Protein shoe upper fabric based on protein fiber yarn and weaving process thereof

Abstract

This invention provides a protein fiber shoe upper fabric based on protein fiber yarn and its weaving process. The preparation process of the protein fiber yarn includes the following steps: cross-linking, coagulation, and bundling of protein through microfluidic or wet spinning to obtain shaped protein fibers; the protein is natural or synthetic protein with a purity of over 90%; the shaped protein fibers are subjected to differential stretching, with a differential stretching ratio of 1-6 times; and the fibers are then wound, collected, and post-treated to obtain the protein fiber yarn. This invention uses high-performance protein fiber yarn prepared by microfluidic or wet spinning technology as raw material, and utilizes multi-strand bundling and weaving techniques to construct a series of protein yarns, which are then used to produce protein shoe upper fabrics through weaving or flyweaving. Compared with conventional polyester shoe uppers, this invention can achieve a weight reduction of approximately 15% for the shoe upper, while maintaining high strength and high toughness, as well as softness, comfort, lightness, breathability, and biodegradability.

Description

Technical Field

[0001] This invention relates to the field of shoe upper molding technology, and in particular to protein shoe upper materials and their weaving processes, including a process for preparing protein fiber yarn, a protein shoe upper fabric and its weaving process. Background Technology

[0002] With the improvement of living standards, people have higher demands for footwear products that are of higher quality, more aesthetically pleasing, and more comfortable. At the same time, concepts such as environmental protection, pollution-free, biodegradable, and recyclable materials are gradually gaining popularity, strongly promoting the continuous development and innovation of new materials for clothing. Currently, commonly used shoe upper materials are made by combining natural leather, synthetic leather, and various chemical fibers (referred to as synthetic fibers) such as nylon with polyester or nylon hot-melt yarn. The mechanical strength of these materials is generally low. To ensure high abrasion resistance and strength, a certain thickness or coarser yarn is usually required, which affects the breathability and comfort of the shoe upper.

[0003] In clothing fabrics, protein fibers are essentially composed of amino acids. Due to the multiple intermolecular forces and multi-level structure between protein molecules, they possess excellent strength and toughness. Simultaneously, protein fibers exhibit excellent breathability and biocompatibility, significantly enhancing the comfort of clothing. However, natural protein fibers currently suffer from disadvantages such as limited production sources and inconsistent material properties. Regenerated protein fibers, due to issues with fiber strength and fiber continuity during the textile process, cannot be processed as quickly as traditional synthetic fibers, greatly limiting their application in shoe upper material manufacturing.

[0004] Therefore, there is an urgent need to develop new bio-protein materials to meet people's demand for new types of comfortable clothing, such as shoe upper materials. Summary of the Invention

[0005] In view of this, the present invention provides a novel protein shoe upper material and its weaving process. Based on protein fiber yarn, the present invention provides a new type of lightweight, soft, comfortable and breathable shoe upper material for high-end sports equipment through weaving process.

[0006] This invention provides a process for preparing protein fiber yarn, comprising the following steps:

[0007] Protein fibers are obtained by cross-linking, coagulation, and bundling of proteins through microfluidic or wet spinning methods; the proteins are natural or synthetic proteins with a purity of over 90%; the coagulation process uses a coagulation bath containing a dehydrating agent, which is one or more of methanol, ethanol, and isopropanol.

[0008] The shaped protein fibers are subjected to differential stretching, with the differential stretching ratio being 1-6 times; after winding, collection, and post-processing, protein fiber yarn is obtained.

[0009] In some embodiments of the present invention, the protein is an elastin-like protein, squid cyclodentin, arthropod elastin, bovine serum albumin, or silk protein.

[0010] In some embodiments of the present invention, the solvent for protein dissolution in the microfluidic or wet spinning process is pure water; the coagulation bath also contains a crosslinking agent, preferably glutaraldehyde.

[0011] In some embodiments of the present invention, the mass content of the dehydrating agent in the coagulation bath is 50% to 90%; and the mass content of the crosslinking agent is 0.5% to 5%.

[0012] In some embodiments of the present invention, the microfluidic or wet spinning extrusion speed is 50-120 μL / min, and the number of extruded fibers is 5-100.

[0013] In some embodiments of the present invention, the post-processing includes twisting, doubling, or braiding; the twist of the twisting process is 0-100T / 10cm; the number of single fibers in the doubling process is 1-100; the number of spindles in the braiding process is 8-16, the braiding density is 20-300 mesh, and the braiding speed is 20-300r / min.

[0014] Compared with existing technologies, this invention provides a protein fiber yarn suitable for shoe uppers and its preparation process. The protein fiber yarn uses natural or recombinant protein with a purity of ≥90% as the fiber-forming raw material. It is shaped into protein fibers through specific methods such as microfluidic or wet spinning, followed by differential stretching, crimping collection, and post-processing. In this invention, the resulting protein fiber yarn applied to shoe uppers is softer and more skin-friendly, improving wearing comfort. Furthermore, the protein raw material has good biocompatibility, meeting the needs of resource renewability and environmentally friendly social development, and has great application potential for producing high-value-added, high-end sports shoes.

[0015] Furthermore, the protein source involved in this invention has a certain degree of designability. Different peptide structure designs can significantly improve the mechanical properties of protein fiber yarns, offering more application possibilities compared to shoe uppers made from natural protein fibers. This invention provides a novel bio-protein material for shoe upper fabrication, possessing high added value in applications.

[0016] This invention provides a protein shoe upper fabric, which is woven from protein fiber yarn obtained by the preparation process described above through weaving or flyweaving.

[0017] In some embodiments of the present invention, the protein upper fabric has a single-layer fabric structure woven from protein fiber yarns;

[0018] Alternatively, the protein upper fabric may include a skin-fitting fabric layer and a reinforcing fabric layer that are combined and covered, both of which are primarily composed of the protein fiber yarns.

[0019] In some embodiments of the present invention, the fabric structure of the protein upper includes one or more of the following: plain weave, pseudo-flat weave, double rib weave, and semi-perforated weave.

[0020] This invention provides a weaving process for protein shoe upper fabric as described above, comprising the following steps:

[0021] The protein fiber yarn is woven or knitted to form a single-layer fabric structure for the protein shoe upper or skin-friendly fabric layer.

[0022] Optionally, the protein fiber yarn can be woven or knitted, and then calendered to form a reinforced fabric layer; the skin-friendly fabric layer and the reinforced fabric layer can be overlapped and sewn together to obtain the protein shoe upper fabric.

[0023] This invention uses high-performance protein fiber yarns prepared from natural or synthetic proteins through microfluidic or wet spinning technology as raw materials. A series of protein yarns are constructed using multi-strand bundling and weaving techniques, and a series of protein shoe upper fabrics are prepared through weaving or flyweaving. Compared with conventional polyester yarns for shoe uppers, this invention can achieve approximately 15% weight reduction in shoe uppers using the same weaving method, while also possessing high strength and toughness, as well as softness, comfort, lightweight breathability, and biodegradability. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a stress / strain curve diagram of the elastic protein fiber of Example 1;

[0026] Figure 2 SEM images of bovine serum albumin fiber cross-sections from Examples 3-5;

[0027] Figure 3 This is a photograph of the actual product of the 16-spindle braided strand of bovine serum albumin fiber used in Examples 3-5;

[0028] Figure 4Examples 3-5 show composite woven shoe upper fabrics made from bovine serum albumin fibers and elastin-like fibers;

[0029] Figure 5 This is a schematic diagram of the weaving process for the silk protein fiber flyknit shoe upper in Example 6;

[0030] Figure 6 Example 6: Silk protein fiber flyknit upper;

[0031] Figure 7 Example 7: Silk protein fiber shoe upper fabric;

[0032] Figure 8 Example 8: Flyknitted shoe upper made of silk protein fiber (unheated melt).

[0033] Figure 9 Example 8: Silk protein fiber (heated melting) flyknit shoe upper. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] According to a first aspect of the present invention, a method for preparing protein fiber yarn is provided, comprising the following steps:

[0036] Protein fibers are obtained by cross-linking, coagulation, and bundling of proteins through microfluidic or wet spinning methods; the proteins are natural or synthetic proteins with a purity of over 90%; the coagulation process uses a coagulation bath containing a dehydrating agent, which is one or more of methanol, ethanol, and isopropanol.

[0037] The shaped protein fibers are subjected to differential stretching, with the differential stretching ratio being 1-6 times; after winding, collection, and post-processing, protein fiber yarn is obtained.

[0038] This invention provides a protein fiber yarn that can be used in shoe upper fabrics, which facilitates the production of lightweight, soft, comfortable and breathable shoe upper fabrics, thereby increasing the added value of footwear and other products.

[0039] The embodiments of this invention first obtain pure proteins, either natural or artificially synthesized, with a purity of 90% or higher. These proteins can be commercially available or synthesized and prepared using microbial synthesis technology. Specifically, this includes: transforming plasmids into an *E. coli* expression strain, conducting microbial fermentation culture, and then preparing recombinant proteins through high-throughput protein purification. This yields a series of natural or artificial recombinant proteins, such as elastin-like proteins (which may be the elastin-like proteins involved in patent document ZL202111676129.0, with a molecular weight of 30,000-80,000), squid cyclodentin (which may be the highly water-soluble chimeric protein involved in patent document ZL202010303454.1), bovine serum albumin (which may be the bovine serum albumin used in the embodiments of patent document ZL201910977518.3), or silk fibroin (mainly silk fibroin obtained after dissolving commercially available silkworm cocoons), etc.

[0040] In this embodiment of the invention, microfluidic or wet spinning technology is used to dissolve the protein from the above steps in pure water to obtain a protein solution with a mass concentration of 100-300 mg / mL. The solution can be slowly extruded into a coagulation bath by an injection pump to form and bundle the fibers, thereby obtaining shaped protein fibers.

[0041] Wet spinning technology typically involves: a spinning solution containing fiber-forming polymers (including biomacromolecules) and its extrusion from a spinneret to form a fine stream; the fine stream of the solution entering a coagulation bath, where it coagulates and precipitates to form highly mobile nascent fibers; and the nascent fibers being bundled together and subjected to certain post-processing. Building upon traditional wet spinning, microfluidic spinning technology utilizes the laminar flow effect of microfluidics, combined with the flow reaction of the spinning solution through microchannels, to prepare micro / nano-scale fibers. Besides microfluidic devices such as microfluidic channels, it also includes injection devices such as spinning solution injection pumps, and fiber receiving devices. This invention does not impose any special limitations on the equipment and components of microfluidics and wet spinning; any components well-known in the art can be used.

[0042] Furthermore, the microfluidic or wet spinning equipment is for large-scale production, with stable structure and reliable production. The number of fibers formed can be freely changed by the device, for example, the number of extruded fibers is 10 to 100. The extrusion speed of the injection pump is preferably 50 to 120 μL / min, more preferably 60 to 100 μL / min. The coagulation bath is a solution containing a dehydrating agent, or may also contain a crosslinking agent. The dehydrating agent is one or more of methanol, ethanol, and isopropanol. The crosslinking agent includes glutaraldehyde, etc. Specifically, in the coagulation bath, the mass content of the alcohol dehydrating agent is 50% to 90%; the mass content of the crosslinking agent glutaraldehyde is 0.5% to 5%, and the remainder is water.

[0043] Among them, after the protein fiber is formed, it is bundled using multi-strand bundling technology (multi-strand fibers are combined into one bundle). The number of bundles is 5-100, or even 5-80. The bundling position is on the surface of the fiber forming coagulation bath solution, which helps to improve the mechanical properties of the fiber.

[0044] In this embodiment of the invention, the obtained shaped fiber bundle is stretched using a differential-speed stainless steel roller, followed by winding, collection, and post-processing to obtain protein fiber yarn; the differential stretching range is 1-6 times or 3-6 times. This embodiment of the invention achieves the stretching effect of the fiber material by adjusting the linear speed of the stainless steel roller to create a relative speed difference between the roller and the fiber.

[0045] In embodiments of the present invention, tension-stable fiber bundles are post-processed and wound onto finished yarn tubes for subsequent fabric processing. Preferably, the post-processing includes three methods: twisting machine, doubling machine, and braiding machine (doubling and twisting are performed using one or both types of equipment, which differs from the function of the braiding machine):

[0046] (1) When there are many tensile stable fiber monofilaments or the thickness meets the requirements (fiber bundle diameter in the range of 200-1000 micrometers), the collected fiber bundles are wound onto the finished yarn tube by a twisting machine to facilitate subsequent unwinding processing. The twisting machine can apply a certain twist to give the fiber a certain strength. The twisting machine has a twist range of 0-100T / 10cm and the twisting direction can be Z twist or S twist.

[0047] (2) When the number of tensile stable fiber monofilaments is small or the thickness is small, the collected fiber bundles are bundled together by a doubling machine and wound onto the finished yarn tube (doubling is the physical synthesis of multiple fibers into a bundle to form a yarn bundle), so that the thickness meets the requirements (the fiber bundle diameter is in the range of 200-1000 micrometers). The fibers obtained in this way are soft and have high strength. The number of doubling strands is in the range of 1-80.

[0048] (3) When the number of tensile-stable fiber monofilaments is small or the fiber thickness is thin, the collected fiber bundles are braided and twisted together on a multi-spindle braiding machine and wound onto the finished yarn tube (braiding is the process of using a braiding machine to cross-link and weave fibers into a single coarse fiber), so that the thickness meets the requirements (fiber bundle diameter in the range of 200-1000 micrometers). Fibers obtained in this way can be used to prepare stiffer fabrics; the preferred number of braiding spindles is 8-16; the braiding density is 20-300 mesh; the braiding speed can be 20-300 r / min. If the process parameters are not within this range, the mechanical properties of the fiber will decrease or the fiber will be prone to breakage during the braiding process. The twisting machine, doubling machine, and braiding machine involved in the embodiments of this invention are all commonly used spinning and weaving equipment in the field.

[0049] This invention provides a protein fiber yarn, prepared by the process described above; its application in shoe uppers results in a softer, more skin-friendly feel and improved wearing comfort. Furthermore, the protein raw material exhibits good biocompatibility, aligning with the societal development requirements of resource renewability and environmental friendliness. The protein source involved in this invention offers a degree of designability; different peptide structure designs can significantly improve the mechanical properties of the protein fiber yarn, offering greater application possibilities compared to shoe uppers made from natural protein fibers.

[0050] This invention provides a protein shoe upper fabric, which is woven from protein fiber yarn obtained by the preparation process described above through weaving or flyweaving. Based on the characteristics of the protein fiber yarn, the protein shoe upper fabric provided by this invention is lightweight, soft, and breathable, making it suitable for use in high-end sports shoes and other products.

[0051] In some embodiments, the protein upper fabric has a single-layer fabric structure woven from protein fiber yarns; in other embodiments, the protein upper fabric includes a skin-fitting fabric layer and a reinforcing fabric layer that are both primarily composed of the protein fiber yarns.

[0052] The present invention provides a weaving process for protein shoe upper fabric as described above, including the following steps:

[0053] The protein fiber yarn is woven or knitted to form a single-layer fabric structure for the protein shoe upper or skin-friendly fabric layer.

[0054] Optionally, the protein fiber yarn can be woven or knitted, and then calendered to form a reinforced fabric layer; the skin-friendly fabric layer and the reinforced fabric layer can be overlapped and sewn together to obtain the protein shoe upper fabric.

[0055] In some embodiments of the present invention, the protein fiber yarns on the finished yarn tubes obtained by the twisting machine or the doubling machine are woven according to the fabric structure by the loom weaving or flat knitting method to form semi-finished shoe uppers with plain weave, double rib, and other structures; the semi-finished shoe uppers define areas to be cut, and the cut semi-finished shoe uppers are edge-sealed, washed, ironed and shaped, and compared with the film to finally obtain the protein shoe uppers that meet the set size.

[0056] In some embodiments of the present invention, the protein fiber yarn on the finished yarn tube obtained by a twisting machine or a doubling machine is woven according to the structure using a loom or a flat knitting machine to form a first semi-finished shoe upper; the first semi-finished shoe upper defines an area to be cut, and the cut first semi-finished shoe upper is used as a skin-adhesive fabric layer and is edge-sealed; and the protein fiber yarn on the finished yarn tube obtained by a twisting machine or a knitting machine is also woven using a loom or a flat knitting machine to form a second semi-finished shoe upper; the second semi-finished shoe upper needs to be calendered (calendering is a shaping process using hot pressing technology, such as a steam iron at 100°C, pressure: pressing down by hand, time 3-5s); the second semi-finished shoe upper defines an area to be cut, and the cut second semi-finished shoe upper is used as a reinforcing fabric layer and is edge-sealed.

[0057] In this embodiment of the invention, the skin-fitting fabric layer and the reinforcing fabric layer are sewn together, and the defined shoelace eyelet forming area is perforated using conventional methods, ultimately obtaining a protein upper fabric that conforms to the set dimensions; there are no special restrictions on the sewing process. This invention uses woven protein fibers to prepare the reinforcing fabric layer of the upper. The weaving technique enhances the abrasion resistance of the protein fibers, making them better suited for the design of the upper reinforcement layer. In the protein upper fabric described in this embodiment of the invention, both the skin-fitting fabric layer and the reinforcing fabric layer are composed entirely of protein fibers, resulting in a lighter, more comfortable upper that allows for more space for design optimization of the internal and external patterns and structures of the upper.

[0058] To better illustrate the present invention, further examples are provided below. Unless otherwise specified, all reagents and raw materials used in the present invention are commercially available products or products that can be prepared by recognized methods. Unless otherwise specified, all proportions are mass proportions.

[0059] Example 1

[0060] 1. Using the ZL202111676129.0 correlation technology, K72 elastin-like fibers were obtained by wet spinning with a protein purity ≥95%. The coagulation parameters were: 70% ethanol / 4% glutaraldehyde / 26% water, with 5-20 extruded bundles and a differential stretching ratio of 1-2 times. The mechanical properties of the prepared elastin-like fibers are shown in Table 1, with a single fiber diameter of 20 micrometers. Figure 1 This is a stress / strain curve of the elastin fiber in Example 1. This graph shows the mechanical properties of the same type of protein fiber; different curves represent the mechanical properties of different fibers, and there is a certain degree of error between different curves. Measurements were performed using a single-fiber mechanical testing instrument, and the prepared elastin fiber is classified as a high-strength, high-toughness protein fiber.

[0061] 2. The collected elastin fibers are distributed onto the braiding machine tubes and braided on a vertical 16-spindle braiding machine in a 1-to-2 full-spindle pressing manner. The braiding speed is set to 100 rpm, the mesh count to be 50 meshes, and the braiding angle to be 50°. The braided yarn is then wound onto the finished yarn tube.

[0062] 3. On the E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. Four 16-spindle braided elastic protein fibers are fed together into one yarn feeder. Four yarn feeders are used at the same time. According to the pattern drawing, the base is made using a pseudo four-flat weave, and the weave is made at a 75-degree angle. The body is made using a double rib weave, and the machine head speed is reduced at the pattern holes.

[0063] 4. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper is then edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed. The shoe upper fabric is washed and ironed to set its shape. After comparison with the film, a protein shoe upper that meets the set size is finally obtained.

[0064] Table 1 Mechanical property data of elastin fibers

[0065] Example 1 Tensile breaking strength (GB / T 528-2009) Young's modulus Fiber toughness unit MPa GPa <![CDATA[MJ / m 3 ]]> 374.3±11.5 1.2±0.6 100.2±10.2

[0066] Example 2

[0067] 1. Using the ZL202010303454.1 related technology, squid ring-tooth (SRT36) protein fibers were obtained by wet spinning. The mechanical properties are shown in Table 2, and the fiber diameter was 18-25 micrometers. This process utilizes the structural protein designed in the related patent for optimized spinning and does not involve pre-crosslinking; the dehydrating agent is 80% ethanol, and other processes are the same.

[0068] 2. The collected squid cyclops protein fibers are packaged onto the braiding machine tubes and braided on a vertical 16-spindle braiding machine in a 1-to-2 full-spindle pressing manner. The braiding speed is set to 100 rpm, the mesh count to be 50 meshes, and the braiding angle to be 50°. The braided yarn is then loaded onto the finished yarn tube.

[0069] 3. On the E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. Four 16-spindle braided squid cyclops protein fibers are fed together into one yarn feeder. Four yarn feeders are used at the same time. According to the pattern drawing, the base is made using a pseudo four-flat weave, and the weave is made at a 75-degree angle. The body is made using a double rib weave, and the machine head speed is reduced at the pattern holes.

[0070] 4. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper is then edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed. The shoe upper fabric is washed and ironed to set its shape. After comparison with the film, a protein shoe upper that meets the set size is finally obtained.

[0071] Table 2 Mechanical properties of squid cyclodentin fiber

[0072]

[0073] Example 3

[0074] 1. Using ZL202111014338.9 correlation technology, bovine serum albumin (BSA) fibers were obtained through microfluidic spinning. The process involved mixing a protein solution (commercially available BSA; this is artificially extracted BSA, and any commercially available brand is acceptable) with 0.2% glutaraldehyde by volume for cross-linking treatment. The coagulation bath consisted of 80% ethanol, 5% glutaraldehyde, and 15% water. The stretching roller speed was gradually increased within the range of 3–40 rpm, ensuring that the final collection roller's total stretch was four times the speed of the first roller. The resulting 20-channel fiber was then wound and collected to obtain protein fibers (single fiber diameter approximately 20 micrometers). The fibers exhibited good wash resistance with a mass loss of only about 4%. The mechanical properties of the obtained protein fibers are shown in Table 3.

[0075] 2. Load the tensile-stable 20-channel fibers onto the braiding machine bobbin. Braid and twist the fibers on a vertical 16-spindle braiding machine using a 1-to-2 full-spindle twisting method, setting the braiding speed to 60 rpm, the mesh count to 50 mesh, and the braiding angle to 50°. Load the twisted yarn onto the finished yarn bobbin. Simultaneously, combine and wind 8 tensile-stable 20-channel fibers onto the finished yarn bobbin using a doubling machine.

[0076] 3. Preparation of the skin-adhesive fabric layer: The fibers on the finished yarn bobbins obtained by the doubling machine are woven using a flat knitting machine to form a semi-finished shoe upper. On an E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. A pseudo-four-needle weave is used for the base, woven at 75 mesh. After turning the needles, the weft plain weave continues, also woven at 75 mesh. Then, the main body of the shoe upper is woven. The skin-adhesive layer fabric requires softness, comfort, and abrasion resistance; therefore, an abrasion-resistant weave is selected, with a mesh setting of 80 and a lower machine head speed of 60. To make this layer of fabric lighter and more breathable, a single-layer weave can be used. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished skin-adhesive layer is then edge-sealed.

[0077] 4. Preparation of the reinforcing fabric layer: The fibers on the finished yarn tubes obtained by braiding and twisting are woven on a loom to form a semi-finished shoe upper. On a rapier loom, elastic protein fibers of the type described in Example 1 are used as warp yarns, and 16 spindles of braided and twisted bovine serum albumin fibers are used as weft yarns. The weaving is done with a warp density of 100 threads / 10cm, a weft density of 300 threads / 10cm, and a reed density of 1 stitch / coil, in a plain weave. Subsequently, the semi-finished shoe upper is calendered (the shoe upper is shaped using hot steam; the hot pressing equipment is a continuous operation device with rollers, the temperature is about 140-180℃, the duration is 3-5 seconds, and the pressure mainly comes from the rollers; pressing is sufficient). The cut semi-finished reinforcing layer is then edge-sealed.

[0078] 5. Sewing of multi-layer uppers: The skin-fitting fabric layer and the reinforcing fabric layer obtained in steps 3 and 4 are bonded and sewn together. At the same time, the defined shoelace eyelet forming area is perforated to finally obtain a protein upper that meets the set size.

[0079] Table 3. Mechanical properties of bovine serum albumin fibers

[0080] Example 3 Tensile breaking strength Young's modulus toughness unit MPa GPa <![CDATA[MJ / m 3 ]]> 351.7±5.2 4.6±0.8 44.1±2.1

[0081] Example 4

[0082] 1. Using the ZL202111014338.9 correlation technology, bovine serum albumin fibers (same as in Example 3) were obtained. In this process, the protein solution was mixed with 0.3% glutaraldehyde by volume for cross-linking treatment. The coagulation bath consisted of 80% ethanol, 5% glutaraldehyde, and 15% water. The speed of the stretching roller was gradually increased within the range of 3 to 40 rpm, so that the total stretch of the final collection roller was three times the speed of the first roller. The obtained ten-channel fiber was then wound up and collected to obtain the protein fiber.

[0083] 2. Load the tension-stabilized ten-channel fibers onto the braiding machine bobbin, and braid them on a vertical 16-spindle braiding machine using a half-spindle 1-to-1 method. Set the braiding speed to 60 rpm and the mesh count to 100 mesh. Load the braided yarn onto the finished yarn bobbin. At the same time, combine and wind 8 tension-stabilized ten-channel fibers onto the finished yarn bobbin using a doubling machine.

[0084] 3. Preparation of the skin-adhesive fabric layer: The fibers on the finished yarn tubes obtained by the doubling machine are woven using a flat knitting machine to form a semi-finished shoe upper. On an E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. The base is made using a pseudo four-stitch weave at 75 mesh. After turning the stitches, the weft plain stitch weave continues at 80 mesh. Then, the main body of the shoe upper is woven using an abrasion-resistant weave at 80 mesh. The machine head speed is set to a low 60. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished skin-adhesive layer is then edge-sealed.

[0085] 4. Preparation of the reinforcing fabric layer: The fibers on the finished yarn tubes obtained from the braided ply are woven on a loom to form a semi-finished shoe upper. On a rapier loom, elastin-like fibers are used as warp yarns, and 8 spindles of braided bovine serum albumin fibers are used as weft yarns. The weave is a plain weave with a warp density of 200 threads / 10cm, a weft density of 400 threads / 10cm, and a weft density of 1 stitch / reed. The semi-finished shoe upper is then calendered, and the cut semi-finished skin-adhesive layer is edge-sealed.

[0086] 5. Sewing of multi-layer uppers: The skin-fitting fabric layer and the reinforcing fabric layer obtained in steps 3 and 4 are bonded and sewn together. At the same time, the defined shoelace eyelet forming area is perforated to finally obtain a protein upper that meets the set size.

[0087] Example 5

[0088] 1. Using the ZL202111014338.9 correlation technology, bovine serum albumin fibers (same as in Example 3) were obtained. In this process, the protein solution was mixed with 0.2% glutaraldehyde by volume for cross-linking treatment. The coagulation bath consisted of 80% ethanol, 5% glutaraldehyde, and 15% water. The speed of the stretching roller was gradually increased within the range of 3 to 40 rpm, so that the total stretch of the final collection roller was 4 times the speed of the first roller. The obtained twenty-channel fibers were then wound up and collected to obtain the protein fibers.

[0089] 2. The tensile-stable 20-channel fiber is loaded onto the braiding machine tube and braided on a vertical 16-spindle braiding machine in a 1-to-2 full-spindle pressing manner. The braiding speed is set to 60 rpm, the mesh count to 50 mesh, and the braiding angle to 50°. The braided yarn is then wound onto the finished yarn tube.

[0090] 3. On the E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. Four 16-spindle tucked bovine serum albumin fibers are fed together into one yarn feeder. Four yarn feeders are used at the same time. According to the pattern drawing, the base is made using a pseudo four-flat weave and knitted at a 75-degree angle. The body is knitted using a double rib weave. The machine head speed is reduced at the pattern holes.

[0091] 4. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper is then edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed. The shoe upper fabric is washed and ironed to set its shape. After comparison with the film, a protein shoe upper that meets the set size is finally obtained.

[0092] in, Figure 2 The cross-sectional view of the multi-strand bovine serum albumin fibers combined in Examples 3-5 is shown; Figure 3 The fiber winding structure of 16-spindle braided strands of bovine serum albumin fiber in Examples 3-5 is shown. Figure 4 The fabric samples shown are composite fabrics from Examples 3-5, in which elastin-like fibers are used as warp yarns and 8 spindles of woven bovine serum albumin fibers are used as weft yarns. Examples 3-4 differ in fiber forming parameters, weaving parameters, and the types of woven protein fibers, resulting in slight differences in their mechanical properties.

[0093] Example 6

[0094] 1. High-performance silk protein fibers were prepared using wet spinning technology. The protein solution was dissolved, and the coagulation bath consisted of an ethanol / water solution. The speed of the stretching roller was gradually increased within the range of 3–40 rpm, so that the total stretch of the final collection roller was 7 times the speed of the first roller. The resulting 20-channel fiber was then wound and collected to obtain the protein fiber. Its mechanical properties are shown in Table 4. The silk protein was obtained by dissolving commercially available silkworm cocoons. The preparation process of the regenerated silk protein was as follows: the silkworm cocoons and silk were degummed in a sodium bicarbonate solution, then completely dissolved in a 9.8M lithium bromide solution, dialyzed for 5 days, and then freeze-dried; the protein purity was ≥95% (the same applies to the following examples).

[0095] 2. Distribute the tensile-stable twenty-channel fibers onto the bundling machine tube, combine 5-30 fibers into a bundle, and wind the twisted yarn onto the finished yarn tube.

[0096] 3. On an E18 double-needle bed computerized flat knitting machine, a pattern is made according to the standard size 40 shoe shape. The upper body is made of double rib fabric. The round holes are formed in the pattern of the upper by the method of moving the needles away from the loop. The round holes maintain good structural stability even when ironing, and the holes are not easy to come apart. The semi-permeable structure connects the loops of the front and back needle beds. The front of the fabric has gaps and has a concave and convex effect, while the reverse side has a structure similar to plain knitting. The flat reverse side of the fabric fits the foot better.

[0097] 4. To ensure the thickness and stiffness of the shoe upper, two bundles of silk protein fibers (approximately 300μm in diameter) are fed simultaneously into a single yarn feeder. Four yarn feeders are used concurrently, and a pseudo-flat weave (e.g., according to the pattern drawing) is employed for the sole fabrication. Figure 5 The fabric is woven at a 75-degree angle, with a double rib knit for the main body. The machine head speed is reduced at the circular holes of the pattern. The resulting semi-finished shoe upper is as follows: Figure 6 As shown.

[0098] 5. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper is then edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed. The shoe upper fabric is washed and then subjected to conventional ironing and heat setting processes. After comparison with film, a protein shoe upper that meets the set size is finally obtained.

[0099] 6. The performance data of the silk protein fiber flyknit upper are shown in Table 5. It can be seen that it has good tensile breaking strength and high toughness. The fabric is lightweight and breathable, with light fastness grade 4, UV fastness grade 4, aging fastness grade 4, and Martindale abrasion resistance (GB / T 21196.2-2007) qualified.

[0100] Table 4. Mechanical properties of silk fibroin fibers

[0101] Example 6 Tensile breaking strength Young's modulus toughness unit MPa GPa <![CDATA[MJ / m 3 ]]> 426.6±12.4 6.64±0.16 84.2±7.2

[0102] Table 5 Performance data of silk protein fiber fabric

[0103]

[0104] Example 7

[0105] 1. High-performance silk protein fibers are prepared using wet spinning technology. The protein solution is dissolved, and the coagulation bath is composed of ethanol / water solution. The speed of the stretching roller is gradually increased in the range of 3 to 40 rpm, so that the total stretch of the final collection roller is 7 times the speed of the first roller. The obtained 20-channel fiber is wound up and collected to obtain the protein fiber.

[0106] 2. Distribute the tensile-stable twenty-channel fibers onto the bundling machine tube, combine 5-30 fibers into a bundle, and wind the twisted yarn onto the finished yarn tube.

[0107] 3. On an E18 double-needle bed computerized flat knitting machine, a pattern is created based on a standard size 40 shoe. Six bundles of silk protein fibers (approximately 70μm in diameter) are woven using a double rib weave. The resulting skin-adhesive fabric is as follows: Figure 7 As shown.

[0108] 4. The performance data of the silk protein fiber fabric after ironing and shaping are shown in Table 6. According to Table 6, it has good tensile breaking strength and high toughness. The fabric is soft and skin-friendly, lightweight and breathable. It has a light fastness of 4, a UV fastness of 4, an aging fastness of 4, and is qualified for Martindale abrasion resistance (GB / T21196.2-2007).

[0109] 5. The skin-friendly fabric layer prepared using this silk protein fiber through a woven method is also lightweight and breathable. On a rapier loom, using silk protein fiber as both warp and weft yarns, with a warp density of 100 threads / 10cm, a weft density of 600 threads / 10cm, and a reed density of 1 weft thread per stitch, it is woven in a plain weave (e.g.) Figure 7 (As shown). The moisture permeability of the fabric was tested according to the test conditions in group b of GB / T12704.1-2009. The moisture permeability of this shoe upper fabric was 84.1 g / (m²). 2 ·h).

[0110] Table 6 Performance data of silk protein fiber fabric

[0111]

[0112] Example 8

[0113] 1. Using the same weave parameters as in Example 5, silk protein fibers (approximately 150 μm in diameter) were used on an E18 double-needle bed computerized flat knitting machine to prepare a semi-finished shoe upper. The resulting semi-finished shoe upper is as follows: Figure 8 As shown, in addition, polyester hot melt yarn of regular size can be mixed and woven together to obtain a semi-finished shoe upper, such as... Figure 9 As shown; one hot-melt wire is mixed in every 1-3 bundles of protein fibers. Figure 8 and Figure 9 The process in steps 2-4 is the same. Whether or not hot melt wire is added is not related to the process, but to the material's shaping state. After heat setting, the fabric is harder after adding hot melt wire, while the fabric without hot melt wire is softer.

[0114] 2. The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper fabric is edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed. The shoe upper fabric is washed and then ironed and heat-set using conventional processes. After comparison with film, a protein shoe upper that meets the set size is finally obtained.

[0115] 3. The performance data of the silk protein fiber flyknit upper are shown in Table 7. It can be seen that it has good tensile breaking strength and high toughness. The light fastness is grade 4, the UV fastness is grade 4, the aging fastness is grade 4, and the Martindale abrasion resistance (GB / T21196.2-2007) is qualified.

[0116] 4. The shoe upper fabric prepared using this silk protein fiber through a woven method is also lightweight and breathable. On a rapier loom, silk protein fiber is used as both warp and weft yarns, with a warp density of 100 ends / 10cm, a weft density of 400 ends / 10cm, and a reed density of 1 weft thread per stitch, in a plain weave. The fabric's moisture permeability was tested according to the test conditions in group b of GB / T 12704.1-2009. The moisture permeability of this skin-adhesive layer fabric is 67.14 g / (m²). 2 ·h).

[0117] Table 7 Performance data of silk protein fiber flyknit shoe uppers (doped with hot melt yarn)

[0118]

[0119] Comparative Example 1:

[0120] On an E18 double-needle bed computerized flat knitting machine, using the same weaving parameters as in Example 8, 150D polyester fibers (approximately 150μm in diameter) are used to prepare a semi-finished shoe upper. In addition, hot melt yarn can be mixed and woven simultaneously.

[0121] The semi-finished shoe upper has a defined area to be cut. The cut semi-finished shoe upper fabric is then edge-sealed. The left and right shoes are checked for matching. After quality inspection, the edges are sealed again. The shoe upper fabric is then washed, ironed, and shaped. By comparing it with the film, a polyester shoe upper that meets the set dimensions can be finally obtained. The performance data of this polyester fiber flyknit shoe upper are shown in Table 7.

[0122] Compared to polyester fiber uppers, protein fiber uppers are 15% lighter for the same fiber diameter, while their bursting strength and tensile breaking strength are significantly higher.

[0123] As can be seen from the above embodiments, this invention uses high-performance protein fiber yarns prepared from natural or synthetic proteins through microfluidic or wet spinning technology as raw materials. A series of protein yarns are constructed using multi-strand bundling and weaving techniques, and a series of protein shoe upper fabrics are prepared through weaving or flyweaving. Compared with conventional polyester yarns for shoe uppers, this invention can achieve a certain degree of weight reduction in shoe uppers under the same weaving method, while also possessing high strength and high toughness, as well as softness, comfort, lightness, breathability, and biodegradability, making it suitable for various applications.

[0124] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the invention. Various variations can be made to the above embodiments of the present invention. All simple and equivalent changes and modifications made in accordance with the claims and description of this application fall within the protection scope of the claims of this patent. All aspects not described in detail in this invention are conventional technical content.

[0125] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A protein shoe upper fabric, characterized in that, It is made of protein fiber yarn and woven by shuttle or fly weave. The protein shoe upper fabric includes a skin-fitting fabric layer and a reinforcing fabric layer that are combined and covered, both of which are mainly composed of the protein fiber yarns. The fabric structure of the protein upper includes one or more of the following: plain weave, pseudo-flat weave, double rib weave, and semi-perforated weave. The preparation process of the protein fiber yarn includes the following steps: Protein fibers are obtained by cross-linking, coagulation, and bundling of proteins through microfluidic or wet spinning methods; the proteins are natural or synthetic proteins with a purity of over 90%; the coagulation process uses a coagulation bath containing a dehydrating agent, which is one or more of methanol, ethanol, and isopropanol. The shaped protein fibers are subjected to differential stretching, with the differential stretching ratio being 1-6 times; after winding, collection, and post-processing, protein fiber yarn is obtained.

2. The protein shoe upper fabric according to claim 1, characterized in that, The protein is an elastin-like protein, squid cyclodentin, arthropod elastin, silk protein, or bovine serum albumin.

3. The protein shoe upper fabric according to claim 1, characterized in that, The solvent used for protein dissolution in the microfluidic or wet spinning process is pure water; the coagulation bath also contains a crosslinking agent, which is glutaraldehyde.

4. The protein shoe upper fabric according to claim 3, characterized in that, The dehydrating agent in the coagulation bath has a mass content of 50% to 90%; the crosslinking agent has a mass content of 0.5% to 5%.

5. The protein shoe upper fabric according to claim 4, characterized in that, The microfluidic or wet spinning extrusion speed is 50~120μL / min, and the number of extruded fibers is 5-100.

6. The protein shoe upper fabric according to any one of claims 1-5, characterized in that, The post-processing includes twisting, doubling, or braiding; the twist degree of the twisting process is 0-100T / 10cm; the number of single fibers in the doubling process is 1-100; the number of spindles in the braiding process is 8-16, and the braiding speed is 20-300r / min.

7. The weaving process of the protein shoe upper fabric as described in any one of claims 1-6, characterized in that, Includes the following steps: Protein fiber yarns are woven or fly-woven to form a single-layer fabric structure that is close to the skin. The protein fiber yarn is woven or fly-woven and then calendered to form a reinforced fabric layer. The skin-adhesive fabric layer and the reinforcing fabric layer are overlapped and sewn together to obtain the protein shoe upper fabric.

Images