Manufacturing method of fluorine-free anti-splashing string technology shoe upper

Abstract

This invention discloses a method for manufacturing a fluorine-free water-repellent upper. The method includes: providing a waterproof layer woven from yarn treated with fluorine-free waterproofing; providing an inner lining layer knitted from cotton blend yarn; sewing multiple deformation-resistant yarns to the surface of the waterproof layer, extending the yarns from the forefoot area to the heel area; overlapping and fixing the waterproof layer and the inner lining layer to form the upper body; and fixing a waterproof and breathable membrane to at least a portion of the outer surface of the waterproof layer to obtain the finished upper. This invention solves the problems of environmental pollution, performance degradation after washing, and easy pore expansion and water seepage in existing water-repellent upper treatments by combining the sewing and fixing of deformation-resistant yarns with fluorine-free waterproofing. It has the advantages of being environmentally friendly, providing long-lasting water repellency, and having strong deformation resistance.

Description

Technical Field This invention relates to the field of shoe upper technology, and specifically to a method for manufacturing a string technology shoe upper with fluorine-free water-repellent function. Background Technology The upper is a crucial component of footwear products, and its performance directly impacts comfort and durability. In outdoor sports shoes, hiking boots, and trekking shoes, the upper is frequently exposed to rain, dew, or damp environments. When the upper gets wet, it increases the shoe's weight, affecting athletic performance; furthermore, moisture seeps into the shoe, keeping the feet damp and potentially causing discomfort, blisters, or even fungal infections.

[0001] In existing technologies, chemical finishing agents are typically used to treat shoe upper materials to impart water-repellent properties. For example, woven uppers are soaked in fluorinated waterproofing agents to form a low-surface-energy water-repellent film on the surface. However, this treatment method has certain problems in practical use: with prolonged wear and increased washing, the water-repellent film gradually wears off or falls off, significantly reducing the water-repellent performance of the upper. Furthermore, in areas of the upper subjected to repeated bending, stretching, or compression (such as the forefoot flexion area), the gaps between the yarns in the upper material widen due to deformation, allowing moisture to more easily penetrate into the shoe through these enlarged gaps. Summary of the Invention The present invention aims to provide a manufacturing method for a fluorine-free water-repellent chord technology shoe upper, in order to solve the problems of environmental pollution, performance degradation after washing, and easy pore expansion and water seepage in the existing technology of water-repellent treatment of shoe uppers.

[0002] The 'string technology' mentioned in this application refers to a biomimetic structure shoe upper technology formed by automatically winding, laying, fixing or welding single or multiple yarns under program control.

[0003] Research has found that the water-repellent properties of shoe uppers treated with existing fluorinated waterproofing agents mainly rely on a low surface energy film layer formed on the surface. During use, this film layer is subjected to mechanical friction, bending, stretching, and the chemical effects of detergents, gradually developing micro-cracks and localized peeling, leading to a decrease in water repellency. While fabrics treated with fluorinated waterproofing agents, completely eliminating fluorinated finishing agents, may initially meet the required waterproofing performance, the bonding force between the fluorinated finishing agent and the fibers is relatively weak, resulting in a more significant decrease in waterproofing performance after repeated washing.

[0004] Further research revealed that during wear, especially in the forefoot flexion area, the gaps between yarns in the shoe upper gradually widen due to repeated bending. When these gaps exceed the critical size that the surface tension of water can withstand, water will seep in under pressure. This phenomenon is particularly pronounced in fluorine-free waterproof shoe uppers because the water-repellent film formed by fluorine-free finishing agents has poor elasticity and is prone to irreversible damage when the yarn gaps widen. Therefore, simply improving the initial waterproof performance of the yarns or fabric cannot completely solve the problem of waterproof failure during long-term use; it is also necessary to simultaneously enhance the deformation resistance of the shoe upper structure to prevent the yarn gaps from widening due to repeated compression.

[0005] The present invention adopts the following technical solution: Option 1 A method for manufacturing a fluorine-free, water-repellent lacing technology upper for shoes includes the following steps: Step 1: Provide a waterproof layer, which is formed by weaving yarn that has undergone fluorine-free waterproofing treatment; Step 2: Provide an inner lining layer, which is knitted from cotton blend yarn; Step 3: Sew multiple deformation-resistant yarns to the surface of the waterproof layer using sewing thread, so that the yarns extend from the forefoot area to the heel area of ​​the waterproof layer; Step 4: Overlap and fix the waterproof layer with the inner lining layer to form the main body of the shoe upper; Step 5: Fix the waterproof and breathable membrane to at least a portion of the outer surface of the waterproof layer to obtain the finished shoe upper.

[0006] Option 1 employs a layered structure with a waterproof layer and an inner lining. The waterproof layer provides primary waterproofing, while the inner lining offers wearing comfort. A longitudinal reinforcing rib structure is formed inside the upper by stitching together deformation-resistant yarns extending from the forefoot to the heel. This effectively resists tensile deformation during bending and prevents the yarn gaps in the forefoot area from widening. A waterproof and breathable membrane further enhances the waterproof barrier. These three elements work synergistically to maintain excellent water-repellent performance even after long-term use and multiple washes.

[0007] Option 2 Based on Scheme 1, the waterproof and breathable membrane mentioned in step 5 is an expanded polytetrafluoroethylene (ePTFE) membrane, and the ePTFE membrane is fixed to the front, side edges and the entry edge of the outer surface of the waterproof layer by a hot pressing process. The hot pressing temperature is 135±5℃, the pressure is 0.4±0.1MPa and the time is 10±2 seconds.

[0008] Option two utilizes the ePTFE membrane, which has a microporous structure that blocks liquid water while allowing water vapor to pass through, achieving a balance between waterproofing and breathability. By fixing it to easily infiltrated areas of the shoe upper (forefoot flexion area, side edges, and entry edges), it precisely covers vulnerable waterproofing areas while maintaining breathability in other areas of the upper. A heat-pressing process physically integrates the ePTFE membrane with the waterproof layer yarns, resulting in a strong bond.

[0009] Option 3 Based on Scheme 1, the deformation-resistant yarn in step 3 is prepared through the following steps: A1: Select TPU yarn as the core yarn and polyester filament as the auxiliary yarn; A2: The polyester filament is twisted and then alkali etched to form a rough surface structure. A3: Twist the TPU core yarn and the treated polyester filament together so that the polyester filament is arranged around the TPU core yarn; A4: The twisted blended yarn is heat-set to allow the softened TPU core yarn to embed into the rough structure of the polyester filament to form a mechanical interlock, thereby obtaining the deformation-resistant yarn.

[0010] Option three involves creating a microscopic rough structure on the surface of the polyester filament through alkaline etching, followed by heat setting to embed the softened TPU core yarn into this rough structure, forming a mechanically interlocked reinforced interface. Unlike traditional melt coating methods, this mechanically interlocked structure creates a high-strength bond between the core yarn and the outer sheath yarn without compromising the integrity of the TPU core yarn. The yarn as a whole exhibits excellent tensile and permanent deformation resistance. When sewn into the shoe upper, this yarn maintains the shoe's shape stability over a long period, preventing irreversible pore-expanding deformation in the forefoot area due to repeated bending.

[0011] Option 4 Based on Scheme 1, the fluorine-free waterproof yarn mentioned in step 1 is prepared through the following steps: S1: High-strength polyester filament is used as the inner core, and fine denier nylon filament is used as the auxiliary yarn. S2: The high-strength polyester filament and fine denier nylon filament are respectively immersed in an acrylic C6 waterproof finishing agent for pretreatment; S3: Using a hollow spindle fancy twisting machine, the high-strength polyester filament is used as the core yarn and the fine denier nylon filament is used as the decorative yarn for the covering process. The covering twist is controlled at 800-1200 twists / meter to obtain the first mixed yarn. S4: Apply a water-based polyurethane coating to the first mixed yarn to form a continuous water-based polyurethane coating layer on the surface of the first mixed yarn. S5: Cool down and rewind to obtain the yarn that has undergone fluorine-free waterproof treatment.

[0012] Option four involves pretreating the core yarn and cover yarn with a C6 waterproofing agent to create a low-surface-energy water-repellent layer on the yarn surface. A continuous, dense waterproof membrane is then formed on the yarn surface using a water-based polyurethane coating. This double-layer waterproof structure gives the yarn excellent water penetration resistance (hydrostatic pressure >5000 mmH2O). Furthermore, because a C6 finishing agent is used instead of C8, the content of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) is extremely low (<1 μg / m²), meeting environmental protection requirements.

[0013] Option 5 Based on Option 1, the sewing and fixing method in step 3 is as follows: waterproof sewing thread is used to fix the deformation-resistant yarn to the outer surface of the waterproof layer with double-needle lockstitch, with a stitch length of 2-4mm, and no heating or welding operation is performed during the fixing process.

[0014] Option 5, using double-needle lockstitch, forms two parallel sewing threads, ensuring that the deformation-resistant yarn is evenly stressed on the surface of the waterproof layer, thus avoiding stress concentration. It eliminates the need for heat welding, ensuring that the original structure and waterproof performance of the waterproof layer yarn are not damaged by heat, while also preventing rigid protrusions at the welding point from affecting wearing comfort.

[0015] Option Six Based on Option 1, before step four or step five, a step is also included in which a polyurethane coating agent is applied to the outer surface of the waterproof layer and / or the side of the inner layer facing the waterproof layer, and after application, the polyurethane coating agent forms a coating with a thickness of 0.05-0.15 mm.

[0016] Using Option Six, the polyurethane coating agent can fill the tiny gaps between the yarns of the waterproof layer, further improving the hydrostatic pressure of the waterproof layer; when applied to the inner layer surface, it can form a second waterproof barrier, so that even if a small amount of water breaks through the waterproof layer, it will be blocked by the inner layer coating and will not come into contact with the feet.

[0017] Option 7 A method for manufacturing a waterproof shoe includes the following steps: Step (1): manufacturing a fluorine-free water-repellent upper using any one of Schemes 1 to 6; Step (2): providing a sole; Step (3): fixing the upper obtained in Step (1) to the sole to obtain a waterproof shoe.

[0018] Option 7 combines the above-mentioned upper manufacturing method with the sole assembly to obtain a waterproof shoe product with durable water-repellent properties.

[0019] Beneficial effects Environmental friendliness: This application uses an acrylic C6 waterproofing agent to replace the traditional C8 fluorine-containing finishing agent, and combines it with a water-based polyurethane coating, so that PFOA and PFOS are not detected in the final shoe upper (<1μg / m²), which meets environmental protection requirements.

[0020] Durable water-repellent performance: Through the synergistic effect of the fluorine-free waterproofing treatment of the waterproof layer yarn, the heat-pressing fixation of the ePTFE membrane, and the sewing reinforcement of the deformation-resistant yarn, the final shoe upper has an overall hydrostatic pressure of >8000mmH2O. The initial water-repellent rating is 5, and it still maintains a rating of 4 after 10 household washes. The degree of water resistance degradation is better than that of traditional C8 fluorine-containing solutions.

[0021] Resistance to pore expansion and deformation: The deformation-resistant yarn is prepared by alkaline etching and heat setting interface fusion. Its TPU core yarn is embedded in the rough surface of polyester filament to form a mechanical interlock, and the yarn elastic recovery rate reaches 92% and the permanent deformation rate is <3%. After the yarn is extended from the forefoot to the heel and sewn to fix it, the puncture resistance of the forefoot area of ​​the shoe is increased by about 60%, which can effectively prevent the yarn gap from widening and water seepage caused by repeated bending.

[0022] Excellent breathability: The microporous structure of the ePTFE membrane and the design of the woven waterproof layer make the finished shoe upper breathable at >5000g / m²·24h, ensuring waterproofness without compromising wearing comfort.

[0023] Structural stability: Double-needle lockstitch is used to sew anti-deformation yarn with uniform stitch spacing and stress dispersion; no heating and welding operations are performed during the entire manufacturing process, avoiding damage to the yarn structure at the welding point and the problem of local hardening of the shoe upper. Attached Figure Description

[0024] Figure 1 This is a flowchart of the manufacturing method of the present invention. Detailed Implementation To make the technical problems, technical solutions, and beneficial effects of this invention clearer and more understandable, the invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0025] 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 preferred embodiments of the present invention and should not be considered as excluding other embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise expressly defined, the use of terms such as "first," "second," or "third" in the claims, description, and accompanying drawings of this invention is for distinguishing different objects and not for describing a specific order.

[0027] Unless otherwise expressly defined, in the claims, description, and accompanying drawings of this invention, the use of directional terms such as "center," "lateral," "longitudinal," "horizontal," "vertical," "top," "bottom," "inner," "outer," "upper," "lower," "front," "rear," "left," "right," "clockwise," and "counterclockwise" to indicate orientation or positional relationships is based on the orientation and positional relationships shown in the accompanying drawings and is only for the convenience of describing the invention and simplifying the description, and is not intended to indicate or imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore should not be construed as limiting the specific scope of protection of this invention.

[0028] Unless otherwise expressly defined, the terms "fixed connection" or "fixed connection" used in the claims, description and drawings of this invention should be interpreted broadly to refer to any connection in which there is no displacement or relative rotation relationship between the two parties, including non-removable fixed connection, detachable fixed connection, integral connection and fixed connection by other means or components.

[0029] In the claims, description and accompanying drawings of this invention, the terms "comprising," "having," and variations thereof are used to mean "including but not limited to."

[0030] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.

[0031] I. Overall Structure Overview like Figure 1 As shown, the manufacturing method of the fluorine-free water-repellent upper provided by this invention mainly includes the following process steps: waterproof layer preparation, inner layer preparation, deformation-resistant yarn preparation and sewing, waterproof layer and inner layer lamination, and ePTFE film hot-pressing fixation. The following is in conjunction with... Figure 1 Each step is explained in detail.

[0032] II. Detailed Description of Each Step (a) Step 1: Providing the waterproof layer Step one, providing a waterproof layer 100. The waterproof layer 100 is formed by weaving yarn that has undergone fluorine-free waterproofing treatment.

[0033] Specifically, the yarn that has undergone fluorine-free waterproofing treatment is prepared using the following method: S1 uses high-strength polyester filament as the inner core and fine denier nylon filament as the auxiliary yarn.

[0034] S2, the high-strength polyester filament and fine denier nylon filament are respectively immersed in an acrylic C6 waterproof finishing agent for pretreatment. In this embodiment, the C6 waterproof finishing agent is Phobotex® JVA manufactured by Huntsman Corporation, with an immersion concentration of 80 g / L. The immersion treatment is carried out at 40°C for 5 minutes, and then pre-dried at 80°C for 5 minutes to allow the finishing agent layer to adhere to its surface.

[0035] S3, using a hollow spindle fancy twisting machine, a wrapping process is performed using the high-strength polyester filament as the core yarn and the fine denier nylon filament as the finishing yarn. The wrapping twist is controlled at 800-1200 twists / meter to obtain the first mixed yarn. In this embodiment, the wrapping is performed at a core yarn speed of 100m / min and a finishing yarn speed of 150m / min, and the preferred wrapping twist is 1000 twists / meter.

[0036] S4, the first mixed yarn is subjected to a water-based polyurethane coating treatment. Specifically, an impregnation tank containing water-based polyurethane (PU) coating adhesive is prepared. The first mixed yarn is output and immersed in the impregnation tank. Then, the first mixed yarn is scraped off excess water-based polyurethane by a circular scraper, controlling the liquid content to 60%. Subsequently, the first mixed yarn enters a segmented drying oven, first pre-drying at 80-100°C to remove moisture, and then baking at 140-160°C to crosslink and cure the coating, forming a strong film. In this embodiment, the water-based polyurethane coating adhesive is Impranil® DLN-SD manufactured by Covestro, with a solid content of 30%.

[0037] S5, Cooling and winding. The coated yarn is cooled and shaped by a cooling roller at 10-15°C, and its uniformity is checked by an electronic yarn clearer. It is then wound up by a precision winding machine to obtain the yarn that has undergone fluorine-free waterproof treatment.

[0038] Then, the fluorine-free waterproof yarn is fed into a rapier loom and woven in a plain weave with a weft density of 25 threads / cm. After cutting, a waterproof layer is formed.

[0039] (II) Step Two: Providing the Inner Layer Step two, providing an inner lining layer 200. The inner lining layer 200 is knitted from cotton blended yarn.

[0040] Specifically, cotton blended yarn is selected as the forming yarn for the inner lining layer. The cotton blended yarn is fed into a high-speed Raschel machine and knitted using a chain knitting structure. After cutting, the inner lining layer is formed.

[0041] (III) Step 3: Preparation and sewing of anti-deformation yarn Step 3: First, prepare the deformation-resistant yarn 300.

[0042] A1. TPU yarn is selected as the core yarn, and polyester filament is selected as the auxiliary yarn. In this embodiment, the TPU yarn has a stiffness of 85D and is purchased from Lubrizol, model ESTANE® 58887; the polyester filament has a specification of 500D.

[0043] A2. The polyester filament is twisted and then subjected to alkaline etching to create a rough surface structure. Specifically, the polyester filament is twisted using a twisting machine to a twist rate of 200 twists / meter. Subsequently, the surface of the polyester filament is degreased in an impregnation tank and then subjected to alkaline etching for 2 minutes in a 70°C aqueous solution containing 3% NaOH and 2% penetrant JFC. After rinsing with water until neutral, it is dried at 80°C. After alkaline etching, the surface roughness Ra of the polyester filament is increased from 0.2 μm to 1.5 μm.

[0044] A3. The TPU core yarn and the treated polyester filament are combined and twisted. Specifically, the TPU core yarn and polyester filament are placed in a yarn doubling and twisting machine. 2-4 polyester filaments are taken and arranged in parallel, and 1 TPU core yarn is placed in the center. The tension of the polyester filament is set to 8-12 cN, and the tension of the TPU core yarn is set to 3-5 cN. Before entering the twisting zone, the polyester filament and TPU core yarn pass through a yarn guide to form an arrangement with TPU in the center and polyester surrounding it. Twisting is then performed in a Z-twist direction at a twist rate of 100-300 twists / meter. The spindle speed of the yarn doubling and twisting machine is 8000-12000 rpm, the working temperature is maintained at 25±2℃, and the relative humidity of the working environment is 65±5%, resulting in a second mixed yarn.

[0045] A4. The twisted blended yarn undergoes heat setting. The second blended yarn is fed into a hot roller setter for preheating at 60℃-80℃ for 15-25 seconds, causing the TPU core yarn to soften. Then, it enters the heat setting stage at 80℃-110℃ for 10 seconds. Under a moderate tension of 15-20 cN and a hot roller pressure of 0.2-0.4 MPa, the softened TPU core yarn surface is fully softened and adheres to the polyester filament, embedding itself into the rough structure of the polyester filament to form a mechanical interlock, resulting in a second blended yarn with an interface fusion structure.

[0046] A5, Cooling and winding. The second blended yarn, after being set, is rapidly cooled and shaped by a cooling roller at 10-15°C. Its uniformity is checked by an electronic yarn clearer, and it is then wound up by a precision winding machine to obtain the deformation-resistant yarn.

[0047] Then, multiple deformation-resistant yarns 300 are sewn and fixed to the surface of the waterproof layer using sewing thread. Specifically, waterproof sewing thread is used as the sewing thread, and the deformation-resistant yarns are fixed to the outer surface of the waterproof layer using a double-needle lockstitch, with a stitch length of 2-4 mm (preferably 3 mm in this embodiment). No heating or welding operation is performed during the fixing process. The deformation-resistant yarns extend from the forefoot area of ​​the waterproof layer to the heel area, forming multiple longitudinal reinforcing structures extending from the forefoot to the heel.

[0048] (iv) Step 4: Overlapping and fixing the waterproof layer and the inner layer Step four: The waterproof layer 100 and the inner lining layer 200 are stacked and fixed together to form the upper body 400.

[0049] Specifically, the waterproof layer 100 and the inner lining layer 200 are stacked together and placed into a mold (not shown in the figure) with the edges aligned. The waterproof layer 100 and the inner lining layer 200 are then sewn together with TPU yarn using a double-needle lockstitch with a stitch length of 3mm. The two layers are sewn together along the edge of the cut piece to form the main body of the shoe upper 400.

[0050] (V) Step 5: Fixing the waterproof and breathable membrane Step 5: Fix the waterproof and breathable membrane to at least a portion of the outer surface of the waterproof layer 100 to obtain the finished shoe upper 500.

[0051] In this embodiment, the waterproof and breathable membrane is an expanded polytetrafluoroethylene (ePTFE) membrane. A 25μm thick ePTFE membrane is cut into strips. At the forefoot, side edges, and entryway edges on the outer surface of the shoe upper body 400, a flat vulcanizing machine is used to hot-press and bond the ePTFE membrane for 10 seconds at 135°C and 0.4MPa pressure, thus obtaining the finished shoe upper 500.

[0052] III. Optional Implementation Methods (a) Application of polyurethane coating agent As a further improvement, before step four or step five, a step of applying a polyurethane coating agent to the outer surface of the waterproof layer 100 and / or the side of the inner layer 200 facing the waterproof layer 100 is included.

[0053] Specifically, a layer of polyurethane coating agent is uniformly sprayed onto the outer surface of the main body 400 of the shoe upper (i.e., the outer surface of the waterproof layer 100), with a wet film thickness of approximately 0.08 mm, and then dried at 80°C for 5 minutes. The polyurethane coating agent is purchased from Stahl GmbH, model Neoprene ML-200. This coating can further increase the hydrostatic pressure of the shoe upper by approximately 15%.

[0054] Alternatively, a layer of polyurethane coating agent can be evenly sprayed onto the side of the inner layer 200 facing the waterproof layer 100, with a wet film thickness of approximately 0.1 mm, and then dried at 80°C for 5 minutes. This coating can increase the hydrostatic pressure of the inner layer 200 from <500 mmH2O to >2000 mmH2O, forming a second waterproof barrier.

[0055] (ii) Secondary twisting of anti-deformation yarn As another improvement, after A4 heat setting, a secondary twisting step is also included. The second blended yarn is fed into a high-precision twister and twisted at a twist rate of 300-500 twists / meter, with a Z-twist direction, a spindle speed of 8000-15000 rpm, and a positive tension controller is used to control the tension range of 15-25 cN, with an overfeed rate of 1%-3%, to obtain the second blended yarn after secondary twisting.

[0056] (III) Finishing after applying oil As a further improvement, after the second twisting, a finishing step is also included: the oil is sprayed onto the second blended yarn in an atomized form through a metering pump and nozzle, with an oiling rate between 0.8% and 1.5%. The oil used is pentaerythritol ester, purchased from Klüber GmbH, Germany, model Kluber® PR 41 / 150.

[0057] IV. Manufacturing of Waterproof Shoes like Figure 1 As shown at the bottom, the finished shoe upper 500 is fixedly connected to the sole to obtain a waterproof shoe. Specifically, a sole is provided, and the lower edge of the finished shoe upper 500 is fixedly connected to the upper edge of the sole by adhesive or sewing to obtain a waterproof shoe.

[0058] V. Performance Test Data The performance of the finished shoe upper 500 obtained in this embodiment was tested, and the results are as follows:

[0059] The foregoing description illustrates and describes preferred embodiments of the present invention. As previously stated, it should be understood that the present invention is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the inventive concept described herein through the foregoing teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of the present invention should be within the protection scope of the appended claims.

Claims

1. A method for manufacturing a fluorine-free, water-repellent lacing technology upper for shoes, characterized in that, Includes the following steps: Step 1: Provide a waterproof layer, which is formed by weaving yarn that has undergone fluorine-free waterproofing treatment; Step 2: Provide an inner lining layer, which is knitted from cotton blend yarn; Step 3: Sew multiple deformation-resistant yarns to the surface of the waterproof layer using sewing thread, so that the yarns extend from the forefoot area to the heel area of ​​the waterproof layer; Step 4: Overlap and fix the waterproof layer with the inner lining layer to form the main body of the shoe upper; Step 5: Fix the waterproof and breathable membrane to at least a portion of the outer surface of the waterproof layer to obtain the finished shoe upper.

2. The manufacturing method of a fluorine-free water-repellent upper according to claim 1, characterized in that, The waterproof and breathable membrane mentioned in step five is an expanded polytetrafluoroethylene (ePTFE) membrane, and the ePTFE membrane is fixed to the front, side edges and the entry edge of the outer surface of the waterproof layer by a hot pressing process. The hot pressing temperature is 135±5℃, the pressure is 0.4±0.1MPa and the time is 10±2 seconds.

3. The manufacturing method of a fluorine-free water-repellent upper according to claim 1, characterized in that, The deformation-resistant yarn mentioned in step three is prepared through the following steps: A1: Select TPU yarn as the core yarn and polyester filament as the auxiliary yarn; A2: The polyester filament is twisted and then alkali etched to form a rough surface structure. A3: Twist the TPU core yarn and the treated polyester filament together so that the polyester filament is arranged around the TPU core yarn; A4: The twisted blended yarn is heat-set to allow the softened TPU core yarn to embed into the rough structure of the polyester filament to form a mechanical interlock, thereby obtaining the deformation-resistant yarn.

4. The manufacturing method of a fluorine-free water-repellent lacing technology shoe upper according to claim 1, characterized in that, The fluorine-free waterproof yarn mentioned in step one is prepared through the following steps: S1: High-strength polyester filament is used as the inner core, and fine denier nylon filament is used as the auxiliary yarn. S2: The high-strength polyester filament and fine denier nylon filament are respectively immersed in an acrylic C6 waterproof finishing agent for pretreatment; S3: Using a hollow spindle fancy twisting machine, the high-strength polyester filament is used as the core yarn and the fine denier nylon filament is used as the decorative yarn for the covering process. The covering twist is controlled at 800-1200 twists / meter to obtain the first mixed yarn. S4: Apply a water-based polyurethane coating to the first mixed yarn to form a continuous water-based polyurethane coating layer on the surface of the first mixed yarn. S5: Cool down and rewind to obtain the yarn that has undergone fluorine-free waterproof treatment.

5. The manufacturing method of a fluorine-free water-repellent upper according to claim 1, characterized in that, The sewing and fixing method described in step three is as follows: waterproof sewing thread is used to fix the deformation-resistant yarn to the outer surface of the waterproof layer with double-needle lockstitch, with a stitch length of 2-4mm, and no heating or welding operation is performed during the fixing process.

6. The manufacturing method of a fluorine-free water-repellent upper according to claim 1, characterized in that, Before step four or step five, a step of applying a polyurethane coating agent to the outer surface of the waterproof layer and / or the side of the inner layer facing the waterproof layer is also included, wherein the polyurethane coating agent forms a coating with a thickness of 0.05-0.15 mm after application.

7. A method for manufacturing waterproof shoes, characterized in that, Includes the following steps: Step (1): Manufacture the fluorine-free water-repellent upper using the method described in any one of claims 1 to 6; Step (2): Provide a shoe sole; Step (3): The upper obtained in step (1) is fixedly connected to the sole to obtain a waterproof shoe.

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