidone). Each carbon atom pendant from the hydrophilic group may optionally be substituted, for example, with C_1-6Alkyl substitution. In some of these aspects, the aliphatic and aromatic groups can be graft polymer groups in which the pendant groups are homopolymeric groups (e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

In some aspects, the pendant hydrophilic groups are polyether groups (e.g., polyethylene oxide groups, polyethylene glycol groups), polyvinylpyrrolidone groups, polyacrylic groups, or combinations thereof.

The pendant hydrophilic groups may be bonded to the aliphatic or aromatic groups through a linking group. The linking group can be any difunctional small molecule (e.g., C) capable of linking a pendant hydrophilic group to an aliphatic or aromatic group_1-20). For example, the linking group may comprise a diisocyanate group as previously described herein which forms a urethane linkage when linked to a pendant hydrophilic group and an aliphatic or aromatic group. In some aspects, the linking group can be 4,4' -diphenylmethane diisocyanate (MDI), shown below.

In some exemplary aspects, the pendant hydrophilic group is a polyoxyethylene group and the linking group is MDI, as shown below.

In some cases, the pendant hydrophilic groups are functionalized to enable them to be bonded to aliphatic or aromatic groups, optionally through linking groups. In various aspects, for example, when the pendant hydrophilic group comprises an alkylene group, it can undergo Michael addition (Michael addition) with a thiol-containing bifunctional molecule (i.e., a molecule having a second reactive group, such as a hydroxyl or amino group), resulting in a hydrophilic group that can react with the polymer backbone, optionally via a linking group, using the second reactive group. For example, when the pendant hydrophilic group is a polyvinylpyrrolidone group, it can react with a thiol group on a mercaptoethanol to produce a hydroxy-functionalized polyvinylpyrrolidone, as shown below.

In some aspects disclosed herein, at least one R is₂The segment comprises a polytetramethylene oxide group. In other exemplary aspects, at least one R₂The segments may comprise aliphatic polyol groups functionalized with polyethylene oxide groups or polyvinylpyrrolidone groups, such as the polyols described in european (E.P.) patent No. 2462908. For example, R₂The segment may be derived from the reaction product of a polyol (e.g., pentaerythritol or 2,2, 3-trihydroxypropanol) with MDI-derivatized methoxypolyethylene glycol (for obtaining compounds as shown in formula 6 or formula 7) or MDI-derivatized polyvinylpyrrolidone (for obtaining compounds as shown in formula 8 or formula 9) that has previously been reacted with mercaptoethanol, as shown below.

In each case, at least one R₂Is a polysiloxane. In these cases, R₂Silicone monomers that can be derived from formula 10, such as disclosed in U.S. patent No. 5,969,076, which is incorporated herein by reference:

wherein:

a is 1 to 10 or greater than 10 (e.g., 1,2, 3, 4,5, 6, 7, 8, 9, or 10);

each R₄Independently of each other is hydrogen, C_1-18Alkyl radical, C_2-18Alkenyl, aryl or polyether; and is

Each R₅Independently is C_1-10Alkylene, polyether or polyurethane.

In some aspects, each R is₄Independently is H, C_1-10Alkyl radical, C_2-10Alkenyl radical, C_1-6Aryl, polyethylene, polypropylene or polybutylene groups. For example, each R₄May be independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, propenyl, phenyl and polyvinyl.

In various aspects, each R⁵Independently contain C_1-10Alkylene (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene). In other cases, each R⁵Is a polyether group (e.g., polyethylene, polypropylene, or polybutylene group). In various instances, each R5 is a polyurethane group.

Alternatively, in some aspects, the polyurethane may comprise an at least partially cross-linked polymeric network comprising copolymer chains that are derivatives of the polyurethane. In such cases, it is understood that the degree of crosslinking is such that the polyurethane retains thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane is capable of softening or melting and resolidifying under the process conditions described herein). This crosslinked polymeric network may be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polymercapto compounds, or combinations thereof, as shown in formulas 11 and 12 below:

wherein the variables are as described above. Additionally, the isocyanates may also be chain extended by bridging two or more isocyanates with one or more polyamino or polythiol chain extenders, as previously described with respect to the polyurethane of formula 2.

In some aspects, the thermoplastic polyurethane consists of MDI, PTMO, and 1, 4-butanediol, as described in U.S. patent No. 4,523,005.

As described herein, thermoplastic polyurethanes can be physically crosslinked (hard segments. in these aspects, component R in formula 1. As shown in FIGS. 1, the thermoplastic polyurethane can be crosslinked by, for example, nonpolar or polar interactions between urethane or urethane groups on the polymer₁And component R in formula 2₁And R₃Form what is often referred to as a "hard segment" of the polymer, and component R₂Forming what is often referred to as a "soft segment" in the polymer. In these aspects, the soft segment can be covalently bonded to the hard segment. In some examples, the thermoplastic polyurethane having physically crosslinked hard and soft segments may be a hydrophilic thermoplastic polyurethane (i.e., a thermoplastic polyurethane comprising hydrophilic groups as disclosed herein).

Commercially available thermoplastic polyurethanes having greater hydrophilicity suitable for current use include, but are not limited to, thermoplastic polyurethanes available under the trade names: "TECOPHILIC", such as TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60 (Lubrizol, Countryside, IL) of Conterey; "ESTANE" (e.g., ALR G500 or 58213; Luborun, Conterey, Ill.).

In various aspects, the thermoplastic polyurethane may be partially covalently crosslinked, as previously described herein.

In various aspects, the thermoplastic polymer can include a thermoplastic polyamide. The thermoplastic 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.

In various aspects, the thermoplastic polymer can be a block copolyamide. For example, the block copolyamide may have hard segment repeating blocks and soft segment repeating blocks. The hard segments may include polyamide segments and the soft segments may include non-polyamide segments. The thermoplastic polymer may be an elastomeric thermoplastic copolyamide comprising or consisting of: a block copolyamide having hard segment repeating blocks and soft segment repeating blocks. In block copolymers, including block copolymers having repeating hard and soft segments, there may be physical cross-linking within the blocks or between the blocks or within and between the blocks.

The thermoplastic 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 blocks. In a particular example, the polyamide segments may comprise or consist of: a polyamide 6 segment, or a polyamide 12 segment, or a polyamide 6 segment and a polyamide 12 segment. In the example 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 a polyether segment and a polyester segment. The copolyamide may be a block copolyamide or may be a random copolyamide. The thermoplastic copolyamide may be formed by polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a block copolyamide (i.e., a block copolymer comprising polyamide segments). Alternatively, the second prepolymer may be a hydrophilic prepolymer.

In some aspects, the thermoplastic polyamide itself or the polyamide segments of the thermoplastic copolyamide may be derived from the condensation of a polyamide prepolymer, such as a lactam, an amino acid, and/or a diamino compound, with a dicarboxylic acid or an activated form thereof. The resulting polyamide segment contains amide linkages (- (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 of the thermoplastic polyamide may be the same or different.

In some aspects, the polyamide segments of the thermoplastic polyamide or thermoplastic copolyamide are derived from the polycondensation of lactams and/or amino acids and comprise amide segments having the structure shown in formula 13 below, wherein R is₆Are segments of polyamides derived from lactams or amino acids.

In some aspects, R₆Derived from a lactam. In some cases, R₆Derived from C_3-20Lactams or C_4-15Lactams or C_6-12A lactam. For example, R₆May be derived from caprolactam or laurolactam. In some cases, R₆Derived from one or more amino acids. In each case R₆Derived from C_4-25Amino acid or C_5-20Amino acid or C_8-15An amino acid. For example, R₆May be derived from 12-aminododecanoic acid or 11-aminoundecanoic acid.

Alternatively, to increase the relative degree of hydrophilicity of the thermoplastic copolyamide, formula 13 may contain polyamide-polyether block copolymer segments, as shown below:

wherein m is 3 to 20 and n is 1 to 8. In some exemplary aspects, m is 4 to 15 or 6 to 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. In various aspects, the polyamide segments of the thermoplastic polyamide or thermoplastic copolyamide are derived from the condensation of a diamino compound with a dicarboxylic acid or an activated form thereof and comprise amide segments having the structure shown in formula 15 below, wherein R is₇Is a segment of a polyamide derived from a diamino compound, R₈Is a segment derived from a dicarboxylic acid compound:

in some aspects, R₇Derived from a compound containing a compound having C_4-15Carbon atoms or C_5-10Carbon atoms or C_6-9Diamino compounds of aliphatic groups of carbon atoms. In some aspects, the diamino compound comprises an aromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Can derive R₇Suitable diamino compounds of (a) include, but are not limited to, Hexamethylenediamine (HMD), tetramethylenediamine, Trimethylhexamethylenediamine (TMD), m-xylylenediamine (MXD), and 1, 5-pentanediamine (1, 5-pentanediamine). In various aspects, R₈Derived from dicarboxylic acids or activated forms thereof, containing compounds having C_4-15Carbon atoms or C_5-12Carbon atoms or C_6-10Aliphatic radicals of carbon atoms. In some cases, R can be derived₈The dicarboxylic acids of (a) or their activated forms contain aromatic groups such as phenyl, naphthyl, xylyl and tolyl. Can derive R₈Suitable carboxylic acids or activated forms thereof include, but are not limited to, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. In some aspects, the copolymer chains are substantially free of aromatic groups.

In some aspects, each polyamide segment of the thermoplastic polyamide (comprising the thermoplastic copolyamide) is independently derived from a polyamide prepolymer selected from the group consisting of 12-aminododecanoic acid, caprolactam, hexamethylenediamine, and adipic acid.

In some aspects, the thermoplastic polyamide comprises or consists of a thermoplastic poly (ether-block-amide). Thermoplastic poly (ether-block-amide) s can be formed from the polycondensation of a carboxylic acid terminated polyamide prepolymer and a hydroxyl terminated polyether prepolymer to form a thermoplastic poly (ether-block-amide), as shown in formula 16. The polyamide blocks of the thermoplastic 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. The number average molecular weight of the polyether blocks may be in the range of about 400g/mol to 3000 g/mol. The number average molecular weight of the Polyamide (PA) blocks may be in the range of about 500g/mol to 5000 g/mol. In particular examples, the Polyether (PE) content (x) of the thermoplastic poly (ether-block-amide) copolymer may be in the range of about 0.05 to about 0.8 (i.e., about 5 mol% to about 80 mol%).

In some examples, the thermoplastic polyamide is physically crosslinked by, for example, nonpolar or polar interactions between the polyamide groups of the polymer. In examples where the thermoplastic polyamide is a thermoplastic copolyamide, the thermoplastic copolyamide may be physically crosslinked by interaction between the polyamide groups, optionally by interaction between the copolymer groups. When the thermoplastic copolyamide is physically crosslinked by interaction between the polyamide groups, the polyamide segments may form what are referred to as "hard segments" in the polymer, and the copolymer segments may form what are referred to as "soft segments" in the polymer. For example, when the thermoplastic copolyamide is a thermoplastic poly (ether-block-amide), the polyamide segments form the hard segment portion of the polymer, and the polyether segments can form the soft segment portion of the polymer. Thus, in some examples, the thermoplastic polymer may comprise a physically cross-linked polymeric network having one or more amide bond-containing polymer chains.

In some aspects, the polyamide segment of the thermoplastic copolyamide comprises polyamide-11 or polyamide-12 and the polyether segment is a segment selected from the group consisting of polyethylene oxide, polypropylene oxide, and polytetramethylene oxide segments, and combinations thereof. Commercially available thermoplastic polyamides suitable for current use include those under the trade names: "platami" (e.g., H2694) and "PEBAX" (e.g., "PEBAX MH 1657" and "PEBAX MV 1074") of Arkema (Arkema, inc., Clear Lake, TX) of clearley, TX, and "SERENE" paint (semdics, Eden Prairie, MN), of idenprep, MN).

Alternatively, the thermoplastic polyamide may be partially covalently crosslinked, as previously described herein. In such cases, it is understood that the degree of crosslinking present in the thermoplastic polyamide is such that when it is heat treated in yarn or fiber form to form the article of footwear of the present disclosure, the partially covalently crosslinked thermoplastic polyamide retains thermoplastic characteristics sufficient for the partially covalently crosslinked thermoplastic polyamide to soften or melt and resolidify during processing.

In various aspects, the thermoplastic polymer can include a thermoplastic polyester. The thermoplastic polyester may be formed by polycondensation of a carboxylic acid with a diol. The thermoplastic polyester may be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester may include 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.

The thermoplastic 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 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 thermoplastic polyester may be a block copolyester having repeating blocks of relatively hard polymer units (segments) (hard segments) of the same chemical structure and repeating blocks of relatively soft polymer segments (soft segments). In block copolyesters, including block copolyesters having repeating hard and soft segments, there can be physical cross-linking within the blocks or between the blocks or both. In a particular example, the thermoplastic material may comprise or consist essentially of: an elastomeric thermoplastic copolyester having repeating blocks of hard segments and repeating blocks of soft segments.

The non-polyester segments of the copolyester may comprise or consist of: a polyether segment, a polyamide segment, or a polyether segment and a polyamide segment. The copolyester may be a block copolyester, or may be a random copolyester. The thermoplastic copolyester may be formed by polycondensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Alternatively, the second prepolymer may be a hydrophilic prepolymer. For example, copolyesters can be formed by 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. In a particular example, the copolyamide may comprise or consist of polyethylene terephthalate.

In some aspects, the thermoplastic polymer can comprise or consist essentially of a thermoplastic polyolefin. Thermoplastic polyolefins may be formed by 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). Illustrative examples of thermoplastic polyolefins may include polyethylene, polypropylene, and thermoplastic olefin elastomers.

High processing temperature polymer compositions

As discussed above, the low processing temperature polymer composition and the high processing temperature polymer composition have different properties. For example, the high processing temperature polymer composition may exhibit a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mHigh creep relaxation temperature T_crVicat softening temperature T_vsThermal deformation temperature T_hdOr melting temperature T_mAt least one of (a). When thermoforming a fabric comprising a low processing temperature polymer composition and a high processing temperature polymer composition according to the present disclosure, thermoforming is conducted under conditions where the high processing temperature polymer composition does not melt or deform and the low processing temperature polymer composition melts.

In one or more aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA melting temperature T at least about 10 ℃ higher_m. In another aspect, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA melting temperature T at least about 20 ℃ higher_m. In certain aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA melting temperature T at least about 40 ℃ higher_m。

In various aspects, the high processing temperature polymer composition exhibits a melting temperature T of about 140 ℃ to about 500 ℃_m. In one or more aspects, the high processing temperature polymer composition exhibits a temperature of about 140 ℃ to about 400 ℃Melting temperature T_m. In certain aspects, the high processing temperature polymer composition exhibits a melting temperature T of about 140 ℃ to about 300 ℃_m。

In certain aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA creep relaxation temperature T of at least about 10 ℃ higher_cr. In one or more aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA creep relaxation temperature T of at least about 30℃ higher_cr. In one aspect, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA creep relaxation temperature T of at least about 50 ℃ higher_cr。

In certain aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mVicat softening temperature T at least about 10 ℃ higher_vs. In one or more aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mVicat softening temperature T at least about 30 ℃ higher_vs. In one aspect, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mVicat softening temperature T at least about 50 ℃ higher_vs。

In certain aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA heat distortion temperature T of at least about 10 ℃ higher_hd. In various aspects, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA heat distortion temperature T at least about 30 ℃ higher_hd. In one aspect, the high processing temperature polymer composition exhibits a melting temperature T that is greater than the melting temperature of the low processing temperature polymer composition_mA heat distortion temperature T at least about 50 ℃ higher_hd。

As stated above, the high processing temperature polymer composition comprises one or more second thermoplastic polymers. One or more of high processing temperature polymer compositionsThe plurality of second thermoplastic polymers may be thermoplastic polymers as described above as exemplary thermoplastic polymers, it being understood that the melting temperature T is a function of_mThe one or more second thermoplastic polymers are different from the one or more first thermoplastic polymers of the low processing temperature polymer composition. The high processing temperature polymer composition comprises one or more second thermoplastic polymers having a sufficiently high melting temperature T_mPresent in the composition in a concentration sufficiently high to cause the creep relaxation temperature T of the high processing temperature polymer composition_crThermal deformation temperature T_hdOr Vicat softening temperature T_vsAbove the melting temperature T of the low melting temperature polymer composition_m。In one aspect, the one or more second thermoplastic polymers may comprise one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins. In certain aspects, the thermoplastic polymer may comprise one or more thermoplastic polymers selected from the group consisting of thermoplastic polyesters, polyethers, polyamides, and combinations thereof. In aspects, the thermoplastic polymer may comprise one or more thermoplastic polymers selected from the group consisting of thermoplastic polyesters, polyamides, and combinations thereof.

In various aspects, the thermoplastic polymer can comprise one or more thermoplastic polyesters. In these aspects, the thermoplastic polyester can comprise polyethylene terephthalate (PET). In certain aspects, the thermoplastic polymer may comprise one or more thermoplastic polyamides. In these aspects, the thermoplastic polyamide may comprise poly (hexamethylene adipamide) (nylon 6,6), polycaprolactam (nylon 6), polydodecalactam (nylon 12), and combinations thereof. In one aspect, the thermoplastic polymer may comprise one or more thermoplastic polyurethanes.

In various aspects, the thermoplastic polymer can comprise one or more copolymers. In aspects, the thermoplastic polymer may comprise one or more copolymers selected from the group consisting of copolyesters, copolyethers, copolyamides, copolyurethanes, and combinations thereof. In one aspect, the thermoplastic polymer may comprise one or more copolyesters. In certain aspects, the thermoplastic polymer can comprise one or more copolyethers. In various aspects, the thermoplastic polymer may comprise one or more copolyamides. In various aspects, the thermoplastic polymer may comprise one or more copolyurethanes. In one aspect, the thermoplastic polymer may comprise one or more polyether block amide (PEBA) copolymers. In various aspects, the copolymer may comprise relatively hard polymer segments copolymerized with relatively soft polymer segments.

Anchoring yarn composition

As discussed above, the anchoring yarns may be used to help restrict the flow of molten materials, such as low processing temperature polymer compositions, during the thermoforming process, and/or to impart some flexibility to the thermoformed material. In these aspects, the anchoring yarns do not melt or deform during the thermoforming process. Thus, in certain aspects, the anchor yarn may comprise an anchor yarn composition comprising one or more third thermoplastic polymers such that the anchor yarn composition exhibits a melting temperature T greater than that of the low processing temperature polymer composition_mHigh creep relaxation temperature T_crVicat softening temperature T_vsThermal deformation temperature T_hdOr melting temperature T_mAt least one of (a). In certain aspects, the anchor yarn composition may have specific ranges related to these properties discussed above with respect to the high processing temperature polymer composition. In certain aspects, the anchor yarns may be formed from the high processing temperature polymer composition, and thus may include any of the thermoplastic polymers discussed above with respect to the high processing temperature polymer composition.

Exemplary aspects of wearing articles and fabrics

As discussed above, certain aspects are directed to one or more fabrics comprising fibers and/or yarns comprising a low processing temperature polymer composition and a high processing temperature polymer composition. In various aspects, such fabrics may form at least a portion of an article of wear.

Turning now to the drawings, and in particular to fig. 1A and 1B, an article of footwear 100 is depicted as an exemplary article of wear. Although fig. 1A and 1B depict an article of footwear 100, it should be understood that other articles of wear are also contemplated by the present disclosure. A non-limiting list of articles of wear contemplated by the present disclosure includes footwear, shirts, pants, socks, jackets or other outerwear, protective equipment, hats, and undergarments, such as bras.

Article of footwear 100 of fig. 1A and 1B may generally include an earthed outsole 110, an ankle collar region 112, lateral and medial midfoot regions 114a and 114B, a toe box region 116, and a heel region 118. In addition, article of footwear 100 may include a plurality of eyelets 120, vamp region 122, tongue region 124, and throat region 126.

The article of footwear 100 depicted in fig. 1A and 1B may incorporate at least one textile 102 that at least partially forms a portion of the article of footwear 100. Fabric 102 of article of footwear 100 may include at least three separate fabric regions, such as fabric region 104, fabric region 106, and fabric region 108, which define particular functional regions of article of footwear 100. In certain aspects, these particular functional regions are at least partially associated with the incorporation of particular fabric media in different amounts, techniques, and orientations combined into the fabric regions (shown in fig. 1A and 1B as fabric regions 104, 106, and 108). It should be understood that while the fabric 102 includes three specific functional zones, more than three functional zones are also contemplated.

In certain aspects, textile region 104 may exhibit a rigid or semi-rigid functionality suitable for use as a ground-contacting outsole 110 of article of footwear 100. Accordingly, in certain aspects, textile region 104 may be positioned to contain at least a portion of a ground-contacting outsole 110 of article of footwear 100. In certain aspects, directionally incorporating a low processing temperature polymer composition into the fabric region 104 of the fabric 102 after thermoforming can provide, at least in part, a rigid or semi-rigid functionality suitable for use as a ground-contacting outsole 110. As used herein, "thermoforming" refers to a process that may involve melting and/or deformation of a low processing temperature polymer composition and/or one or more thermoplastic polymers and subsequent cooling of the melted and/or deformed material to form a sheet or film, which may be rigid or semi-rigid. The thermoforming process is discussed in detail below.

Further, in various aspects, another fabric region, such as fabric region 108, can exhibit flexibility and/or softness to accommodate movement of the wearer. In some aspects, textile region 108 may include ankle collar region 112, tongue region 124, and/or throat region 126 of article of footwear 100. In various aspects, the fabric region 108 can comprise a high processing temperature polymer composition.

In certain aspects, another fabric, such as fabric region 106, can be positioned between fabric region 104 and fabric region 108. In certain aspects, textile region 106 may be included on article of footwear 100 in at least a portion of lateral midfoot region 114a and/or medial midfoot region 114 b. In certain aspects, the fabric region 106 can comprise a combination of the low processing temperature polymer composition of the fabric region 104 and the high processing temperature polymer composition of the fabric region 108. In these aspects, this combination of fabric media present in fabric region 106 enables fabric region 106 to transition between the rigid or semi-rigid functionality of fabric region 104 and the flexible, soft functionality of fabric region 108, enabling a more gradual transition of fabric 102 from rigid to flexible.

Further, in these aspects, fabric region 106 can exhibit a lower degree of rigidity or semi-rigidity than fabric region 104, but can exhibit a higher degree of rigidity or semi-rigidity than fabric region 108. Further, in the same or alternative aspects, fabric region 106 can exhibit a lower degree of flexibility as compared to fabric region 108, but can exhibit a higher degree of flexibility as compared to fabric region 104.

Alternatively or additionally, three fabric regions 104, 106, and 108 can be located at least partially within a midfoot region, such as lateral midfoot region 114a and/or medial midfoot region 114 b.

In certain aspects, the combination of the low processing temperature polymer composition present in fabric region 104 and the high processing temperature polymer composition present in fabric region 108 in fabric region 106, when exposed to a thermoforming process, can impart one or more structural properties to article of footwear 100, such as a semi-rigid support in lateral midfoot region 114a and/or medial midfoot region 114b, and/or a three-dimensional shape or structure to one or more portions of article of footwear 100.

In some aspects, as can be seen in fig. 1A, fabric region 106 extends from fabric region 104 toward eyelets 120. In these aspects, the combination of a textile medium comprising a low processing temperature polymer composition and a textile medium comprising a high processing temperature polymer composition enables the transfer of forces transmitted from eyelets 120 or other lacing mechanisms to this textile medium combination present in lateral midfoot region 114a and/or medial midfoot region 114 b. In certain aspects, with respect to successful transfer of forces transmitted from eyelets 120, the low processing temperature polymer composition present in fabric region 104 and/or fabric region 104 can terminate at region 128 at a distance of at least about 0.5cm, about 1.0cm, or about 2.0cm from eyelets 120, and/or at region 128 at a distance of at least about 3 stitches, at least about 4 stitches, or at least about 5 stitches below eyelets 120 when fabric 102 is a knit fabric formed on a commercial knitting machine. In these aspects, the flexible and soft nature of the high processing temperature polymer composition present in fabric region 108 adjacent to eyelet 120 helps to transfer forces transmitted from eyelet 120 to the low processing temperature polymer composition present in fabric region 106 and/or lateral midfoot region 114a and/or medial midfoot region 114 b.

In the aspect depicted in fig. 1A and 1B, the textile region 106 is located in a toe cap region 116 and a heel region 118. In these aspects, the combination of the low processing temperature polymer composition and the high processing temperature polymer composition can provide structure and/or support because of the rigidity provided by the thermoformed material. In addition, the thermoformed material can provide wear resistance in the toe cap region 116 and/or the heel region 118. In alternative aspects, to increase rigidity or increase wear resistance, the fabric region 104 can form at least a portion of the toe cap region 116 and/or the heel region 118 because the fabric region 104 includes a greater amount of the low processing temperature polymer composition than the fabric region 106, or the low processing temperature polymer composition is otherwise positioned (e.g., outer woven surface).

Fig. 1C depicts an alternative aspect of article of footwear 100 a. In these aspects, article of footwear 100a may generally include at least three types of textile regions: fabric region 104a, fabric region 106a, and fabric region 108 a. In certain aspects, textile regions 104a, 106a, and 108a may have the same characteristics and parameters as textile regions 104, 106, and 108, respectively, of article of footwear 100 discussed above with respect to fig. 1A.

In the aspect depicted in fig. 1C, portions of textile region 104a, such as portions 104b and 104C, can extend from the outsole region up through midfoot region 115a and toward the plurality of eyelets 120 a. In these aspects, the rigid or semi-rigid functionality provided by portions 104b and 104c extending from the outsole region through midfoot region 115a to plurality of eyelets 120a can improve wearer stability in midfoot region 115 a. Further, in various aspects, the force applied by one or more of the plurality of eyelets 120a may be at least partially transferred onto the rigid or semi-rigid portions 104b and 104c extending through the midfoot region 115a and into the rigid or semi-rigid fabric region 104a present in the outsole region, resulting in improved support for the wearer and wearer comfort.

In certain aspects, the thermoformed material can provide a waterproof or water-resistant surface in addition to providing structure, rigidity, strength, and/or support to one or more regions of the article of wear.

Fig. 2A and 2B depict a shirt 200 as one exemplary article of apparel. The shirt 200 depicted in fig. 2A and 2B includes at least one fabric 202 that at least partially forms a portion of the shirt 200. As best seen in fig. 2B, the fabric 202 may include three separate fabric regions: 204. 206a to 206d, and 208, which may identify particular functional areas of shirt 200. In certain aspects, the particular functional regions are associated, at least in part, with incorporation of particular fabric media in different amounts and orientations combined into the fabric regions 204, 206 a-206 d, and 208.

In certain aspects, fabric region 204 may include a reinforced area, such as an exterior-facing film (exterior-facing film) or patch 210, which may, for example, provide abrasion resistance to elbow region 212 of shirt 200. In these aspects, directionally integrating the low processing temperature polymer composition into the fabric region 204 can at least partially form the patch 210, when the fabric 202 is thermoformed, by melting or deforming the low processing temperature polymer composition and then allowing the melted material to cool and solidify to form the patch 210.

In various aspects, the fabric region 208 can exhibit flexibility and/or softness similar to conventional shirt materials. In these aspects, the fabric region 208 can comprise or only comprise the high processing temperature polymer composition. Further, in certain aspects, the fabric region 206 can provide, at least in part, a transition in the fabric 202 from a rigid or semi-rigid patch 210 present in the fabric region 204 to a flexible, soft portion present in the fabric region 208. In these aspects, the fabric regions 206 a-206 d can comprise a combination of a low processing temperature polymer composition present in the fabric region 204 and a high processing temperature polymer composition present in the fabric region 208. Although not shown in fig. 2A and 2B, fabric region 206B to fabric region 206d also provide a transition to a soft, flexible material, such as that present in fabric region 208.

In certain aspects, such a combination of the low processing temperature polymer composition from fabric region 204 and the high processing temperature polymer composition present in fabric region 208, as discussed above with respect to fabric region 106 of fabric 102 in fig. 1A and 1B, may provide a seamless or integral transition from patch 210 to the flexible, soft portion present in fabric region 208 of shirt 200.

While this exemplary illustration of fabric regions 204, 206 a-206 d, and 208 in fig. 2A and 2B refers to elbow regions of an article of apparel, such as shirt 200, it should be understood that fabric regions 204, 206 a-206 d, and 208 and related features apply to other regions of a shirt or other article of apparel, such as the knees, thighs, buttocks, chest, and/or lower back regions of the article of apparel, or regions requiring reinforcement, such as regions proximate fasteners, such as zippers, buttons, snaps, lanyards, and the like.

Turning now to fig. 3, a plan view of an exemplary fabric 300 is provided. It is understood that the fabric 300 may be any type of fabric known to those skilled in the art. A non-limiting list of fabrics suitable for use in the articles of wear and methods disclosed herein includes knitted fabrics, woven fabrics, non-woven fabrics, and wound fabrics.

Similar to the fabric 102 of fig. 1A and 1B and the fabric 202 of fig. 2A and 2B, the fabric 300 of fig. 3 includes three types of fabric regions. For example, the fabric 300 includes: fabric region 302, which may comprise fibers and/or yarns comprising a low processing temperature polymer composition, fabric regions 306a and 306b, which may comprise a high processing temperature polymer composition, and fabric regions 304a and 304b, which may comprise a combination of fibers and/or yarns comprising a low processing temperature polymer composition and fibers and/or yarns comprising a high processing temperature polymer composition. In fabric 300 of fig. 3, fabric regions 304a and 304b may be located on either side of fabric region 302, while fabric regions 306a and 306b may be located on opposite sides of fabric regions 304 and 304b, respectively.

In certain aspects, the fibers and/or yarns comprising the low processing temperature polymer composition present in the fabric region 302 are capable of imparting structural or functional properties to the fabric 300 that are useful in forming articles of wear when exposed to a thermoforming process. For example, fabric region 302 may represent fabric region 104 of fabric 102 of fig. 1A and 1B, which forms at least a portion of outsole 110. In various aspects, the fibers and/or yarns comprising the high processing temperature polymer composition present in textile regions 306a and 306B can impart flexibility or softness to textile 300, such as textile region 108 of article of footwear 100 depicted in fig. 1A and 1B. Further, in various aspects, the fabric regions 304a and 304b can comprise a combination of fibers and/or yarns comprising the low processing temperature polymer composition present in the fabric region 302 and fibers and/or yarns comprising the high processing temperature polymer composition present in the fabric region 306a and 306b to provide structural support and three-dimensional structure to a particular article of wear. Further, as discussed above, in certain aspects, this combination of fibers and/or yarns comprising the low processing temperature polymer composition and fibers and/or yarns comprising the high processing temperature polymer composition in the fabric regions 304a and 304b can provide an integral transition between the rigid thermoformed material in the fabric region 302 and the flexible, soft high processing temperature polymer composition in the fabric regions 306a and 306 b.

In one or more aspects, the fabric regions 304a and 304b can comprise a plurality of zones (zones), such as zone 305a, zone 305b, zone 305c, and zone 305d of fabric region 304a, which zones can comprise different combinations and/or different orientations of fibers and/or yarns comprising the low processing temperature polymer composition and fibers and/or yarns comprising the high processing temperature polymer composition. In certain aspects, zone 305a can comprise fibers and/or yarns comprising a low processing temperature polymer composition, but not fibers and/or yarns comprising a high processing temperature polymer composition present in fabric region 306a and/or fabric region 306 b. In the same or alternative aspects, zone 305d can comprise fibers and/or yarns comprising a high processing temperature polymer composition, but not fibers and/or yarns comprising a low processing temperature polymer composition present in fabric region 302.

It should be understood that although only a partition of the fabric region 304a is further described herein, such description also applies to partitions present in the fabric region 304 b. Further, it should be understood that if in certain descriptions only fabric region 304a and/or fabric region 306a are discussed further, such descriptions also apply to fabric region 304b and fabric region 306b, respectively.

In certain aspects, the fabric 300 can have different concentrations of the low processing temperature polymer composition and/or the high processing temperature polymer composition in the fabric regions 302, 304a, 306a depending on the relative positioning of the fibers and/or yarns comprising the low processing temperature polymer composition and the fibers and/or yarns comprising the high processing temperature polymer composition in these fabric regions 302, 304a, 306 a.

As used herein, the term "concentration" refers to clustering or aggregation in a particular volume. Thus, the term concentration encompasses measuring a specified volume (e.g., cm)³) Amount of material (e.g., weight, in grams). For example, in a woven fabric, a first portion of a single woven layer of the fabric has an increased first yarn concentration as compared to a second portion of the fabric by having more first yarn weaves (e.g., weave, tuck, and/or float) than a second portion of the same size. In another example, in a nonwoven fabric, if the fabric is formed with more first fibers (e.g., weight in grams) than a second portion of the same size, then the first portion of the fabric may have an increased concentration of first fibers.

In various aspects, the fabric region 302 can include an increased concentration of fibers and/or yarns including the low processing temperature polymer composition as compared to the fabric region 304a and/or the fabric region 306 a. For example, in these aspects, the fabric region 302 can have at least 5 wt% more fibers and/or yarns comprising the low processing temperature polymer composition than the fabric region 304a and/or the fabric region 306 a. In another aspect, the fabric region 302 can have at least 10% more fibers and/or yarns comprising the low processing temperature polymer composition by weight than the fabric region 304a and/or the fabric region 306 a. In one aspect, fabric region 302 can have at least 25% more fibers and/or yarns comprising the low processing temperature polymer composition by weight than fabric region 304a and/or fabric region 306 a.

In the same or alternative aspects, the fabric region 304a can include an increased concentration of fibers and/or yarns comprising the low processing temperature polymer composition as compared to the fabric region 306 a. For example, in these aspects, the fabric region 304a can have at least 5 wt% more fibers and/or yarns comprising the low processing temperature polymer composition than the fabric region 306 a. In another aspect, the fabric region 304a can have at least 10% more fibers and/or yarns comprising the low processing temperature polymer composition by weight than the fabric region 306 a. In one aspect, fabric region 304a can have at least 25% more fibers and/or yarns comprising the low processing temperature polymer composition by weight than fabric region 306 a.

In various aspects, the fabric region 306a can include an increased concentration of fibers and/or yarns comprising the high processing temperature polymer composition as compared to the fabric region 302 and fabric region 304 a. For example, in these aspects, the fabric region 306a can have at least 5% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than the fabric region 302 and/or the fabric region 304 a. In another aspect, the fabric region 306a can have at least 10% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than the fabric region 302 and/or the fabric region 304 a. In one aspect, fabric region 306a can have at least 25% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than fabric region 302 and/or fabric region 304 a.

In certain aspects, the fabric region 304a can comprise an increased concentration of fibers and/or yarns comprising the high processing temperature polymer composition as compared to the fabric region 302. For example, in these aspects, the fabric region 304a can have at least 5% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than the fabric region 302. In another aspect, the fabric region 304a can have at least 10% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than the fabric region 302. In one aspect, the fabric region 304a can have at least 25% more fibers and/or yarns comprising the high processing temperature polymer composition by weight than the fabric region 302.

Fig. 4A-4D schematically depict exemplary cross-sections of fabric region 302, fabric region 304A, and fabric region 306a of fabric 300. In general, fig. 4A depicts an exemplary cross-section of the fabric region 306a and further illustrates how this portion of the fabric region 306a includes fibers and/or yarns that include the high processing temperature polymer composition in certain aspects, but does not include fibers and/or yarns that include the low processing temperature polymer composition present in the fabric region 302. Fig. 4B depicts an exemplary cross-section of the fabric region 302 and also illustrates how this portion of the fabric region 302 includes fibers and/or yarns that include a low processing temperature polymer composition in various aspects, but does not include fibers and/or yarns that include a high processing temperature polymer composition present in the fabric region 306 a. Fig. 4C and 4D depict two exemplary cross-sections of the fabric region 304a and further illustrate how fibers and/or yarns comprising the low processing temperature polymer composition and fibers and/or yarns comprising the high processing temperature polymer composition are present in these exemplary portions of the fabric region 304 a.

The cross-sections depicted in fig. 4A-4D will now be described from the perspective that the fabric 300 is a woven fabric. Various processes for forming woven fabrics and the types of yarns that may be used are discussed in detail below. It is contemplated that a variety of weaving techniques may be implemented to achieve the results. For example, in some aspects, a purl stitch (purl stitch) may be substituted for a "knit stitch" to achieve similar results with different aesthetics and/or texture. For simplicity herein, "woven structure" will be discussed, although it is contemplated that functional equivalents may be substituted. Similarly, "tuck tissue" may be discussed in certain aspects, but it is contemplated that alternative suturing techniques may also be implemented to achieve similar results. While relatively simple weave structures are depicted and discussed, numerous warp and weft knit structures are formed by, for example, flat knitting (flat knitting), wide tube circular knitting (wide tube circular knitting), narrow tube circular knitting jacquard (narrow tube circular knitting jacquard), single needle circular knitting jacquard (single needle circular knitting jacquard), double needle circular knitting jacquard (double needle circular knitting jacquard), warp knitting jacquard (warp knitting jacquard), and warp knit (tricot).

It should be understood that the cross-sections depicted in fig. 4A-4D are schematic and that each cross-section is organized into different portions to highlight potential braided structures that may be present. First, potential weave structures that may exist in different portions of these cross-sections are described.

Fig. 5A-5J depict exemplary potential braided structures that may be present in different portions of the cross-sections depicted in fig. 4A-4D. FIG. 5A depicts a knit stitch (or Jersey stitch) structure 502 formed by back needle bed 504. It should be understood that, according to the traditional organizational scheme, the row of small circles associated with back needle bed 504 represents the needles of back needle bed 504 (e.g., needles 505). Furthermore, this also applies to front needle beds, such as front needle bed 508 depicted in fig. 5B; that is, the small circle in the row associated with the front needle bed 508 represents a needle (e.g., needle 507) in the front needle bed 508.

Figure 5B depicts a knitted structure 506 formed by a front needle bed 508. FIG. 5C depicts a float stitch and tuck stitch construction 510 having a tuck stitch formed by a front needle bed 512 and a back needle bed 514. FIG. 5D depicts another float and tuck stitch construction 516 having a tuck stitch formed by a front needle bed 518 and a back needle bed 520. Fig. 5E depicts a floating line weave structure 522. Fig. 5F depicts a knit and tuck stitch structure 524 having a knit stitch 524a formed by the back needle bed 528 and a tuck stitch 524b formed by the front needle bed 526. FIG. 5G depicts a knit and miss stitch construction 530 having a knit stitch formed on the front needle bed 532. FIG. 5H depicts a knit and miss stitch construction 534 having a knit stitch formed on the back needle bed 536. FIG. 5I depicts a tuck stitch and float stitch structure 538 with a tuck stitch formed by the front needle bed 540. FIG. 5J depicts a tuck stitch and float stitch construction 542 having a tuck stitch formed on the back needle bed 544.

Returning now to section 4A through section 4D of fabric 300. Generally, the depicted sections 4A-4D are similar in structure because of the primary structure of the woven fabric. For example, in various aspects, there is a tubular knit structure that includes a knit structure formed primarily from the back needle bed (e.g., knit structure 502 depicted in fig. 5A) and a knit structure formed primarily on the front needle bed (e.g., knit structure 506 depicted in fig. 5B). Further, in these aspects, this tubular knit structure is connected with the float stitch structure by one or more tuck stitches, with the tuck stitches formed by the back and front needle beds (tuck and float stitch structure 510 and tuck and float stitch structure 516 as depicted in fig. 5C and 5D, respectively).

This joined tubular braided structure is schematically depicted in three prominent courses in the depicted cross sections 4A to 4D. For example, fig. 4A depicts cross-section 402 of the fabric region 306a of fig. 3 comprising a high processing temperature polymer composition.

The cross-section 402 of fig. 4A schematically depicts a top portion 404, a middle portion 406, and a bottom portion 408. Top portion 404 and bottom portion 408 represent knit structures used to form tubular knit structures, while middle portion 406 represents tuck stitch and float stitch structures used to connect tubular knit structures together. Thus, in certain aspects, the top portion 404 may include one or more of the braided structures 502 and the braided and tuck stitch structures 524 depicted in fig. 5A and 5F, respectively. The bottom portion 408 may include the braided structure 506 depicted in fig. 5B. The intermediate portion 406 may contain one or more of the float and tuck stitch structures 510 and 516 depicted in fig. 5C and 5D, respectively.

Fig. 4B depicts a cross-section 410 of the fabric region 302 including yarns comprising the low processing temperature polymer composition. Cross-section 410 includes a top portion 412, a middle portion 414, and a bottom portion 416, which may include the same braided structures identified above with respect to top portion 404, middle portion 406, and bottom portion 408 of cross-section 402 of fig. 4A.

In certain aspects, it may be desirable to increase the low processing temperature polymer composition in the fabric region 302 to provide a desired thickness and rigidity to the thermoformed fabric region 302, such as to form a ground-contacting outsole for an article of footwear. In these aspects, the fabric region 302 can include repeating stitches (stilches) to increase the concentration of yarns including the low processing temperature polymer composition relative to other fabric regions, such as fabric region 304a and/or fabric region 306 a. In certain aspects, the repeating tissue may be provided, for example, by including a plurality of tissue structures in any or all of the top portion 412, middle portion 414, and bottom portion 416 of the cross-section 410. In one example, a plurality of overlapping tuck-stitch and float-stitch structures (such as the structures depicted in fig. 5C, 5D, 5I, and 5J) may be provided in the middle portion 414 of the cross-section 410.

In certain aspects, in areas of the fabric 300 containing a significant number of yarns comprising the low processing temperature polymer composition, such as the fabric region 302, anchoring yarns 413 can be provided in the fabric 300 to help restrict the flow of the molten low processing temperature polymer composition and/or provide some flexibility to the thermoformed material. In the cross-section 410 depicted in fig. 4B, the anchor yarn 413 is depicted as being present in the middle portion 414 between the top portion 412 and the bottom portion 416. In these aspects, this positioning of the anchor yarns 413 may cause the anchor yarns 413 to be embedded or encapsulated by the low processing temperature polymer composition after thermoforming of the fabric 300.

Although the anchoring yarns 413 are depicted in fig. 4B as being straight lines, it should be understood that this is a schematic illustration of the anchoring yarns 413 and is not meant to designate any particular type of weave structure. For example, the anchoring yarns 413 may be present in the fabric 300 in many different types of woven structures, such as one or more of the structures depicted in fig. 5E and 5G-5J. In certain aspects, the weave selection of the anchoring yarns 413 may depend on the desired elongation resistance of the material in which the anchoring yarns 413 extend. For example, an anchor yarn weave that floats five stitches between tuck stitches or knit stitches will provide greater stretch resistance to the material in which the anchor yarn 413 extends than an anchor yarn weave that floats only 2 or 3 stitches between tuck stitches or knit stitches. In this example, the difference in resistance to elongation between the float lengths is a result of the non-linear portions (e.g., tissue coils) being more prone to elongation than the linear portions, which results in a difference in resistance to elongation.

In certain aspects, when the anchoring yarn 413 is present as one or more of the braided structures depicted in fig. 5G-5J, the anchoring yarn 413 extends as a float weave along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition, as the yarn comprising the low processing temperature polymer composition is also present in one or more of the braided structures of fig. 5A and 5B. Also in certain aspects, the anchor yarn 413 may extend as a float weave along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition and may also form at least a portion of a tuck weave and/or a knit weave with the yarn comprising the low processing temperature polymer composition. In these aspects, the segment between the tuck stitch or knit stitch is formed at least in part from a yarn comprising the low processing temperature polymer composition and an anchor yarn 413, which may extend along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition. In the same or alternative aspects, anchor yarn 413 may be stitched with loops, such as tuck stitch or knit stitch, at an amount of spacing, represented by the number of needles of a common needle bed, that is within 50% or within 25% of the gauge of a knitting machine used to form at least a portion of fabric 300.

Fig. 4C and 4D depict cross-sections of fabric region 304a and portions of fabric regions 302 and 306 a. For example, cross-section 418 of fig. 4C includes a portion 422 corresponding to fabric region 302 and a portion 420 corresponding to fabric region 306 a. The portion 424a, the portion 424b, the portion 424c, and the portion 424d correspond to the section 305a, the section 305b, the section 305c, and the section 305d, respectively, of the fabric region 304a of the fabric 300. The cross-sections of fig. 4C to 4E are schematically simplified; however, it is contemplated that one or more regions and/or portions of the cross-section may contain several different configurations and different concentrations of fibers and/or yarns. For example, the portion 424c in the middle portion 428 may include: fibers and/or yarns comprising a low processing temperature polymer composition and fibers and/or yarns comprising a high processing temperature polymer composition, but in different configurations/concentrations, as found in section 424b and/or section 424d of intermediate portion 428. In other words, the different construction techniques achieve a combination of fibers and/or yarns in a given portion and fabric region by varying the fiber and/or yarn concentration at the portion and/or fabric region level through a variation in the method (e.g., tissue selection) of combining, containing, connecting, depositing, or applying the fibers and/or yarns.

Section 418 of fig. 4C includes the same types of generally tubular braided structures discussed above with respect to section 402 and section 410 of fig. 4A and 4B, respectively. Thus, cross-section 418 includes a top portion 426, a middle portion 428, and a bottom portion 430. Top portion 426, middle portion 428, and bottom portion 430 may comprise the same braided structures discussed above with respect to top portion 404, middle portion 406, and bottom portion 408, respectively, of cross-section 402 of fig. 4A.

In section 418 of fig. 4C, portions 422 and 424a comprise woven structures made with yarns comprising low processing temperature polymer compositions, while portions 420, 424d and 424C comprise woven structures made with yarns comprising high processing temperature polymer compositions. However, as provided above, it is contemplated that combinations of fibers and/or yarns based on different stitching techniques may be implemented in different sections to achieve a transition from one primary material to another.

Portion 424b comprises a tubular braided structure made from yarns comprising a high processing temperature polymer composition; however, the knitted structure formed by the front and back needle beds (having yarns comprising the high processing temperature polymer composition) is joined by floats and tucks (or similar effective stitches) with yarns comprising the low processing temperature polymer composition. This section 424b illustrates how the low processing temperature polymer composition, when melted and solidified, physically joins the two outer woven layers together through a sheet or film of thermoformed material after the fabric 300 has undergone thermoforming. In these aspects, articles of wear having tubular knit structures of this type that have been thermoformed and joined by an integral thermoformed material primarily contain a typical layer of knitting yarns on opposite outer surfaces of the fabric joined together by a thermoformed film. Such a structure may be used to provide water/water resistance or other weather resistance to the article of wear, while still maintaining the aesthetics and feel of a typical woven article.

As with section 418 of fig. 4C, section 432 of fig. 4D includes a portion 436 corresponding to fabric region 302 and a portion 434 corresponding to fabric region 306 a. Portion 438a, portion 438b, portion 438c, and portion 438d correspond to section 305a, section 305b, section 305c, and section 305d, respectively, of fabric region 304a of fabric 300.

The top, middle, and bottom regions 440, 442, 444 of the cross-section 432 of fig. 4D may include the same braided structures as discussed above with respect to the top, middle, and bottom portions 404, 406, 408, respectively, of the cross-section 402 of fig. 4A, so as to provide the same type of generally tubular structure.

In one exemplary aspect, portions 434 and 438D of section 432 of fig. 4D comprise a braided structure comprising yarns comprising a high processing temperature polymer composition, while portions 436, 438a and 438b comprise a braided structure made from yarns comprising a low processing temperature polymer composition. However, as additionally provided above, it is contemplated that a primary, but not exclusive, choice of materials may be used. For example, in portion 438b, there may be a yarn comprising a high processing temperature polymer composition in the intermediate zone 442 to aid in the transition of the material. The concentration of yarn comprising the high processing temperature polymer composition in portion 438b may be less than that present in portion 438c of the same intermediate zone 442. For example, the portion 438b can have at least 5 wt.%, 10 wt.%, or 25 wt.% less yarn comprising the high processing temperature polymer composition than is present in the portion 438c of the same intermediate zone 442.

Section 438c comprises a tubular structure having yarns comprising a low processing temperature polymer composition joined by floats and tucks with yarns comprising a high processing temperature polymer composition. In these aspects, after thermoforming, this portion 438c may encapsulate the yarn comprising the high processing temperature polymer composition in a sheet of thermoformed material after melting and cooling. In certain aspects, such a structure can provide some flexibility to an otherwise rigid thermoformed material.

For example, fig. 4E depicts a cross-section 446 that is the same as cross-section 432 of fig. 4D, except that an anchoring yarn 448 is added to at least a portion of the region comprising yarns comprising the low processing temperature polymer composition. In certain aspects, the anchoring yarn 448 may have any or all of the characteristics discussed above with respect to the anchoring yarn 413 of fig. 4B. For example, one or more of the braided structures depicted in fig. 5E and 5G-5J may be used to incorporate anchoring yarns into a fabric.

As can be seen in fig. 4E, anchoring yarns 448 extend from portion 450 of cross-section 446 corresponding to fabric region 302 and into portions 452a and 452b corresponding to sections 305a and 305b of fabric region 304 a. Further, in these aspects, fig. 4E illustrates that, at least in the same portion of the fabric as anchoring yarn 448, there is also a yarn comprising the low processing temperature polymer composition (e.g., as a yarn having one or more of the weave structures present in fig. 5A and 5B). Thus, in certain aspects, the anchoring yarns 448 can extend as floats along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition. Also in certain aspects, the anchoring yarn 448 can extend as a float weave along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition and can also form at least a portion of a tuck weave and/or a knit weave with the yarn comprising the low processing temperature polymer composition. In these aspects, the anchoring yarn 448 may extend along at least two, at least three, at least four, or at least five adjacent loops of the yarn comprising the low processing temperature polymer composition between the tuck stitch or weave stitch formed at least in part by the yarn comprising the low processing temperature polymer composition and the anchoring yarn 448. In the same or alternative aspects, anchor yarns 448 may be stitch-stitched at stitch intervals by an amount, such as tuck stitch or knit stitch, that is within 50% or within 25% of the gauge of the knitting machine used to form at least a portion of fabric 300.

As discussed above, in one or more aspects, anchoring yarns 448 can extend from fabric region 302 into fabric region 304a and toward fabric region 306 a. In these aspects, the anchoring yarns 448 may not extend from the fabric region 302 into the fabric region 304a and toward the fabric region 306a as long as the yarns comprising the low processing temperature polymer composition extend into the fabric region 304a and toward the fabric region 306a, as there is less need to restrict flow during thermoforming and/or less need to provide flexibility to the material after thermoforming, as there are also yarns from the fabric region 306a comprising the high processing temperature polymer composition in the fabric region 304 a.

For example, in section 446 of fig. 4E, the anchor yarn extends from portion 450 (corresponding to the portion of fabric region 302) and into portion 452b (corresponding to section 305b of fabric 300). Further, cross-section 446 illustrates top portion 456 and bottom portion 460 of cross-section 446 showing that the yarns comprising the low processing temperature polymer composition extend from portion 450 and into portion 452c, toward portion 454 (corresponding to fabric region 306a), which exceeds the extension of anchoring yarns 448 in the same direction. However, in intermediate portion 458, in portions 452c and 452d, there are yarns comprising high processing temperature polymer compositions that can provide flexibility to the thermoformed fabric and/or restrict flow during thermoforming.

As discussed above, in certain aspects, when fabric 300 is a woven fabric, the cross-section of the fabric depicted in fig. 4A-4E is depicted as having a top portion, a bottom portion, and a middle portion, wherein the top portion and the bottom portion may form a tubular woven structure having a top and bottom woven layer (and wherein the tuck stitch or other connecting stitch present in the middle portion may also form a portion of a tubular or general woven structure). In these aspects, the top and bottom outer braids may each include a plurality of interconnected courses.

Further, as can be seen in fabric 300 of fig. 3, in fabric region 304a, section 305a through section 305d have at least one staggered interface, such as staggered interface 306. The staggered interfaces, such as staggered interface 306, provide a staggered or non-linear transition between the zones of fabric 300 along the width w of the fabric. In these aspects, these staggered interfaces provide a further improved overall transition between the rigid region formed by the low processing temperature polymer composition in fabric region 302 and the flexible, soft region formed by the yarns comprising the high processing temperature polymer composition in fabric region 306a when fabric 300 is thermoformed. In various aspects, this improved integral transition provided at least in part by the staggered interface can improve the durability or tear resistance of the thermoformed fabric 300, as opposed to a similar fabric having a straight abrupt transition between the integral rigid material and the flexible material.

In aspects where fabric 300 is a woven fabric, interlace 306 can depict how different courses of yarn on the top or bottom outer knit layer may have different amounts of stitches (or general stitch selection) of yarn comprising the low processing temperature polymer composition and/or yarn comprising the high processing temperature polymer composition. Because the fabric may have multiple layers (e.g., top, middle, and bottom layers), the interlaced interface may be present in any combination of layers and is not limited to surface exposure or delineation. Rather, as provided herein and as contemplated, the transition from a first primary material (e.g., fibers and/or yarns comprising a high processing temperature polymer composition) to a second primary material (e.g., fibers and/or yarns comprising a low processing temperature polymer composition) that forms a fabric can occur only at the intermediate layer or in a combination of the intermediate layer and one or more outer layers. It should be understood that for purposes of the following discussion of woven layers, it is assumed that the view of fabric 300 depicts a top layer when fabric 300 of fig. 3 is a woven fabric. Furthermore, the above description applies equally to the bottom braid.

Fig. 6 schematically depicts one exemplary portion 600 of the top layer of the fabric 300, showing a portion of the staggered interface 306. As can be seen in portion 600 of fig. 6, a first row of coils 602 is interconnected with a second row of coils 604. It should be understood that while only two interconnected courses are depicted in fig. 6, there may be more than two courses interconnected in the top braid of fabric 300. As used herein, "interconnected," when referring to interconnected courses, refers to how at least a portion of a coil in a first course is tied to at least a portion of a coil in a second course. One exemplary aspect of an interconnected course is depicted in fig. 6, wherein individual coils from the second course 604 are intermeshed with individual coils from the first course 602. As used herein, "interlooping" refers to how stitches from one course wrap around stitches of another course, such as in a knit, and also refers to how one stitch pulls another portion of the yarn through the stitch (or through the stitch and around the yarn forming the stitch) to form a second stitch, such as in a crocheting process.

As can be seen in portion 600 of fabric 300, first course of stitches 602 and second course of stitches 604 each comprise two types of yarns: a first yarn 606 that may include a high processing temperature polymer composition and a second yarn 608 that may include a low processing temperature polymer composition. Although only two courses are depicted in portion 600, it should be understood that the top braid of fabric 300 may contain any number of courses. In various aspects, the courses present in the top knit layer of fabric 300 may each comprise two or more types of yarns, as depicted in fig. 6.

As can be seen in fig. 6, each course, such as first course 602 and second course 604, can extend from fabric region 302 to fabric region 306a (in various aspects, the courses can each extend from fabric region 306a to fabric region 306 b). In some aspects, as can be seen in fig. 6, the second yarn 608 in the first course 602 and the second course 604 may extend from the fabric region 302 into the fabric region 304 a. In the same or alternative aspects, first yarn 606 may extend from textile region 304a into textile region 306 a. It should be understood that although the schematic portion 600 of the fabric 300 depicts each stitch as having only a single yarn, more than one yarn may be present in one or more stitches (e.g., another yarn may form a tuck stitch with the stitches of the portion 600 of fig. 6), as depicted in the cross-sections of fig. 4A-4E.

As discussed above, portion 600 of the outer woven layer of fabric 300 exhibits at least a portion of the interlace 306. In certain aspects, the interlaced interface 306 (and any other interlaced interfaces) can be formed by the same type of yarn in multiple courses extending different distances from one area (or zone) to the next. For example, as can be seen in fig. 6, in the first course of loops 602, the second yarn 608 extends from the fabric region 302 into the fabric region 304a and toward the fabric region 306a farther than the second yarn extends from the fabric region 302 into the fabric region 304a and toward the fabric region 306 a. In these aspects, the difference in the distance that second yarn 608 extends into fabric region 304a results in a different amount of loops in second yarn 608 for each of first course 602 and second course 604, which may change the yarn concentration for a given area/zone. Thus, in these aspects, within the fabric region 304a, at the first ridge 609, the loops of the second yarn 608 in the second course 604 may be interlooped with the loops of the second yarn 608 in the first course 602, and at the second ridge 610, the second yarn 608 of the first course 602 may be interlooped with the loops of the first yarn 606 in the second course 604. In the same or alternative aspects, within the textile region 304a, at the third ribs 612, the first yarns 606 in the first course 602 may be interlooped with the first yarns 606 in the second course 604.

In one or more aspects, interlacing an interface, such as interlacing interface 306, may cause adjacent courses of the plurality of courses in fabric 300 to have different numbers of stitches of the yarn comprising the low processing temperature polymer composition and the yarn comprising the high processing temperature polymer composition. For example, as can be seen in the portion 600 of the upper knit layer of the fabric 300 depicted in fig. 6, in at least a portion of the fabric region 304a, the first course of stitches 602 and the second course of stitches 604 have a different number of stitches of the first yarn 606 and/or the second yarn 608. Further, in the same or alternative aspects, adjacent ribs can have one or more loops of different yarns within at least a portion of the fabric region 304 a. For example, as shown in portion 600 of the upper knit layer of fabric 300 in fig. 6, second ridge 610 includes loops of first yarn 606 and second yarn 608, while third ridge 612 includes loops of first yarn 606.

As discussed above, the fabrics described herein, which may comprise fibers and/or yarns comprising the low processing temperature polymer composition, are capable of being thermoformed to impart a characteristic structure to the article of wear. Furthermore, as discussed above, the thermoforming process can cause at least a portion of the low processing temperature polymer composition present in the fabric to melt or deform, and subsequently solidify.

Fig. 7A schematically depicts portion 700 of upper braid fabric region 304a of fabric 300 of fig. 3 prior to a thermoforming process. Portion 700 includes a first course of stitches 702 and a second course of stitches 704 having a first yarn 708 comprising a high processing temperature polymer composition. The section also includes a third course 706 of second yarns 710 comprising the low processing temperature polymer composition. In this aspect, third courses 706 of stitches of second yarn 710 may be interconnected, e.g., intertwined, with first courses 702 and second courses 704 of first yarn 708.

Fig. 7B depicts the portion 700 after exposure to the thermoforming process. As can be seen by comparing fig. 7A and 7B, a second yarn 710 comprising a low processing temperature polymer composition is thermoformed from a yarn material into a non-yarn material 712. In certain aspects, the heating step of the thermoforming process at least partially causes the low processing temperature polymer composition in the second yarn 710 to melt and flow, and then subsequently solidify into a non-yarn material 712 by the time the thermoforming process is complete.

In various aspects, as can be seen in fig. 7A and 7B, the thermoforming process also transforms at least a portion of the knit structure of portion 700 of the upper knit layer of fabric 300 of fig. 3. For example, the first course of stitches 702, the second course of stitches 704, and the third course of stitches 706 depicted in fig. 7A are transformed such that the portion 700 no longer includes interconnected courses of stitches including yarns of the low processing temperature polymer composition and yarns including the high processing temperature polymer composition, at least in part because the second yarns 710 in the third course of stitches 706 are transformed into non-yarn material 712. As can be seen in fig. 7B, the remaining first courses 702 and second courses 704 may be connected by non-yarn material 712, although the thermoforming process may eliminate the interconnected loops in portion 700 of the upper knit layer of fabric 300 of fig. 3. In these aspects, this portion 700 of the upper knit layer of fabric 300 of fig. 3 may fix the position of first course of coils 702 and second course of coils 704 relative to each other, as opposed to when first course of coils 702 and second course of coils 704 are interconnected by third course of coils 706 prior to thermoforming. Moreover, in these aspects, the top portions 714 of the stitches of the first course 702 may still be freely interconnected with other courses of yarn, thereby adjusting the level of rigidity and/or three-dimensional form provided by the fabric region 304 a.

Fig. 8 depicts a cross-section of portion 700 of the upper braid of fabric 300 of fig. 3 along cut line 8 shown in fig. 7B. As can be seen in fig. 8, at least a portion of first yarn 708 may be encapsulated within non-yarn material 712. Depending on the conditions used during the thermoforming process, the non-yarn material 712 is capable of solidifying into a film-like structure around at least a portion of the loops of the first course of loops 702 and the second course of loops 704 of the first yarn 708 comprising the high processing temperature polymer composition.

As can be seen in the aspects depicted in fig. 7B and 8, the first yarn 708 comprising the high processing temperature polymer composition does not melt or deform after exposure to the thermoforming process. Further, in certain aspects, first yarn 708 may contain a dye 716 (depicted as speckles (speckling) within first yarn 708) that does not leach out after exposure to the thermoforming process. For example, as can be seen in fig. 7B and 8, no significant dye 716 leaches from the first yarn 708 into adjacent regions of the non-yarn material 712, such as adjacent region 718. In certain aspects, at least about 80%, at least about 90%, at least about 95%, or at least 99% by weight of dye 716 is retained within first yarn 708 or within thermoformed portion 700 of the upper knit layer of fabric 300 of fig. 3. In the same or alternative aspects, after thermoforming, no significant dye leaches into any additional material associated with the final worn article in which portion 700 of the upper knit layer of fabric 300 of fig. 3 is incorporated.

Fig. 9A and 9B depict an aspect in which portion 700 of the upper knit layer of fabric 300 of fig. 3 is exposed to a thermoforming process, but only causes deformation of the low processing temperature polymer composition in second yarns 710, without eliminating at least a portion of interconnected first, second, and third courses 702, 704, 706 of fig. 7A. As used herein, "deformation" and "deforming" in the context of a thermoforming process for weaving a fabric refers to altering the structure of the yarns such that the yarns do not melt and flow in a manner that substantially eliminates the woven structure of the fabric (e.g., eliminates one or more interconnected loops or courses of loops that are interlocked with one another).

Fig. 9A depicts a cross-section of portion 700 of the upper braid of fabric 300 of fig. 3 along cut line 9A-9A prior to the thermoforming process, and fig. 9B depicts the same cross-section after the thermoforming process. As can be seen in fig. 9B, second yarn 710 in third course 706 has an altered yarn structure 710a after exposure to the thermoforming process, while the structure of first yarn 708 is unchanged. In this aspect, second yarn 710 in third course 706 remains interlooped with first and second courses 702, 704 and the entire knit structure of portion 700 of the upper knit layer of fabric 300 of fig. 3.

In some aspects, this modified yarn structure 710a may cause a mechanical connection or physical bond of the second yarn 710 with another yarn, such as the first yarn 708 (or with another portion of the second yarn 710). In certain aspects, during the thermoforming process, second yarn 710 is exposed above the glass transition temperature, T, of the low processing temperature polymer composition_gBut not above the melting temperature of the low processing temperature polymer composition. In these aspects, when the second yarn 710 is exposed to such high temperatures, the second yarn softens and becomes soft, but does not melt, such that the yarn is slightly formed around at least a portion of the adjacent yarn, e.g., the first yarn 708, and after cooling, this altered yarn structure may be mechanically locked in place, physically bonding with the adjacent yarn.

Fig. 10A-10C depict a portion 1000 of the fabric region 302 of the upper knit layer of the fabric 300 of fig. 3 before and after thermoforming. Fig. 10A depicts three courses 1010, 1012, 1014 of yarn comprising a low processing temperature polymer composition. Fig. 10A additionally depicts the presence of anchoring yarns 1016 extending in float stitches 1016a and tuck stitches 1016 b.

Fig. 10B depicts a portion 1000 of fabric region 302 of the upper knit layer of the same fabric 300 of fig. 3 after exposure to a thermoforming process. As can be seen in fig. 10B, the interlooped courses 1010, 1012, and 1014 of yarn have been converted to non-yarn material 1018. Further, as can be seen in fig. 10B and 10C, fig. 10C is a section along cut line 10C of fig. 10B, with anchoring yarn 1016 maintaining its yarn structure and now encapsulated within non-yarn material 1018. It should be understood that although in fig. 10B, the anchoring yarn 1016 is depicted as being encapsulated within the non-yarn material 1018, it is also contemplated that the anchoring yarn 1016 may be at least partially embedded within the non-yarn material 1018 such that at least a portion of the anchoring yarn 1016 is not completely covered in the non-yarn material 1018.

As discussed above, in certain aspects, the fabrics described herein may comprise woven fabrics, such as portions of woven fabrics as depicted in fig. 4A-10C. The woven upper of an article of footwear is an exemplary woven fabric. In these aspects, at least a portion of the braided upper of the article of footwear, and in some aspects substantially the entire upper, may be formed from a braided fabric. The woven fabric may additionally or alternatively form another element of the article of footwear, such as a midsole or a ground-contacting outsole. The woven fabric may have a first side that forms an interior surface of the upper (e.g., facing a void of the article of footwear) and a second side that forms an exterior surface of the upper. An upper containing a woven textile may substantially enclose a void so as to substantially enclose a person's foot when the article of footwear is in use. The first side and the second side of the woven fabric may exhibit different characteristics (e.g., the first side may provide wear resistance and comfort, while the second side may have a relatively greater rigidity and provide water resistance).

In various aspects, the woven fabric may be formed as a unitary, one-piece element during a weaving process, such as a weft knitting process (e.g., using a flat knitting machine or circular knitting machine), a warp knitting process, or any other suitable weaving process. That is, the knitting process may substantially form the knit structure of the knitted fabric without requiring significant post-knitting processes or steps. Alternatively, two or more portions of the woven fabric may be formed separately and then joined. In some embodiments, the knitted fabric may be shaped after the knitting process to form and maintain a desired upper shape (e.g., through the use of a foot-shaped last). The molding process may include joining the knitted fabric to another object (e.g., strobel) and/or joining one portion of the knitted component to another portion of the knitted component at a seam by sewing, by using an adhesive, or by another suitable joining process.

Forming the upper with a knitted textile may provide the upper with advantageous characteristics including, but not limited to, a particular degree of elasticity (e.g., expressed in Young's modulus), breathability, flexibility, strength, moisture absorbency, weight, and abrasion resistance. These features may be achieved by: by selecting a particular single or multi-layer weave structure (e.g., a rib weave structure, a single jersey weave structure, or a double jersey weave structure), by varying the size and tension of the weave structure, by using one or more yarns formed from a particular material (e.g., a polyester material, a monofilament material, or an elastomeric material, such as spandex (spandex)), by selecting a particular size (e.g., denier)), or a combination thereof.

Woven fabrics may also provide desirable aesthetic characteristics by incorporating yarns having different colors or other visual characteristics arranged in a particular pattern. The knit structure of the yarns and/or knit fabric may be different at different locations such that the knitted component has two or more portions with different properties (e.g., the portion forming the throat area of the upper may be relatively elastic while another portion may be relatively inelastic). In some aspects, the woven fabric may incorporate one or more materials having properties that change in response to a stimulus (e.g., temperature, moisture, current, magnetic field, or light).

In some aspects, the woven fabric may comprise one or more yarns or strands, referred to herein as "tensile strands," that are at least partially embedded or otherwise inserted within the woven structure of the woven fabric during or after the weaving process. The tensile strands may be substantially inelastic and thus have substantially fixed lengths. The tensile strand may extend through multiple courses of the woven fabric or through a channel within the woven fabric and may limit stretch of the woven fabric in at least one direction. For example, the tensile strands may extend generally from the bite line (biteline) of the upper to the throat area of the upper to limit lateral (lateral) stretch of the upper. The tensile strand may form one or more lace apertures for receiving a lace and/or may extend around at least a portion of the lace apertures formed in the braided structure of the woven fabric.

In an alternative aspect, the fabric described herein can comprise a nonwoven fabric. The nonwoven fabrics described herein may be produced by any conventional process, such as any conventional mechanical, chemical, or thermal process for lapping fibers together, including needle entangling and water entangling.

Fig. 11A-11C depict aspects of the fabric 300 of fig. 3 being a non-woven fabric and undergoing a thermoforming process. Fig. 11A is a schematic depiction of a portion 1100 of the fabric region 304a of the fabric 300 of fig. 3. As can be seen in FIG. 11A, a portion comprises a first grouping 1110 of first fibers 1116 comprising a high processing temperature polymer composition, a second grouping 1112 of first fibers 1116, and a third grouping 1114 of second fibers 1118 comprising a low processing temperature polymer composition. It should be understood that the portion 1100 of the fabric 300 is schematic and that the placement and spacing of the first fibers 1116 and the second fibers 1118 in the fabric may be different.

Although not depicted in fig. 11A-11C, in aspects in which the fabric 300 is a non-woven fabric, one or more interfaces between different portions of different fibers may also include one or more interlaced interfaces, such as interlaced interface 306. In these aspects, the staggered interface 306 may depict how transitions between regions or zones having different concentrations of fibers comprising the low processing temperature polymer composition and/or fibers comprising the high processing temperature polymer composition do not occur in a linear fashion along the width w of the fabric 300 of fig. 3.

Returning now to fig. 11A-11C and in particular fig. 11C, in aspects where the thermoforming process causes the low processing temperature polymer composition in the second fibers 1118 to melt and flow, the second fibers 1118 have been converted to a non-fibrous material 1120 while the first fibers 1116 have not been converted and thus remain in fibrous form. In these aspects, the non-fibrous material 1120 may connect the first grouping 1110 of first fibers 1116 with the second grouping 1112 of first fibers 1116. Fig. 11C illustrates a cross-section along cut line 11C, which illustrates how, in certain aspects, at least a portion of the first fibers 1116 are encapsulated within a non-fibrous material 1120. In aspects, it is contemplated that at least a portion of the first fibers 1116 can be at least partially embedded within the non-fibrous material 1120 such that the first fibers 1116 are not completely encapsulated by the non-fibrous material 1120.

Although not depicted in the figures, in certain aspects, the second fibers 1118 may not melt and flow, but may instead deform and change shape after exposure to the thermoforming process. Such deformation of the fiber or yarn is depicted in fig. 9A and 9B. Similar to the texturing of the fiber or yarn discussed above with respect to fig. 9A and 9B, in certain aspects the second fiber can be textured and formed over and mechanically connected or physically bonded to another first or second fiber (or the same fiber).

Preheating forming process and hot forming process

As discussed above, in certain aspects, the above-described fabric, such as fabric 300 of fig. 3, may form at least a portion of an article of wear, such as an article of footwear. In these aspects, the textile may form an upper for an article of footwear, where the upper includes a ground engaging outsole portion.

In certain aspects, the textile may be combined with additional materials to form an upper for an article of footwear. For example, in one or more aspects, the textile may be combined or layered with one or more of an ankle collar lining, ankle collar foam material, upper lining, or upper foam layer. In certain aspects, one or more of these additional materials may be secured to the fabric prior to thermoforming of the fabric, for example by weaving, stitching, or adhesive.

In certain aspects, to provide additional comfort and/or support to a wearer of an article of footwear formed at least in part from a fabric as described herein, an internal support device or chassis may be provided. Fig. 12 and 13 depict an article of footwear 1200 that includes a chassis 1210. Article of footwear 1200 includes a textile 1212 that forms an upper 1214 with a ground-contacting outsole portion 1216. In certain aspects, as best seen in fig. 13, fig. 13 depicts a cross-section of an article of footwear 1200, a chassis 1210 is located in an interior portion 1218 of the article of footwear 1200 and contacts an interior surface 1220 of a fabric 1212. In certain aspects, the base plate 1210 can comprise a polymeric material, such as a high processing temperature polymeric material, for example a polyether block amide, that is capable of not melting or deforming during the thermoforming process described herein.

In various aspects, the heel counter 1222 may be positioned on the interior portion 1218 of the article of footwear with respect to heel support of the wearer. In various aspects, similar to chassis 1210, heel stabilizer 1222 may comprise a polymeric material, such as a high processing temperature polymeric material, e.g., a polyether block amide, that is capable of not melting or deforming when exposed to a thermoforming process.

In some aspects, footbed 1224 may be located at the top of chassis 1210 in interior portion 1218 of article of footwear 1200. In these aspects, footbed 1224 may include conventional footbed materials, such as one or more layers of foam or memory foam and a fabric layer. It should be understood that while chassis 1210, heel counter 1222, and sockliner 1224 are depicted as additional materials for forming an upper of an article of footwear, other materials, such as plates, toe caps (toe caps), and/or structures along the sides may also be added.

In various aspects, heel counter 1222 and chassis 1210 may be located in interior portion 1218 of article of footwear 1200 prior to thermoforming. In certain aspects, the footbed may be applied after the thermoforming process is complete.

In certain aspects, such as the aspect depicted in fig. 14, ground engaging stud 1410 may be applied to article of footwear 1400. In various aspects, article of footwear 1400 may incorporate the same features as article of footwear 1200 described above with respect to fig. 12 and 13. As can be seen in fig. 14, ground contacting stud 1410 may be applied to ground-contacting sole region 1412 of article of footwear 1400 to provide increased stability and traction. In aspects, ground-contacting stud 1410 may be applied against ground-out region 1412 after the thermoforming process is complete. In other aspects, ground-contacting stud 1410 may be applied against ground-sole region 1412 as part of a thermoforming process.

In various aspects, the fabric and any of the above additional materials may be woven, knitted, braided, or preformed into an upper having a ground-engaging outsole portion in the general shape of a boot, as depicted in upper 1500 of fig. 15, prior to thermoforming of the article of footwear. In these aspects, upper 1500 may also include a chassis or heel counter located on interior 1510 of upper 1500, such as chassis 1210 and heel counter 1222 discussed above with respect to fig. 12.

To prepare upper 1500 for the thermoforming process, upper 1500 is placed on last 1520 such that last 1520 enters interior 1510 of upper 1500. In certain aspects, the last 1520 can be formed from a polymeric material, such as a high processing temperature polymeric composition. In a particular aspect, the last 1520 may be made of a material having a melting temperature T greater than 250 ℃ or greater than 300 ℃_mOr a degradation temperature, such as a silicone polymer. Last 1520 may be made of other types of materials so long as such materials do not deform or melt during the thermoforming process or otherwise adversely affect the thermoforming of the upper. Fig. 16 depicts upper 1500 positioned on last 1520. As can be seen in fig. 16, upper 1500 encircles last 1520 to cover bottom portion 1522 of last 1520, forefoot portion 1524 of last 1520, and the shoeHeel portion 1526 of last 1520. In these aspects, the ground-engaging outsole portion 1512 of the upper covers the bottom portion 1522 of last 1520. Although upper 1500 is shown in fig. 15 and 16 as having a sock-like structure that encircles and covers bottom portion 1522, forefoot portion 1524, and heel portion 1526 of last 1520, in other aspects upper 1500 may only partially encircle last 1520. Similarly, in other aspects, upper 1500 may cover only bottom portion 1522 of last 1520, only forefoot portion 1524 of last 1520, only heel portion 1526 of last 1520, or a combination thereof. In other aspects, upper 1500 may cover only a portion of bottom portion 1522 of last 1520, a portion of forefoot portion 1524 of last 1520, a portion of heel portion 1526 of last 1520, or a combination thereof.

Fig. 17 shows a cross section of upper 1500 on last 1520 along cut line 17. Section 1700 shows that last 1520 contacts interior surface 1540 of upper 1500. Section 1700 also shows that there are two types of materials in upper 1500. For example, cross-section 1700 shows three types of textile regions that form the textile of upper 1500. As can be seen in fig. 17, textile region 1710, which is associated with the outsole portion 1512 of the upper, covers a bottom portion 1522 of last 1520. In these aspects, when the upper is a woven fabric forming a woven upper, at least a portion of the yarns comprising the low processing temperature polymer composition cover at least a portion of bottom portion 1522 of last 1520.

In addition, fabric region 1714 covers forefoot portion 1524 of last 1520, while fabric region 1712 covers midfoot portion 1528 of the last. In certain aspects, fabric regions 1710, 1712, and 1714 can have any or all of the characteristics discussed above with respect to fabric regions 302, 304a, 306a, respectively, of fig. 3.

In certain aspects, the low processing temperature polymer composition melts and flows during the thermoforming process. In various aspects, it may be desirable to limit the flow of the molten low processing temperature polymer composition. In these aspects, the upper may be on the lastA protective sheath is applied. For example, as can be seen in fig. 18 and 19, sleeve 1800 is positioned on upper 1500, and upper 1500 is positioned on last 1520. In certain aspects, the protective casing 1800 may be formed from a polymeric material, such as a high processing temperature polymeric composition. In a particular aspect, the protective casing 1800 may be formed from a material having a melting temperature T greater than 250 ℃ or greater than 300 ℃_mOr an elastic polymer material at a degradation temperature, such as a silicone polymer. Protective sleeve 1800 may be made of other types of materials so long as such materials do not deform or melt during the thermoforming process or otherwise adversely affect the thermoforming of the upper. In various aspects, protective sleeve 1800 may apply a compressive force to outer surface 1530 of upper 1500, which helps to restrict the flow of the molten low processing temperature polymer composition. Further, in these aspects, a vacuum may be drawn on the combination of the last 1520, the upper 1500 positioned on the last, and the protective sleeve positioned on the upper 1500. For example, a bag under vacuum may be compressed on the exterior of the sock 1800 to apply a compressive force to the sock 1800 to ensure that the sock 1800 is in direct contact with the exterior surface 1530 of the upper 1500. The vacuum bag is also discussed in detail below.

In certain aspects, protective sleeve 1800 may be used to provide a pattern or indicia on the exterior surface of upper 1500. For example, the interior surface 1810 of the protective sleeve 1800 may include a mark or pattern that may be embossed or stamped onto the exterior surface 1530 of the upper 1500 during the thermoforming process because the low processing temperature polymer composition in the upper 1500 melts and cools and the protective sleeve 1800 (and optionally the vacuum bag) applies a compressive force to the upper 1500. In these aspects, because the protective sleeve 1800 may cover the entire upper 1500, it is possible for the protective sleeve 1800 to emboss or stamp the pattern onto any portion of the exterior surface 1530 of the upper 1500 that includes the low processing temperature polymer composition.

In certain aspects, protective sleeve 1800, when used alone and in a vacuum, can effectively reduce the number of air bubbles trapped in the low processing temperature polymer material during the thermoforming process as compared to the same upper thermoformed under similar conditions except that protective sleeve 1800 is not used.

In the aspect depicted in fig. 15-19, last 1520 is formed of a rigid material. Moreover, in these aspects, when the last 1520 is made of a rigid material, the compressive force applied through the protective sleeve 1800 (and/or vacuum bag) creates a force or pressure differential between the inner surface 1540 and the outer surface 1530 of the upper 1500 (as the rigid last 1520 at least partially resists this compressive force, resulting in the upper 1500 being subjected to a compressive force). In these aspects, this pressure differential can at least partially provide the environment required to restrict the flow of the molten low processing temperature polymer composition and/or provide embossing or patterning to outer surface 1530 of upper 1500.

In certain aspects, when formed of a rigid material, upper 1500 may be positioned on last 1520 and outer surface 1530 of upper 1500 (with or without protective sleeve 1800 present) may be exposed to a pressure above atmospheric pressure to create this pressure differential. In another aspect, upper 1500 may be positioned on last 1520 and negative pressure may be applied between inner surface 1540 of upper 1500 and last 1520 to compress upper 1500 onto rigid last 1520.

In various aspects, the pressure differential between inner surface 1540 and outer surface 1530 of upper 1500 also facilitates forming the three-dimensional structure of the article of footwear during the thermoforming process. That is, in these aspects, as the low processing temperature polymer composition melts, the molten material and upper 1500 are pressed onto rigid last 1520, which when cooled, causes upper 1500 to assume the shape of last 1520.

In alternative aspects, this force or pressure differential between interior surface 1540 and exterior surface 1530 of upper 1500 may be achieved in another manner. For example, in certain aspects, last 1520 may be an expandable last 1520, which may apply an outward force to interior surface 1540 of upper 1500. In these aspects, to achieve a pressure differential, outer surface 1530 of upper 1500 may be contacted by some type of material that will at least partially resist the outward force applied by the expansion of last 1520.

As discussed above, a vacuum bag may be applied to upper 1500 located on last 1520 with or without protective sleeve 1800. Fig. 20A depicts upper 1500 positioned on last 1520 within vacuum bag 2010. The term "vacuum bag" as used herein refers to any material capable of being compressed onto the outer surface of an object.

In the aspect depicted in fig. 20A, the vacuum bag 2010 may contain a valve 2012 for reducing the internal pressure of the vacuum bag 2010. For example, the pressure between the outer surface 1530 of the upper 1500 (or the outer surface of the protective sleeve 1800 on the upper 1500) and the interior 2014 of the vacuum bag 2010 may be reduced, thereby compressing the vacuum bag onto the outer surface 1530 of the upper 1500 (or the outer surface of the protective sleeve 1800 on the upper 1500). Fig. 20B depicts vacuum bag 2010 being compressed onto outer surface 1530 of upper 1500 (or the outer surface of protective sleeve 1800 on upper 1500). As discussed above, compressing the vacuum bag 2010 onto the upper 1500 may provide, at least in part, the pressure differential discussed above with respect to fig. 15-19.

Fig. 21 depicts a thermoforming system 2100. The thermoforming system 2100 of fig. 21 may include an upper 1500 positioned on a last 1520, and the vacuum bag 2010 is compressed onto the upper 1500, as discussed above with respect to fig. 20A and 20B.

As discussed above, the thermoforming process includes raising the temperature of the textile material, such as upper 1500, to a temperature capable of causing at least a portion of the low processing temperature polymer composition present in upper 1500 to melt and flow or deform. In addition, the thermoforming process involves subsequently lowering the temperature of upper 1500 to solidify the molten low processing temperature polymer composition into a desired shape, such as an article of footwear.

Thermoforming system 2100 includes heating zone 2110 that may be configured to heat the entire upper 1500. In various aspects, heating zone 2110 heats the entire upper 1500 above the melting temperature T of the low processing temperature polymer composition present in upper 1500_mThe temperature of (2).

In various aspects, heating the entire upper 1500 may provide a more efficient streamlined thermoforming process. For example, because the fibers and/or yarns comprising the low processing temperature polymer composition and the fibers and/or yarns comprising the high processing temperature polymer composition are selected and oriented in specific areas of the upper, it is not necessary to thermoform only a portion of the upper (e.g., by covering a portion of the upper or applying heat to only a portion of the upper), because the high processing temperature polymer composition is able to withstand any deformation or melting under conditions that enable thermoforming of the low processing temperature polymer composition.

As discussed above, it is desirable that the thermoforming process not distort or alter the fibers and/or yarns comprising the high processing temperature polymer composition. In these aspects, heating zone 2110 can heat the entire upper 1500 below the creep relaxation temperature T of the high processing temperature polymer composition or the fibers and/or yarns comprising the high processing temperature polymer composition_crThermal deformation temperature T_hdOr Vicat softening temperature T_vsTemperature of at least one of the above.

In one or more aspects, heating zone 2110 can increase the temperature of the entire upper 1500 to a temperature of about 90 ℃ to about 240 ℃. In various aspects, heating zone 2110 can increase the temperature of the entire upper 1500 to a temperature of about 90 ℃ to about 200 ℃. In one aspect, heating zone 2110 can increase the temperature of the entire upper 1500 to a temperature of about 110 ℃ to about 180 ℃.

In certain aspects, the temperature of the entire upper 1500 may be increased for about 10 seconds to about 5 minutes. In various aspects, the temperature of the entire upper 1500 may be increased for about 30 seconds to about 5 minutes. In one aspect, the temperature of the entire upper 1500 may be increased for about 30 seconds to about 3 minutes.

In one or more aspects, heating zone 2110 can expose the entire upper 1500 to temperatures of about 90 ℃ to about 240 ℃. In various aspects, heating zone 2110 can expose the entire upper 1500 to a temperature of about 90 ℃ to about 200 ℃. In one aspect, heating zone 2110 can expose the entire upper 1500 to a temperature of about 110 ℃ to about 180 ℃.

In certain aspects, the entire upper 1500 may be exposed to one or more of the heating zone 2110 temperatures or ranges discussed above for about 10 seconds to about 5 minutes. In various aspects, the entire upper 1500 may be exposed to one or more of the heating zone 2110 temperatures or ranges discussed above for about 30 seconds to about 5 minutes. In one aspect, the entire upper 1500 may be exposed to one or more of the heating zone 2110 temperatures or ranges discussed above for about 30 seconds to about 3 minutes.

In certain aspects, heating zone 2110 may expose the entire upper 1500 to pressures of about 50kPa to about 300 kPa. In various aspects, heating zone 2110 may expose the entire upper 1500 to pressures of about 50kPa to about 250 kPa. In one aspect, heating zone 2110 may expose the entire upper 1500 to pressures of approximately about 100kPa to about 300 kPa.

In certain aspects, the entire upper 1500 may be exposed to heating zone 2110 under the above conditions twice in succession, prior to the cooling step.

In various aspects, after increasing the temperature of the entire upper 1500, the temperature of the entire upper 1500 is reduced below the melting temperature T of the low processing temperature polymer composition_mFor a time sufficient to lower the processing temperature and to solidify the polymer composition. For example, heating zone 2110 can provide heat using conventional heaters, such as convection heating and/or infrared heating. Moreover, in certain aspects, the entire upper 1500 may be exposed to heating zone 2110 by: by moving the entire upper 1500 into the heating zone 2110 or by moving the heating zone 2110 to the location of the upper 1500, and then removing the heating zone 2110 after the heating step. The movement of upper 1500 and/or heating zone 2110 can be automated or semi-automated using conventional conveyor systems.

In certain aspects, after heating the entire upper 1500, the entire upper 1500 is cooled below the melting temperature T of the low processing temperature polymer composition_mThe temperature of (2). In these aspects, the entire upper 1500 may be exposed to a reduced temperature in cooling zone 2112 by moving to cooling zone 2112 or moving upper 1500 through cooling zone 2112. Cooling zone 2112 may expose the entire upper 1500 to a pressure of approximately 0 kPa.

In one or more aspects, the entire upper 1500 may be exposed to a temperature of about-25 ℃ to about 25 ℃ when in cooling zone 2112. In various aspects, the entire upper 1500 may be exposed to a temperature of about-10 ℃ to about 25 ℃ when in cooling region 2112. In one aspect, the entire upper 1500 may be exposed to temperatures of approximately about-10 ℃ to about 10 ℃ when in cooling zone 2112.

In certain aspects, the entire upper 1500 may be exposed to one or more of the cooling zone 2112 temperatures or ranges discussed above for about 10 seconds to about 5 minutes. In various aspects, the entire upper 1500 may be exposed to one or more of the cooling zone 2112 temperatures or ranges discussed above for about 10 seconds to about 3 minutes. In one aspect, the entire upper 1500 may be exposed to one or more of the cooling zone 2112 temperatures or ranges discussed above for about 10 seconds to about 2.5 minutes.

In certain aspects, after upper 1500 has cooled as described above, vacuum bag 2010 and protective sleeve 1800 may be removed. In these aspects, any additional components, such as ground engaging stud 1410 of FIG. 14, may now be applied to upper 1500.

Fig. 22 depicts another aspect of a thermoforming system 2200 for thermoforming an article. In aspects, the thermoforming system 2200 may include a heating station 2210, a cooling station 2212, and an under-pressure generating system 2214. In certain aspects, thermoforming system 2200 may also include a bracket 2216.

In certain aspects, thermoforming system 2200 is used to expose an article, such as upper 1500 discussed above with respect to fig. 15-19, to a thermoforming process while at least partially sealing the article within a molding material or vacuum bag. As discussed herein, at least partially sealing the article within the modeling material or vacuum bag means that the modeling material or vacuum bag is compressed onto the outer surface of the article. Sealing the article within the molding material or vacuum bag is discussed in detail above with respect to fig. 20A and 20B. It should be understood that compressing the modeling material or vacuum bag onto the exterior surface of the article also includes compressing the modeling material or vacuum bag onto a protective sleeve located on the exterior surface of the article, as discussed above with respect to fig. 18-19.

In various aspects, to seal an article, such as upper 1500, within molding material 2220 or vacuum bag, upper 1500 may be inserted into or at least partially covered by molding material 2220 or vacuum bag, and the pressure between outer surface 1530 of upper 1500 and molding material 2220 or vacuum bag may be reduced to a pressure below atmospheric pressure. In these aspects, this reduced pressure can compress the modeling material 2220 or vacuum bag onto the outer surface of the article. In some aspects, molding material 2220 or vacuum bag may be compressed onto the entire exterior surface of an article, such as upper 1500. In these aspects, this can provide a compressive force on the outsole portion of upper 1500 in addition to the midfoot region and collar region of upper 1500. Also in these aspects, such overall compressive force across upper 1500 is capable of providing the force required to shape or form upper 1500 into a shoe as upper 1500 undergoes a heating step in which a portion of the article (e.g., the portion containing the yarns or fibers comprising the low processing temperature polymer composition) melts or deforms and a cooling step in which the melted or deformed portion of the article cools and solidifies, thereby forming a thermoformed article, such as a shoe. In certain aspects, this compressive force may be enhanced by covering the article with a protective sleeve prior to compressing the molding material 2220 or vacuum bag onto the upper 1500, as described above with respect to fig. 18 and 19. Further detailed discussion regarding the forces and pressure differentials that may be employed in the thermoforming of an article is discussed above with respect to fig. 15-19.

In certain aspects, negative pressure generating system 2214 may be employed to reduce the pressure between exterior surface 1530 of upper 1500 and molding material 2220 or vacuum bag to a pressure below atmospheric pressure. In certain aspects, the negative pressure generating system 2214 can reduce the pressure between the outer surface 1530 of the upper 1500 and the modeling material 2220 or vacuum bag to a pressure of about 0.093MPa (700mm Hg) or less than about 0.093 MPa. In one or more aspects, the negative pressure generating system 2214 can reduce the pressure between the outer surface 1530 of the upper 1500 and the modeling material 2220 or vacuum bag to a pressure of about 0.091MPa (680mm Hg) or less than about 0.091 MPa.

In various aspects, negative pressure generating system 2214 is capable of reducing the pressure between outer surface 1530 of upper 1500 and modeling material 2220 or vacuum bag to a pressure below atmospheric pressure in about 10 seconds or less than 10 seconds. In aspects, negative pressure generating system 2214 is capable of reducing the pressure between exterior surface 1530 of upper 1500 and modeling material 2220 or vacuum bag to a pressure below atmospheric pressure in about 5 seconds or less than 5 seconds. In one aspect, negative pressure generating system 2214 is capable of reducing the pressure between outer surface 1530 of upper 1500 and molding material 2220 or vacuum bag to a pressure below atmospheric pressure in about 3 seconds.

In certain aspects, the negative pressure generating system 2214 may comprise a negative pressure generating device 2224, a molding material 2220 or vacuum bag, and a sealing member 2218. In these aspects, generally, the article may be placed within the molding material 2220 or vacuum bag and may be sealed, for example, by the sealing member 2218, and the pressure between the outer surface of the article and the molding material 2220 may be reduced in order to compress the molding material 2220 onto the outer surface of the article. Further, in these aspects, the negative pressure generating device 2224 may be coupled to the sealing member 2218 or directly to the molding material 2220, e.g., via a tube 2226, to provide reduced pressure. In certain aspects, the negative pressure generating device 2224 can comprise any commercially available vacuum pump or other commercially available device capable of reducing the internal pressure of a material. The molding material 2220 and sealing member 2218 will be discussed in detail below with respect to fig. 26. It should be appreciated that negative pressure generating system 2214 is one example of a system that can be used to compress a molding material, such as molding material 2218, onto an exterior surface of an article, such as upper 1500.

As discussed above, thermoforming system 2200 includes heating station 2210 and cooling station 2212 to expose articles, such as upper 1500, to different temperatures during different steps of the thermoforming process. In these aspects, thermoforming system 2200 may move an article, such as upper 1500, between heating station 2210 and cooling station 2212, or may move heating station 2210 and cooling station 2212 to upper 1500, or both. Further, as discussed above, upper 1500 is exposed to various thermoforming process steps, such as heating and cooling, while at least partially sealed within molding material 2220 or vacuum bag. While the thermoforming process may be described with respect to moving an article, such as upper 1500, between heating station 2210 and cooling station 2212, one skilled in the art will appreciate that relevant portions of the processes and systems described herein may be applied to move heating station 2210 and cooling station 2212 to receive a secured article, such as upper 1500.

As discussed above, thermoforming system 2200 may expose an article, such as upper 1500, to a heating step and a separate cooling step while at least partially sealed within molding material 2220, molding material 2220 providing a continuous compressive force on the exterior surface of upper 1500. In these aspects, the negative pressure generating system 2214 can be connected to one or more other portions of the thermoforming system 2200 such that the upper 1500 can be received by the heating station 2210 and/or the cooling station 2212 while still being sealed within the molding material 2220.

In certain aspects, at least a portion of the negative pressure generating system 2214 can be connected with a bracket 2216, and the bracket 2216 can be configured to move the sealed upper 1500 between the heating station 2210 and the cooling station 2212. For example, the sealing member 2218 of the negative pressure generating system 2214 can be coupled to the bracket 2216. In these aspects, the sealing member 2218 and the bracket 2216 can be connected to each other in any manner known to those skilled in the art.

In various aspects, the sealing member 2218 and the bracket 2216 may cooperate to move the shoe upper 1500 between the heating station 2210 and the cooling station 2212 while sealed in the molding material 2220 or vacuum bag. For example, in certain aspects, the bracket may be connected to upper 1500 by last 1520 that has been inserted into the article, as described above with respect to fig. 15-17. In these aspects, last support 1521 may extend outward from last 1520 and be inserted into a portion of bracket 2216 for securing last 1500 to bracket 2216.

In various aspects, after a last article, such as upper 1500 on last 1520, is attached to bracket 2216, sealing section 2218 can be attached to bracket 2216 prior to sealing molding 2220 to the article. Fig. 26 depicts one exemplary aspect of the sealing member 2218. In these aspects, the sealing member 2218 can include a through opening 2221 for enabling the sealing member 2218 to receive the upper 1500 and connect to the bracket 2216. For example, in these aspects, the sealing member 2218 can be placed over the bracket 2216 such that the upper 1500 extends through the through opening 2221.

In certain aspects, the sealing component 2218 can be connected to the molding material 2220 or vacuum bag. In certain aspects, as can be seen in fig. 26, a portion of the molding material 2220 may be located between the top and bottom portions 2218a and 2218b of the sealing member 2218 and extend into the through opening 2221 and outwardly away from the sealing member 2218 to form a pouch shape. In these aspects, the sealing member 2218 may also comprise a valve 2219 or other connection member for connecting to the negative pressure generating device 2224, such as by a tube 2226. In these aspects, this configuration of molding material 2220 and sealing member 2218 may enable upper 1500 to be sealed within molding material 2220 when sealing member 2218 is placed over upper 1500 and attached to bracket 2216. For example, as can be seen in fig. 22, the molding material 2220 may be compressed over the entire upper 1500 and a portion of the last 1520 and a portion of the sealing member 2218.

Molding material 2220 may be made of any type of material that is capable of being compressed onto outer surface 1530 of upper 1500 and that does not melt or deform during the heating and/or cooling steps described herein. In various aspects, molding material 2220 does not substantially change the compressive force applied to outer surface 1530 of upper 1500 under the heating and cooling conditions described herein. In various aspects, the molding material 2220 may exhibit a decomposition temperature T greater than about 135 ℃_dMelting temperature T_mCreep relaxation temperature T_crThermal deformation temperature T_hdOr Vicat softening temperature T_vsAt least one of (a). Decomposition temperature T_dRefers to the time when a material undergoes a thermal decomposition reaction, chemically decomposing the material into constituent elements or simpler moleculesThe temperature of (2). In various aspects, thermal decomposition may be detected by traces of charring and/or burning or by thermogravimetric analysis. In certain aspects, the molding material 2220 may exhibit a decomposition temperature T greater than about 135 ℃_dMelting temperature T_mOr both. In the same or alternative aspects, shaped material 2220 may exhibit a decomposition temperature T greater than about 150 ℃_dMelting temperature T_mOr both. In various aspects, modeling material 2220 may have reduced, minimal, or no air permeability such that the modeling material is able to compress onto exterior surface 1530 of upper 1500 when exposed to a sub-atmospheric pressure.

It should be appreciated that the particular configuration of the negative pressure generating system 2214 and the carriage 2216 is merely exemplary and that other configurations or assemblies may be employed to effect movement of an article, such as the upper 1500, between the heating station 2210 and the cooling station 2212 while at least partially sealed in a molding material.

As discussed above, in certain aspects, thermoforming system 2200 may alter the position of sealed upper 1500 between heating station 2210 and cooling station 2212. For example, as depicted in fig. 22, in certain aspects, the carriage 2216 can be connected to the track 2222, and the carriage 2216 can move along the track 2222. In these aspects, the carriage 2216 and the track 2222 may be movably connected to one another in any manner known to those skilled in the art. It should be understood that the carriage 2216 and the tracks 2222 are just one exemplary aspect of how an article, such as the upper 1500, may be moved back and forth between the heating station 2210 and the cooling station 2212.

In certain aspects, after an article, such as upper 1500, is sealed within molding material 2220 and connected to bracket 2218 as discussed above, bracket 2216 may transfer upper 1500 to heating station 2210. In these aspects, heating station 2210 may move to receive upper 1500 into an interior portion of heating station 2210. For example, as depicted in fig. 22, the heating station 2210 may move up and down along rails 2228. In certain aspects, after receiving the upper 1500 into an interior portion of the heating station 2210, the end surface 2210b of the heating station 2210 may cooperatively interact with the sealing component 2218 and/or the bracket 2216 to provide a sealed interior environment within at least a portion of the interior of the heating station 2210, which enables a more efficient heating process.

In certain aspects, in an interior portion of heating station 2210, an article, such as upper 1500, may be exposed to (and/or brought to) a temperature sufficient to cause at least a portion of the article to melt and flow or deform. In these aspects, this portion of upper 1500 may include yarns or fibers that include the low processing temperature polymer composition. In aspects, the heating parameters discussed above with respect to the heating zone 2110 of the thermoforming system 2100 of fig. 21, such as temperature range and time, may be applied to the heating station 2210 of the thermoforming system 2200.

In one or more aspects, the heating parameters may be limited, at least in part, based on the type of material used in the article forming process. For example, in certain aspects, yarns or fibers formed from high processing temperature polymer compositions may contain dyes such that when such yarns or fibers are exposed to high temperatures, such as temperatures near the time of dyeing a yarn or fiber package, the dyes begin to leach into the surrounding other undyed yarns or fibers. In these aspects, it may be desirable to expose the article to elevated temperatures at which such dye leaching does not occur. In this aspect, an article, such as upper 1500, may be exposed to an elevated temperature of about 135 ℃ or less than about 135 ℃ within heating station 2210.

In some aspects, when the article is a shoe upper, such as upper 1500, an exterior bottom portion of upper 1500 may protrude within an interior portion of heating station 2210. For example, as can be seen in fig. 22, upper 1500 is positioned on bracket 2216 such that ground outsole portion 1512 is opposite bracket 2216 such that ground outsole portion 1512 (which may contain more yarn or fiber that is melted during the thermoforming process than other portions of the upper) is closer to one or more thermal elements located on end surface 2210a of heating station 2210 than other portions of upper 1500. In aspects, this positioning of upper 1500 within heating station 2210 also enables the entire upper 1500 to be positioned within heating station 2210 without obstruction or contact with other portions of thermoforming system 2200, such as bracket 2216 or sealing member 2218. The heating station 2210 and associated thermal elements are discussed in further detail below.

In various aspects, as the article is being heated and a portion of the article melts or deforms, air bubbles can be generated during the process that can reduce the structural integrity and/or reduce the aesthetic quality of the thermoformed article. In certain aspects, the reduced pressure generated by the negative pressure generating system 2214 may be insufficient to facilitate removal of air bubbles from the article as the article is subjected to the heating step. In these aspects, the interior portion of the heating station 2210 may be pressurized, which can facilitate or assist in removing such gas bubbles from the exterior surface of the article as the article is subjected to the heating step. In certain aspects, pressurizing the interior portion of the heating station 2210 may also provide additional compressive force on the exterior surface of the article.

In certain aspects, at least a portion of the interior of the heating station 2210 can be pressurized using any conventional system, such as by pushing air, e.g., hot air, into the sealed interior environment. In one or more aspects, the internal environment or internal portion of the heating station 2210 can be pressurized to about 0.6MPa (about 6 kg/cm)²) The pressure of (a). In certain aspects, the internal environment or internal portion of the heating station 2210 can be pressurized to about 0.4MPa (about 4 kg/cm)²) The pressure of (a). In one aspect, the internal environment or internal portion of the heating station 2210 can be pressurized to about 0.1MPa (about 1 kg/cm)²) To about 0.6MPa (about 6 kg/cm)²) The pressure of (a).

In certain aspects, after upper 1500 is received into an interior portion of heating station 2210 and exposed to elevated temperatures as discussed above, upper 1500 may be transferred to cooling station 2212 through bracket 2216. In these aspects, to receive upper 1500 and provide a sealed interior portion for upper 1500 to be exposed to the reduced temperature, cooling station 2212 may be moved up and/or down along rails 2229. The cooling parameters discussed above with respect to the cooling zone 2112 of the thermoforming system 2100 of fig. 21, such as temperature and time, may be applicable to the cooling station 2212. In certain aspects, the cooling region 2112 can direct air onto the articles using any conventional cooling system or process, such as air knife forced air cooling, to transfer thermal energy away from the articles. In the same or alternative aspects, the system may utilize a cooling chamber, e.g., using a refrigerant, to cool the interior portions of the cooling station 2212 that may receive the articles.

In certain aspects, to maintain additional compressive force against outer surface 1530 of upper 1500 or to facilitate removal of air bubbles from upper 1500, cooling areas 2212 may pressurize interior portions of cooling station 2212. In these aspects, the parameters discussed above with respect to pressurizing the interior portion of the heating station 2210 may be applicable to pressurizing the interior portion of the cooling station 2212.

It should be understood that additional heating and cooling stations may be provided in thermoforming system 2200, for example, to achieve higher throughput (throughput). For example, in one aspect, the time required to cool an article may be longer than the time required to heat another article, so to increase throughput, the article may be exposed to a first cooling station for a first block of time, then transferred to another cooling station for a second block of time, and another article that has just left the heating station may be received into the first cooling station.

In certain aspects, the molding material 2220 may be removed from the article once the compressive force on the outer surface of the article is no longer needed after the article has completed the cooling step. In these aspects, to release the compression of the article by the molding material 2220, the pressure between the outer surface of the article and the molding material may be increased back to atmospheric pressure (e.g., the vacuum pressure may be removed). In the same or alternative aspects, the pressure between the surface of the article and the modeling material can be increased to a pressure above atmospheric pressure in order to facilitate removal of the modeling material 2220 from the exterior surface of the article. In certain aspects, this increase in pressure between the surface of the article and the molding material can be provided by the negative pressure generating device 2224.

FIG. 23 depicts another exemplary aspect of a thermoforming system 2300. As can be seen in the aspect depicted in fig. 23, the thermoforming system 2300 may include a heating station 2310, a cooling station 2312, a negative pressure generating system 2314, and a carriage 2316.

In certain aspects, in general, thermoforming system 2300 functions similarly to thermoforming system 2200 of fig. 22. For example, in various aspects, an article, such as upper 1500, which may be located on a last 1520, is at least partially sealed within molding material 2320 prior to being received into heating station 2310 and cooling station 2312 in a manner that enables the article to be subjected to the heating and cooling steps of the thermoforming process while sealed within molding material 2320, the sealed within molding material 2320 being capable of providing a compressive force on the exterior surface of the article.

In these aspects, the negative pressure generating system 2314 may function similar to that described above with respect to the negative pressure generating system 2214 of fig. 22, and may contain similar functional components. For example, the negative pressure generating system 2314 may include a negative pressure generating device 2326 connected to the sealing member 2318 by a tube 2328 or conduit. In various aspects, sealing component 2318 is coupled to molding material 2320 in a manner that can provide a sealed environment to reduce pressure between an exterior surface of the article, such as exterior surface 1530 of upper 1500 and molding material 2320, such that the molding material provides a compressive force on the exterior surface of the article.

In certain aspects, a sealing member 2318 may be coupled to the carriage 2316 to move the sealed articles between the heating station 2310 and the cooling station 2312. In the aspect depicted in fig. 23, the bracket 2316 may include a bracket connection member 2324 and a bracket connection member 2322 for connecting the bracket 2316 with the rail 2321, and the bracket 2316 may travel along the rail 2321 through the bracket connection member 2324 and the bracket connection member 2322. In certain aspects, the bracket connection member 2324 and the bracket connection member 2322 may extend the item into the interior portion 2310a of the heating station 2310 and into the interior portion 2312a of the cooling station 2312. In the same or alternative aspects, the track 2321 may move downward to transfer the items to the heating station 2310 and the cooling station 2312. It should be understood that the carriage 2316, carriage coupling members 2322 and 2324, and the tracks 2321 are but one exemplary aspect that may be used to transfer the sealed articles to the heating and cooling stations 2310 and 2312 and that other transfer systems are within the scope of the present invention.

In certain aspects, similar to the thermoforming system 2200 of fig. 22, the carriage 2318 and the heating station 2310 may be used to provide an enclosed environment for articles while located in the interior portion 2310a of the heating station 2310 or the interior portion 2312a of the cooling station 2312. For example, in certain aspects, the bracket 2316 is shaped and sized to seal an opening 2311 of the heating station 2310 through which the articles enter.

In certain aspects, the heating station 2310 and the cooling station 2312 may expose the articles to the same temperature and time parameters as discussed above with respect to the respective heating station 2210 and cooling station 2212 of fig. 22. In the same or alternative aspects, the heating station 2310 and the cooling station 2312 can provide an increased pressure environment while heating or cooling the article, as discussed above with respect to the thermoforming system 2200 of fig. 22.

Further, in certain aspects, after the heating and cooling steps of the thermoforming process are completed, increased pressure may be provided between the article exterior surface and the molding material 2320 when the thermoforming system 2300 is employed in order to facilitate release of the molding material 2320 from the article exterior surface.

Turning now to fig. 24 and 25, the heating station 2210 of the thermoforming system 2200 of fig. 22 is depicted in further detail. It should be understood that while fig. 24 and 25 may depict different features of the heating station 2210 of the thermoforming system 2200 of fig. 22, any or all of these features may be present in the heating station 2310 of the thermoforming system 2300 of fig. 23.

In certain aspects, the heating station 2210 may include one or more side walls 2210c positioned between the opposing end surfaces 2210a and 2210b, forming a partially enclosed structure 2211. In certain aspects, heating station 2210 is sized to receive an article, such as an upper 1500 of a shoe. In certain aspects, as discussed above, the end surface 2210b may be used to receive an article, such as the upper 1500, into the interior portion 2210d and to attach the heating station 2210 to at least a portion of the bracket 2216 or sealing component 2218. It should be understood that these general characteristics of the heating station 2210 also apply to the cooling station 2212.

As discussed above, the heating station 2210 may include one or more thermal elements to provide high temperatures to interior portions of the heating station 2210. For example, the heating station 2210 depicted in fig. 24 and 25 may include a plurality of thermal elements 2420 located in an interior portion 2210d of the heating station 2210. In certain aspects, the thermal elements 2420 can comprise any type of commercially available thermal elements that are capable of increasing the temperature in the interior portion 2210d of the heating station 2212 in the manner described herein. In certain aspects, the thermal element 2420 is used to heat the interior portion 2210d of the heating station 2212 to at least 200 ℃ or at least 250 ℃ in about 40 to 60 seconds. In certain aspects, the plurality of thermal elements 2420 can comprise one or more sources of infrared radiation. In one or more aspects, the plurality of thermal elements 2420 can comprise about 10, about 14, or about 19 individual sources of infrared radiation or other thermal elements. In one aspect, the one or more infrared radiation sources may comprise one or more infrared lamps.

In certain aspects, multiple thermal elements 2420 can be independently controlled or can be defined in regions to achieve zone control. In these aspects, this enables a uniform temperature distribution and/or numerous combinations may be provided to ramp up the temperature in the interior portion 2210d of the heating station 2210 individually, in sections, or collectively. In various aspects, controlling the thermal element may include turning the thermal element on and/or off once or more than once, and/or may include controlling the amount of thermal energy generated when the thermal element is turned on.

In certain aspects, a plurality of thermal elements 2420, such as one or more sources of infrared radiation, are sized to cover an entire largest dimension (e.g., length) of an article, such as upper 1500. In these aspects, one or each of the plurality of thermal elements 2420, e.g., one or more infrared radiation sources, can extend forward a distance of about 300mm to about 400 mm. It should be understood that the plurality of thermal elements 2420 depicted in fig. 24 and 25 are merely schematic and may or may not represent the actual type or shape of one or more of the thermal elements 2420.

In one or more aspects, a plurality of thermal elements 2420, such as one or more sources of infrared radiation, can be positioned on one or more of end surfaces 2210a and 2210b, one or more side walls 2210c, or a combination thereof. For example, as can be seen in the aspects depicted in fig. 24 and 25, individual thermal elements 2422, 2423, 2424, 2425, and 2426 are placed on individual walls or end surfaces within the heating station 2210. In these aspects, having separate thermal elements (or thermal element areas) located on different walls or end surfaces within heating station 2210 enables uniform distribution of heat applied to an article, such as upper 1500. For example, in these aspects, having the thermal elements on one or more side walls 2210c and one or more end surfaces 2210a, 2210b enables 360 degree heating of the entire article. In various aspects, all exterior surfaces or sides of the articles may directly face the one or more thermal elements (e.g., when thermal elements are located on each side wall and one or more end surfaces of the heating station 2210), thereby achieving an even distribution of thermal energy across the articles. In one aspect not depicted in the figures, a plurality of thermal elements 2420 can each be located on an end surface 2210a of the heating station 2210.

In certain aspects, specific positioning of multiple thermal elements 2420, such as on one or more side walls 2210c or one or more end surfaces 2210a and 2210b of the heating station 2210, alone or in combination with the ability to control (e.g., turn on or off) the multiple thermal elements 2420, either alone, collectively, or in zones, may achieve a uniform distribution of thermal energy or a targeted distribution of thermal energy across different portions of the article. For example, in certain aspects, an article, such as upper 1500, may include different concentrations and/or different types of materials (e.g., yarns or fibers comprising a low processing temperature polymer composition and yarns or fibers comprising a high processing temperature polymer composition) at different locations of the upper that, when exposed to thermal energy, cause these different materials (and/or different concentrations of materials) to conduct thermal energy at different rates. In this aspect, continued exposure of the article to continuous thermal energy may cause overheating of certain areas of one type or concentration of material while heating another area of the article having another type or concentration of material to a desired temperature. In aspects, individually, regionally, or collectively turning on and/or off thermal elements (one or more than one time) may reduce the likelihood of overheating an item or a portion of an item.

In certain aspects, in addition to measuring the temperature of the interior portion or opposing surface of the article, the surface temperature of the article exposed to thermal energy in the heating station 2210 may also be measured at one or more regions of the article. In these aspects, these temperatures may be used to tailor the heating profile of a particular article such that while the article is located within the heating station 2210 during the heating step, some (or all) of the thermal elements (once or more than once), such as the regions of the thermal elements located on the end surface 2210a, may be turned on and/or off to provide a desired amount of thermal energy to all or a portion of the article located closest to the thermal elements on the end surface 2210 a.

In one exemplary aspect, an article such as upper 1500 may include a ground-contacting outsole portion having a greater concentration of yarns or fibers comprising the low processing temperature polymer composition than other portions of upper 1500, such as the ankle collar region. In this aspect, the ground-engaging outsole portion of upper 1500 that includes a higher concentration of yarns or fibers that include a low processing temperature polymer composition may require additional or less thermal energy than another portion of upper 1500 that has a lower concentration of yarns or fibers that include a low processing temperature polymer composition. In this aspect, the thermal elements may be turned on and/or off once or repeatedly, and to compensate for the different thermal conductivity characteristics of the different materials of the different portions of upper 1500, the thermal elements may be turned on and/or off individually or in zones so that a portion of upper 1500 does not overheat and/or heat different portions of the upper to a desired temperature.

In certain aspects, as discussed above, it may be desirable to provide flowing air into the interior portion 2210d of the heating station 2210 to evenly distribute thermal energy or heat therein. In one such aspect, an air circulation device 2410, such as a convection fan or other air circulation system, may be located on at least one of the one or more side walls 2210c or the end surfaces 2210a or 2210b to provide air circulation in the interior portion 2210d of the heating station 2210. It should be understood that while a convection fan is schematically depicted as one exemplary air circulation device 2410 in fig. 24 and 25, other air circulation systems may be employed.

As discussed above, in certain aspects, the heating station 2210 may provide increased pressure in the interior portion 2210d, e.g., to facilitate removal of gas bubbles from the heated article. For example, in these aspects, the bores 2412 may be located on at least one of the one or more side walls 2210c or one or more of the end surfaces 2210a or 2210b to provide conduits for providing air, e.g., hot air, into the inner portion 2210d to increase the pressure therein. In one aspect, the air used to increase the pressure in the heating station may exhibit a temperature of about 100 ℃. In certain aspects not depicted in the figures, the air circulation device 2410 may be employed to provide such air to increase the pressure therein. In this aspect, the air circulation device 2410 may not simultaneously provide convective air circulation and air for pressurizing the interior portion 2210 d.

In certain aspects, the use of increased pressure in the plurality of thermal elements 2420, e.g., one or more sources of infrared radiation, the air circulation device 2410, and the interior portion 2210d of the heating station 2210, and the compressive force of the molding material 2220 may provide an even distribution of heat throughout the article, e.g., throughout the upper 1500, while also exerting an even distribution of compressive force throughout the article, e.g., throughout the upper 1500.

In certain aspects, the heating station 2210 may first utilize thermal elements, alone or in combination with convection, to distribute thermal energy and, after a duration of time, pressurize the heating station 2210 to facilitate removal of bubbles from the heated articles. In these aspects, convection or air circulation may not be employed when pressurizing the heating station 2210.

Fig. 27 depicts one aspect of a method 2700 for thermoforming an article. Method 2700 may include step 2710: an item is received. In certain aspects, an article may include upper 1500 discussed above with respect to fig. 15-19. In one or more aspects, the upper may include directionally incorporated: 1) a yarn or fiber as described above comprising the low processing temperature polymer composition; and/or 2) a yarn or fiber comprising the high processing temperature polymer composition described above.

Furthermore, as discussed above, upper 1500 may be located on a last, such as last 1520, and may also include a protective sleeve, such as protective sleeve 1800, located over upper 1500.

Step 2720 includes compressing a molding material, such as molding material 2220, onto an exterior surface of an article, such as exterior surface 1530 of upper 1500, forming a sealed article, as discussed above with respect to thermoforming system 2200 of fig. 22. In these aspects, as discussed above, the compressive force of the molding material 2220 against the outer surface of the article may help shape the article as the article is subjected to the heating and cooling steps of the thermoforming process.

In one or more aspects, step 2730 can include exposing the sealed article to thermal energy. In these aspects, the sealed article may be exposed to thermal energy at any of the parameters discussed above with respect to the thermoforming system 2200 of fig. 22 or the thermoforming system 2300 of fig. 23. In aspects, the sealed article may be exposed to thermal energy while maintaining a pressure between the outer surface of the article and the modeling material at a pressure below atmospheric pressure, and while pressurizing at least a portion of the heating station containing the sealed article to a pressure above atmospheric pressure. In these aspects, by maintaining the pressure between the outer surface of the article and the molding material at a pressure below atmospheric pressure during the heating of step 2730, as a portion of the article, such as a fiber or yarn comprising the low processing temperature polymer composition, melts or deforms, a compressive force on the outer surface of the article is maintained, thereby restricting the flow of the melted material and/or facilitating the molding or formation of the article. In certain aspects, the sealed article may be exposed to thermal energy using the heating station 2210 and other components of the thermoforming system 2200 of fig. 22, such as the carriage 2216 and the negative pressure generating system 2214 (or the heating station 2310 and other components of the thermoforming system 2300 of fig. 23).

As discussed above, in certain aspects, air in an interior portion of the heating station used to expose the sealed articles to thermal energy may be circulated to provide uniform heat distribution to the articles.

In various aspects, step 2740 can include locating the sealed article in a cooling station after exposing the sealed article to thermal energy. In these aspects, the cooling station 2212 of fig. 22 (or the cooling station 2312 of fig. 23) may be employed, including corresponding cooling parameters. In certain aspects, as discussed above, the sealed article may be located in a cooling station while maintaining a pressure between the outer surface of the article and the molding material at a pressure below atmospheric pressure. In these aspects, by maintaining the pressure between the outer surface of the article and the molding material at a pressure less than atmospheric pressure during the cooling of step 2740, the compressive force on the outer surface of the article is maintained, which allows any portion of the article that was melted or deformed during the previous heating step (e.g., portions of upper 1500) to cool and solidify into a desired shape, such as the shape provided at least in part by last 1520. In certain aspects, the sealed articles may be located in the cooling station 2212 (or the cooling station 2312 and other components of the thermoforming system 2300 of fig. 23) by way of other components of the thermoforming system 2200 of fig. 22, such as the carriage 2216 and the negative pressure generating system 2214.

In certain aspects, as discussed above with respect to the cooling station 2212 of fig. 22, the pressure in an interior portion of a heating station, such as the heating station 2212, may be increased, for example, to facilitate removal of air bubbles in the article.

Definition of

As used herein, the following terms, unless otherwise indicated, have the meanings provided below:

the term "fabric" refers to a collection of woven, nonwoven or knitted materials and includes fabrics before and after thermoforming.

The term "polymer" refers to a polymeric molecule having one or more monomeric species, and includes homopolymers and copolymers. The term "copolymer" refers to a polymer having two or more monomer species and includes terpolymers (i.e., copolymers having three monomer species).

Reference to "a" compound "refers to one or more molecules of the compound, and is not limited to a single molecule of the compound. Furthermore, one or more molecules may be the same or may be different, as long as they are within the class of compounds. Thus, for example, "polyamide" should be construed as comprising one or more polyamide polymer molecules, wherein the polymer molecules may be the same or may be different (e.g., different molecular weights and/or isomers).

The terms "at least one" and "one or more" elements are used interchangeably and have the same meaning as encompassing a single element and a plurality of elements and may also be denoted by the suffix "(s)" at the end of the element. For example, "at least one polyamide", "one or more polyamides", and "polyamides(s)", are used interchangeably and have the same meaning.

The term "receiving," such as "receiving an upper of an article of footwear," when recited in the claims, is not intended to require any particular delivery or receipt of the received article. Rather, the term "receiving" is used merely for clarity and ease of reading to describe items which will be referred to in subsequent elements of the claims.

The terms "about" and "substantially" are used herein with respect to measurable values and ranges because of expected variations (e.g., limitations and variability of measurements) known to those skilled in the art.

Unless otherwise indicated, the temperatures referred to herein are based on atmospheric pressure (i.e., one atmosphere).

Characterisation and characterisation programme

The different properties and characteristics of the parts and support materials described herein were evaluated by different test procedures as described below:

_crcreep relaxation temperature T measuring method

Creep relaxation temperature T_crDetermined according to the exemplary technique described in U.S. Pat. No. 5,866,058. Creep relaxation temperature T_crCalculated as the temperature at which the stress relaxation modulus of the test material is 10% relative to the stress relaxation modulus of the test material at the solidification temperature of the material, measured according to ASTM E328-02Amount of the compound (A). The solidification temperature is defined as a temperature at which there is little change in the stress relaxation modulus or little change in creep at about 300 seconds after applying stress to the test material, which can be observed by plotting the stress relaxation modulus (in Pa) as a function of temperature (in ° c).

_vsVicat softening temperature T measuring method

Vicat softening temperature T_vsLoad A and rate A are preferably used as determined according to the test methods detailed in ASTM D1525-09 Standard test method for Vicat softening temperatures of plastics.

_hdMethod for measuring thermal deformation temperature T

Thermal deformation temperature T_hdMeasured using 0.455MPa applied stress according to the test method detailed in ASTM D648-16 Standard test method for deformation temperature of plastics under bending load at edgewise locations.

_{m g}Method for measuring melting temperature T and glass transition temperature T

The melting temperature T is determined using a commercially available Differential Scanning Calorimeter ("DSC"), such as TA Instruments DSC Q2000_mAnd glass transition temperature T_g。

In this method, 10 to 15 grams of the sample is placed into a DSC aluminum pan and then lead sealed with a crimper press. The DSC was configured to scan from-100 ℃ to 225 ℃ at a heating rate of 20 ℃/min, held at 225 ℃ for 2 minutes, and then cooled to 25 ℃ at a rate of-10 ℃/min. Then used for determining the glass transition temperature T_gAnd melting temperature T_mThe DSC curve resulting from this scan was analyzed by standard techniques.

Melt flow index determination method

Melt flow index is determined by a squeeze plastometer according to the test method detailed in the standard test method for melt flow rate of ASTM D1238-13 thermoplastics, using procedure A described therein.

Method for measuring cold roll bending

The cold roll bending test was performed according to the following test method. The purpose of this test was to evaluate the cracking resistance of the samples under repeated bending at 60 degrees in a cold environment. The thermoformed sheet of test material was sized to fit inside the bend tester. Each material was tested as five independent samples.

The bend tester is capable of bending the sample to 60 degrees at a rate of 100+/-5 cycles/minute. The diameter of the mandrel of the machine was 10 mm. Suitable machines for this test are Emerson AR-6, Sara STM 141F, Gotech GT-7006, and Shin II Scientific SI-LTCO (DaeSung science).

The samples were inserted into the machine according to the specific parameters of the bending machine used. The machine was placed in a freezer set at-6 ℃ for testing. The motor was turned on to begin bending and the bending cycles were counted until the sample cracked. Cracking of the sample means that the surface of the material is physically cracked. A distinct fold line that does not actually penetrate the surface is not a crack. The samples were measured until the samples had cracked but had not been broken into two pieces.

Modulus measurement method

The modulus of thermoformed plaques of the material was determined according to the test methods detailed in ASTM D412-98 vulcanized rubber and thermoplastic elastomer tensile Standard test methods, with the following modifications. The sample size was ASTM D412-98 die C and the sample thickness used was 2.0 mm +/-0.5 mm. The type of clamp used is a pneumatic clamp with a metal serrated clamping surface. The clamping distance used was 75 mm. The loading rate used was 500 mm/min. The modulus (initial) was calculated by taking the slope of stress (MPa) versus strain in the initial linear region.

The modulus of the yarn was determined according to the test method detailed in EN ISO 2062 (Textiles-reeled Yarns (Textiles-Yarns from Packages)) -determination of the Single-End Breaking Force and the Elongation at Break (Elongation at Break) of the individual yarn using a Constant Rate of Elongation (CRE) tester, with the following modifications. The length of the sample used was 600 mm. The equipment used was an Instron and high iron (Gotech) fixture. The clamping distance used was 250 mm. The pre-load was set to 5 grams and the loading rate used was 250 mm/min. To avoid using the damaged yarn, the first meter of yarn is thrown away. The modulus (initial) was calculated by taking the slope of stress (MPa) versus strain in the initial linear region.

Method for measuring tenacity and elongation

Tenacity and elongation of the yarn can be determined according to the test method detailed in EN ISO 2062 using a constant-speed elongation tester to determine the tenacity at break and elongation at break of the individual yarns, set at a pre-load of 5 grams.

Shrinkage rate measuring method

The individual shrinkage of the fibers and/or yarns can be determined by the following method. The sample fiber or yarn was cut to a length of about 30 mm with the lowest tension at near room temperature (e.g., 20 ℃). The cut samples were placed in a 50 ℃ or 70 ℃ oven for 90 seconds. The samples were removed from the oven and measured. Using the pre-oven and post-oven measurements of the samples, the percent shrinkage was calculated by dividing the post-oven measurement by the pre-oven measurement and multiplying by 100.

Method for measuring melting enthalpy

The enthalpy of fusion is determined by the following method. Samples of 5mg to 10mg of fiber or yarn were weighed to determine the sample mass, placed into a DSC aluminum pan, and the lid of the DSC pan was sealed using a beader. The DSC was configured to scan from-100 ℃ to 225 ℃ at a heating rate of 20 ℃/minute, held at 225 ℃ for 2 minutes, and then cooled to room temperature (e.g., 25 ℃) at a rate of-10 ℃/minute. The melting enthalpy is calculated by integrating the area of the melting endotherm peak and normalizing by the sample mass.

Examples of the invention

The disclosure is further specifically described in the following examples, which are intended to be illustrative only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art.

Example 1: evaluation of commercially available Polymer materials suitable for use as a component of Low processing temperature Polymer compositions Material

In this example, twenty-five commercially available polymers were evaluated for suitability as components of a low processing temperature polymer composition. Evaluation of polymer samples in the form of yarns and/or resins to determine the melting temperature T of these samples_mThe number of cycles they can withstand under the cold ross bending (CRF) test, their shrinkage in the form of a yarn, and their physical appearance after thermoforming. The results are provided in table 1 below.

Table 1: evaluation of commercially available Polymer materials

While most of these commercially available materials have a melting temperature, Tm, in the desired range of less than about 125 ℃, most materials do not have the ideal balance of properties that make them suitable for use in articles of footwear and apparel. For example, many materials have a yellow tint or are opaque when thermoformed. Some materials, when extruded to form yarns, produce yarns with unacceptably high degrees of shrinkage. In addition, many materials become somewhat brittle under low temperature conditions and therefore cannot withstand more than 150,000 test cycles using the cold ross bend test method, making the materials undesirable for some footwear applications.

With respect to applications where embrittlement of the material under low temperature conditions is unacceptable, Platamid H2694/Pebax 4023 SA from akoma was found to be a test polymer capable of passing the cold ross bend (CRF) test at the desired level. Such materials exhibit all other advantageous polymer properties desirable for use in the low processing temperature polymer compositions described herein, such as an advantageous melting temperature T_mAnd remain transparent during thermoforming。

The present disclosure may be described in terms of the following numbered clauses.

Clause 1. a system for thermoforming an article, the system comprising: a heating station to obtain and maintain a pressure above atmospheric pressure; a cooling station; a negative pressure generating system comprising a molding material, a sealing member, and a negative pressure generating device, wherein the negative pressure generating system is to at least partially seal the article within the molding material by exposing the article to a pressure below atmospheric pressure, wherein the negative pressure generating system and the heating station cooperate to simultaneously expose the article to: thermal energy, the sub-atmospheric pressure when the article is at least partially sealed within the modeling material, and the super-atmospheric pressure; and wherein the negative pressure generating system and the cooling station cooperate to expose the article to a temperature that is lower than that to which the article is subjected in the heating station when the article is at least partially sealed within the modeling material and exposed to the pressure that is lower than atmospheric pressure.

Clause 2. the system for thermoforming an article of clause 1, wherein the molding material exhibits a melting temperature T greater than about 135 ℃_mDecomposition temperature T_dOr both.

Clause 3. the system for thermoforming an article according to any of clauses 1 and 2, wherein the heating station comprises one or more thermal elements.

Clause 4. the system for thermoforming an article of clause 3, wherein the one or more thermal elements each comprise a source of infrared radiation.

Clause 5. the system for thermoforming an article according to any of clauses 1-4, wherein the heating station further comprises an air pressurization device to pressurize air in an interior portion of the heating station.

Clause 6. the system for thermoforming an article according to any of clauses 1-5, wherein the article is an upper of a shoe, and wherein the molding material is sized to seal the entire upper within the molding material.

Clause 7. the system for thermoforming an article of any of clauses 1-6, further comprising a bracket connected to the negative pressure generating system, wherein the bracket is to be connected to the article when the article is at least partially sealed within the molding material.

Clause 8. the system for thermoforming an article of clause 7, wherein the carriage is to be coupled to the heating station while at least a portion of the article is located in the interior portion of the heating station.

Clause 9. the system for thermoforming an article of any of clauses 1-8, wherein the cooling station comprises a positive pressure source and is to maintain the pressure above atmospheric pressure while the article is at least partially sealed within the molding material and exposed to the pressure below atmospheric pressure.

Clause 10. the system for thermoforming an article according to any of clauses 1-9, wherein the article comprises an upper of a shoe, the upper comprising an outsole portion, and wherein the outsole portion protrudes beyond at least a portion of the one or more thermal elements when the upper is located in the interior portion of the heating station.

Clause 11. a method for thermoforming an article, the method comprising: receiving an article; compressing a molding material onto an outer surface of the article by reducing a pressure between the outer surface of the article and the molding material to a pressure below atmospheric pressure, thereby forming a sealed article; exposing the sealed article to thermal energy in a heating station while: maintaining a pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure and pressurizing at least a portion of the heating station containing the sealed article to a pressure above atmospheric pressure; and after exposing the sealed article to thermal energy, locating the sealed article in a cooling station while maintaining the pressure between the outer surface of the article and the modeling material at the sub-atmospheric pressure.

Clause 12. the method of clause 11Method for thermoforming an article, wherein the molding material exhibits a melting temperature T above about 135 ℃_mDecomposition temperature T_dOr both.

Clause 13. the method for thermoforming an article according to any of clauses 11 and 12, wherein at least a portion of the article is covered in a protective sleeve.

Clause 14. the method for thermoforming an article according to any of clauses 11-13, wherein the article comprises an upper of a shoe, the upper comprising an outsole portion, and wherein the method further comprises placing the upper on a last such that the outsole portion covers a bottom portion of the last.

Clause 15. the method for thermoforming an article of any of clauses 11-14, wherein the heating station comprises a closed structure having an interior portion defined by first and second opposing end faces and at least one sidewall, and wherein the first end face is to receive at least a portion of the sealed article, and wherein the closed structure is capable of maintaining the above-atmospheric pressure.

Clause 16. the method for thermoforming an article according to any of clauses 11-15, wherein the article comprises an upper of a shoe, the upper comprising an outsole portion, and wherein the method further comprises positioning the upper in the interior portion of the heating station such that the outsole portion protrudes beyond the one or more thermal elements.

Clause 17. the method for thermoforming an article according to any of clauses 11-16, after locating the sealed article in the cooling station, increasing the pressure between the exterior surface of the article and the modeling material to a pressure above atmospheric pressure such that the modeling material is no longer compressed onto the exterior surface of the article.

Clause 18. the method for thermoforming an article of any of clauses 11-17, further comprising transferring the sealed article from the heating station to the cooling station using a carriage while maintaining the pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure.

Clause 19. the method for thermoforming an article according to clause 18, wherein the carrier is connected to a negative pressure generating system, and wherein the carrier, the negative pressure generating system, and the heating station cooperate to expose the sealed article to a temperature of about 135 ℃ or less than about 135 ℃ in an interior portion of the heating station while maintaining the pressure between the exterior surface of the article and the molding material at the sub-atmospheric pressure and while pressurizing at least the portion of the heating station containing the sealed article to the above-atmospheric pressure.

Clause 20. the method for thermoforming an article according to clause 18 or 19, wherein the carriage, the negative pressure generating system, and the cooling station cooperate to simultaneously expose the sealed article to: a temperature of about 25 ℃ or less than about 25 ℃ in an interior portion of the cooling station while maintaining the pressure between the outer surface of the article and the molding material at the sub-atmospheric pressure; and a positive pressure above atmospheric pressure.

Although the present disclosure has been described with reference to preferred aspects, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the disclosure.