Moisture-absorbing and air-permeable collagen fiber-based insole leather and preparation method thereof
By combining modified collagen fibers with modified mesoporous nano-silica and waterborne polyurethane, the problems of low collagen fiber recycling rate and harmful solvent residues are solved, and high-performance, moisture-wicking and breathable shoe lining leather is prepared, which improves the overall performance of shoe lining leather and reduces environmental pollution.
Patent Information
- Application Number
- CN202611171118.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-04
- Publication Date
- 2026-11-03
AI Technical Summary
The current leather processing industry suffers from low collagen fiber recycling rates, short fiber bundles, and insufficient flexibility. Furthermore, the production process of traditional shoe lining leather often results in harmful solvent residues posing significant health risks. This makes it difficult to meet the requirements of high-performance, moisture-wicking, and breathable shoe lining leather. The production process of environmentally friendly shoe lining leather also presents numerous environmental pollution problems due to the presence of harmful solvent residues.
A composite finishing agent consisting of modified collagen fibers, modified mesoporous nano-silica, and waterborne polyurethane is used to form a stable fiber network through cross-linking and covalent bonds, thereby enhancing the mechanical properties of the base fabric and creating micro-nano pores in the coating to achieve moisture absorption and breathability.
It improves the mechanical strength, moisture absorption, breathability and soft feel of shoe lining leather, avoids harmful solvent residues, and achieves an environmentally friendly and efficient manufacturing process.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of shoe lining technology, specifically to a moisture-wicking and breathable collagen fiber-based shoe lining and its preparation method. Background Technology
[0002] Leather is widely used in clothing, sofas, bags, and decoration. Early processing methods included grinding it into powder for animal feed and recycling it for glue extraction, eventually leading to landfill or incineration. However, due to the easy decomposition of collagen components producing odors and the difficulty of natural degradation of leather, serious environmental pollution has occurred. Existing debonding processes generally achieve a collagen fiber extraction rate of less than 15% from scraps, resulting in extremely low fiber recycling rates. The resulting base fabric has defects such as poor tear resistance, short fiber bundles, and insufficient flexibility, making it difficult to meet the requirements of high-performance shoe lining leather. At the same time, with increasing environmental awareness, the drawbacks of traditional oil-based shoe lining leather are becoming increasingly apparent: its production process requires the use of large amounts of organic solvents, especially dimethylformamide, which remains adsorbed inside the leather and is slowly released during use, posing potential health risks to the skin and respiratory system. Therefore, developing an efficient recycling and green preparation process based on waste leather collagen fibers, and endowing shoe lining leather with comprehensive properties such as moisture absorption, breathability, and no harmful solvent residues, has significant environmental and industrial value. Summary of the Invention
[0003] The present invention aims to provide a moisture-wicking and breathable collagen fiber-based shoe lining leather and its preparation method, so as to solve the related technical problems existing in the prior art.
[0004] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows: Step 1: The modified collagen fibers are laid in a two-horizontal-one-vertical cross-laying method to obtain a collagen fiber web; the collagen fiber web is pre-wetted, subjected to high-pressure hydroentangling, and squeezed dry to obtain the base fabric; Step 2: Polish the surface of the base fabric to obtain a pretreated base fabric; dye the pretreated base fabric to obtain a dyed base fabric; Step 3: The dyed base fabric is immersed in a modified waterborne polyurethane finishing agent prepared by mixing modified mesoporous nano silica and waterborne polyurethane. After two dips and two rolls in a rolling mill, it is dried, cured and shaped to obtain a semi-finished product. Step 4: Use a pattern roller to emboss the semi-finished product to obtain moisture-wicking and breathable collagen fiber-based shoe lining leather.
[0005] Preferred working conditions for the pre-wetting treatment in step 1 are: pressure of 10~12MPa and time of 1~3s; working conditions for the high-pressure hydroentangling treatment are: pressure of 150~250MPa; and the dyeing temperature in step 2 is 95~105℃.
[0006] Preferably, the immersion time in step 3 is 10-12 minutes, and the drying, curing and shaping conditions are: temperature 95-105℃, time 5-10 minutes; the embossing temperature in step 4 is 140-150℃.
[0007] Preferably, the preparation steps of the modified collagen fiber are as follows: S1: Under 4℃ conditions, take cowhide scraps, immerse them in sodium chloride solution for 3-4 hours, rinse them with distilled water 3-5 times and filter them, then soak them in degreasing agent for 23-25 hours, wash them with distilled water 3-5 times, and air dry them to obtain pre-treated cowhide. S2: Add distilled water to pretreated cowhide, then add acetic acid to make the concentration 1.2 mol / L, and add pepsin. Stir magnetically at 36-37℃ for 70-72 h, filter the reaction solution and centrifuge at 3000 rpm at 2-4℃ for 25-30 min. Collect the supernatant and dialyze it at 4℃ to obtain a collagen solution. Pre-freeze the collagen solution for 10-12 h, then freeze-dry it for 46-48 h to obtain collagen. S3: Weigh 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, dissolve them in 0.5 mol / L glacial acetic acid solution to prepare a crosslinking agent; add collagen to the crosslinking agent, stir and react at 2~4℃ for 10~11 h to obtain a modified spinning solution; inject the modified spinning solution into a syringe, set the spinning voltage to 14~16 kV, the spinning feed speed to 1~2 mL / h, and the receiving distance to 14~16 cm, and perform electrospinning to obtain modified collagen fibers.
[0008] Preferably, in S1, the sodium chloride solution has a mass concentration of 12%, and the degreasing agent is prepared by mixing sodium carbonate, isopropanol, and deionized water in a mass ratio of 6:8:86; in S2, the ratio of pretreated cowhide to distilled water is 1:25, and the amount of pepsin added is 1% of the mass of cowhide scraps; in S3, the mass ratio of 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride to N-hydroxysuccinimide is 3:1, the mass concentration of the crosslinking agent is 15%, and the mass ratio of collagen to the crosslinking agent is 3:20.
[0009] Preferably, the dialysis working conditions described in S2 are magnetic stirring, changing the distilled water every 6 hours, and continuous dialysis for 3 days.
[0010] Preferably, the preparation steps of the modified waterborne polyurethane finishing agent are as follows: Step a: Dry mesoporous nano-silica at 115~120℃ for 40~50min, add anhydrous ethanol and stir to obtain a nanoparticle suspension, add dichlorodimethylsilane and deionized water in sequence, heat to 130℃ and reflux for 45~55min to obtain a high-concentration nano-dispersion, centrifuge and wash 2~3 times with anhydrous ethanol, dry at 95~105℃, grind to obtain modified mesoporous nano-silica; Step b: Weigh the waterborne polyurethane and dilute it with deionized water. Stir for 10-15 minutes to prepare a waterborne polyurethane emulsion. Transfer the waterborne polyurethane emulsion to a water bath, adjust the temperature to 48-52℃, and stir magnetically. Add modified mesoporous nano silica to the emulsion within 1 minute, add defoamer, and stir for 45-55 minutes. Reduce the water bath temperature to 20-23℃ and maintain stirring for 18-22 minutes to obtain the modified waterborne polyurethane finishing agent.
[0011] Preferably, the mass concentration of the nanoparticle suspension in step a is 4.8%, and the amount of dichlorodimethylsilane added is 15% of the mass of the mesoporous nano silica.
[0012] Preferably, the concentration of the aqueous polyurethane emulsion in step b is 10 g / L, and the mass ratio of the aqueous polyurethane emulsion, modified mesoporous nano silica, and defoamer is 100:1.5:0.1.
[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention describes a moisture-wicking and breathable collagen fiber-based shoe lining leather and its preparation method. It utilizes 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide to activate the carboxyl groups of collagen and undergo amidation crosslinking with amino groups, generating -CO-NH- bonds. This stabilizes the three-dimensional network of collagen fibers under mild aqueous conditions without disrupting their natural conformation, thereby significantly improving the mechanical strength and moisture and heat resistance of the base fabric. Dichlorodimethylsilane reacts with the hydroxyl groups on the surface of mesoporous nano-silica to form Si-O-Si covalent bonds and is then grafted onto the surface. The hydrophobic methyl groups ensure low surface energy and uniform dispersion of nanoparticles within the waterborne polyurethane, preventing aggregation. Subsequently, modified mesoporous nano-silica is blended and cured with the waterborne polyurethane. The nanoparticles act as physical crosslinking points, enhancing the coating's abrasion resistance and forming micro-nano pores within the coating. This, in conjunction with the inherent hydrophilic groups -COOH and -NH2 of collagen fibers, enables unidirectional moisture conduction and rapid evaporation. Simultaneously, the urethane groups of the waterborne polyurethane form hydrogen bonds with the collagen fiber surface, undergoing moderate self-crosslinking after two dips, two tumblers, and high-temperature drying, further improving interfacial adhesion. Therefore, the resulting shoe lining leather possesses high moisture absorption, good breathability, a soft feel, and excellent mechanical properties. Detailed Implementation
[0014] The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the embodiments described are only some, not all, implementations of the present invention. Other implementations that can be obtained by those skilled in the art based on the embodiments of the present invention without creative effort all fall within the protection scope of the present invention.
[0015] In the following examples and comparative examples, the pepsin activity was 1200 U / g; the molecular weight cutoff of the dialysis bag was 14000 Da; the mesoporous nano-silica had a particle size of 500 nm and a pore size of 2-3 nm; the waterborne polyurethane had a viscosity of 1500 mPa·s at 23°C, a solid content of 30%, and a pH of 7-8; the defoamer was of type NXZ and had a viscosity of 300-900 mPa·s at 25°C; the sodium chloride, sodium carbonate, isopropanol, acetic acid, 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and anhydrous ethanol were all of analytical grade; and the dichlorodimethylsilane was of industrial grade.
[0016] Example 1: A moisture-wicking and breathable collagen fiber-based shoe lining leather and its preparation method, comprising the following steps: Step 1: The modified collagen fibers are laid in a two-horizontal-one-vertical cross-web pattern to obtain a basis weight of 450 g / m². 2 Collagen fiber web; the collagen fiber web is pre-wetted under a pressure of 10 MPa for 1 second, then subjected to high-pressure hydroentangling under a pressure of 150 MPa, and then squeezed dry to obtain the base fabric; Step 2: Polish the surface of the base fabric to obtain a pretreated base fabric; put the pretreated base fabric into a dyeing pot and dye it at a temperature of 95℃ to obtain the dyed base fabric; Step 3: Immerse the dyed base fabric in a modified waterborne polyurethane finishing agent prepared by mixing modified mesoporous nano silica and waterborne polyurethane for 10 minutes. After two dips and two rolls in a rolling mill, dry at 95°C for 5 minutes to cure and shape the coating to obtain a semi-finished product. Step 4: Emboss the semi-finished product using a pattern roller at a temperature of 140℃ to obtain moisture-wicking and breathable collagen fiber-based shoe lining leather; The preparation steps of the modified collagen fiber are as follows: S1: At 4℃, take 100g of cowhide scraps, immerse them in a 12% sodium chloride solution for 3 hours to remove impurities, rinse them three times with distilled water and filter them, then soak them in a degreasing agent prepared by mixing 6g of sodium carbonate, 8mL of isopropanol and 86mL of deionized water for 23 hours to remove impurities, protein and fat, wash them three times with distilled water, and air dry them to obtain pretreated cowhide; S2: Take pretreated cowhide, add distilled water at a material-to-liquid ratio of 1:25, then add acetic acid to make the concentration 1.2 mol / L, and add 1 g of pepsin to dissolve the cowhide. After magnetic stirring at 36℃ for 70 h, filter the reaction solution and centrifuge at 2℃ and 3000 rpm for 25 min. Collect the supernatant, transfer the obtained supernatant into a dialysis bag and seal it. Place it in a large beaker containing distilled water and dialyze at 4℃. During the dialysis process, keep magnetic stirring and change the distilled water every 6 h. Continue dialysis for 3 days to obtain a collagen solution. Pre-freeze the collagen solution for 10 h, transfer it to a freeze dryer and freeze-dry for 46 h to obtain collagen. S3: Weigh 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in a mass ratio of 3:1, dissolve them in 0.5 mol / L glacial acetic acid solution to prepare a crosslinking agent with a mass concentration of 15%; take 15g of collagen, add 100mL of crosslinking agent, stir and react at 2℃ for 10h to obtain a modified spinning solution; inject the modified spinning solution into a syringe and install it on an injection pump, set the spinning voltage to 14kV, the spinning feed speed to 1mL / h, and the receiving distance to 14cm, and perform electrospinning to obtain modified collagen fibers; The preparation steps of the modified waterborne polyurethane finishing agent are as follows: Step a: Take 5g of mesoporous nano silica and dry it at 115℃ for 40min. Add anhydrous ethanol and stir to prepare a nanoparticle suspension with a mass concentration of 4.8%. Add 0.75g of dichlorodimethylsilane and 4mL of deionized water in sequence. Heat to 130℃ and reflux for 45min. After the reaction is completed, a high-concentration nano dispersion is obtained. Wash twice with anhydrous ethanol by centrifugation, dry in an oven at 95℃, and grind to obtain modified mesoporous nano silica. Step b: Weigh the waterborne polyurethane and dilute it with deionized water. Stir with a glass rod for 10 minutes to ensure uniform dispersion of the emulsion and prepare 300 mL of waterborne polyurethane emulsion with a concentration of 10 g / L. Transfer the waterborne polyurethane emulsion to a constant temperature water bath, adjust the water bath temperature to 48℃, and stir magnetically. Add 4.5 g of modified mesoporous nano silica to the emulsion within 1 minute to fully mix the nanoparticles with the emulsion. Add 0.3 g of defoamer and continue stirring for 45 minutes. After the reaction is complete, lower the water bath temperature to 20℃ and continue stirring for 18 minutes to obtain the modified waterborne polyurethane finishing agent.
[0017] Example 2: A moisture-wicking and breathable collagen fiber-based shoe lining leather and its preparation method, comprising the following steps: Step 1: The modified collagen fibers are laid in a two-horizontal-one-vertical cross-web pattern to obtain a basis weight of 450 g / m². 2Collagen fiber web; the collagen fiber web is pre-wetted at 11 MPa for 2 seconds, then subjected to high-pressure hydroentangling at 200 MPa and squeezed dry to obtain the base fabric; Step 2: Polish the surface of the base fabric to obtain a pretreated base fabric; put the pretreated base fabric into a dyeing pot and dye it at a temperature of 100℃ to obtain the dyed base fabric; Step 3: After dyeing, the base fabric is immersed in a modified waterborne polyurethane finishing agent prepared by mixing modified mesoporous nano silica and waterborne polyurethane for 11 minutes. After two dips and two rolls in a rolling mill, it is dried at 100°C for 7 minutes to cure and shape the coating, thus obtaining a semi-finished product. Step 4: Emboss the semi-finished product using a pattern roller at a temperature of 145℃ to obtain moisture-wicking and breathable collagen fiber-based shoe lining leather; The preparation steps of the modified collagen fiber are as follows: S1: At 4℃, take 200g of cowhide scraps, immerse them in a 12% sodium chloride solution for 3.5h to remove impurities, rinse 4 times with distilled water and filter dry, then soak them in a degreasing agent prepared by mixing 12g sodium carbonate, 16mL isopropanol and 172mL deionized water for 24h to remove impurities, protein and fat, wash 4 times with distilled water, and air dry to obtain pretreated cowhide; S2: Take pretreated cowhide, add distilled water at a material-to-liquid ratio of 1:25, then add acetic acid to make the concentration 1.2 mol / L, and add 2g of pepsin to dissolve the cowhide. After magnetic stirring at 36℃ for 71h, filter the reaction solution and centrifuge at 3000rpm for 27min at 3℃. Collect the supernatant, transfer the obtained supernatant into a dialysis bag and seal it. Place it in a large beaker containing distilled water and dialyze at 4℃. During the dialysis process, keep magnetic stirring and change the distilled water every 6h. Continue dialysis for 3 days to obtain a collagen solution. Pre-freeze the collagen solution for 11h, transfer it to a freeze dryer and freeze-dry for 47h to obtain collagen. S3: Weigh 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in a mass ratio of 3:1, dissolve them in 0.5 mol / L glacial acetic acid solution to prepare a crosslinking agent with a mass concentration of 15%; take 30g of collagen, add 200mL of crosslinking agent, stir and react at 3℃ for 10.5h to obtain a modified spinning solution; inject the modified spinning solution into a syringe and install it on an injection pump, set the spinning voltage to 15kV, the spinning feed speed to 1.5mL / h, and the receiving distance to 15cm, and perform electrospinning to obtain modified collagen fibers; The preparation steps of the modified waterborne polyurethane finishing agent are as follows: Step a: Take 10g of mesoporous nano silica and dry it at 117℃ for 45min. Add anhydrous ethanol and stir to prepare a nanoparticle suspension with a mass concentration of 4.8%. Add 1.5g of dichlorodimethylsilane and 8mL of deionized water in sequence. Heat to 130℃ and reflux for 50min. After the reaction is completed, a high-concentration nano dispersion is obtained. Wash it three times with anhydrous ethanol by centrifugation, dry it in an oven at 100℃, and grind it to obtain modified mesoporous nano silica. Step b: Weigh out waterborne polyurethane and dilute it with deionized water. Stir with a glass rod for 13 minutes to ensure uniform dispersion of the emulsion and prepare 600 mL of waterborne polyurethane emulsion with a concentration of 10 g / L. Transfer the waterborne polyurethane emulsion to a constant temperature water bath, adjust the water bath temperature to 50℃, and stir magnetically. Add 9 g of modified mesoporous nano silica to the emulsion within 1 minute to fully mix the nanoparticles with the emulsion. Add 0.6 g of defoamer and continue stirring for 50 minutes. After the reaction is complete, lower the water bath temperature to 22℃ and continue stirring for 20 minutes to obtain the modified waterborne polyurethane finishing agent.
[0018] Example 3: A moisture-wicking and breathable collagen fiber-based shoe lining leather and its preparation method, comprising the following steps: Step 1: The modified collagen fibers are laid in a two-horizontal-one-vertical cross-web pattern to obtain a basis weight of 450 g / m². 2 Collagen fiber web; the collagen fiber web is pre-wetted under a pressure of 12 MPa for 3 seconds, then subjected to high-pressure hydroentangling under a pressure of 250 MPa, and then squeezed dry to obtain the base fabric; Step 2: Polish the surface of the base fabric to obtain a pretreated base fabric; put the pretreated base fabric into a dyeing pot and dye it at a temperature of 105℃ to obtain the dyed base fabric; Step 3: After dyeing, the base fabric is immersed in a modified waterborne polyurethane finishing agent prepared by mixing modified mesoporous nano silica and waterborne polyurethane for 12 minutes. After two dips and two rolls in a rolling mill, it is dried at 105°C for 10 minutes to cure and shape the coating, thus obtaining a semi-finished product. Step 4: Emboss the semi-finished product using a pattern roller at a temperature of 150℃ to obtain moisture-wicking and breathable collagen fiber-based shoe lining leather; The preparation steps of the modified collagen fiber are as follows: S1: At 4℃, take 300g of cowhide scraps, immerse them in a 12% sodium chloride solution for 4 hours to remove impurities, rinse them 5 times with distilled water and filter them, then soak them in a degreasing agent prepared by mixing 18g of sodium carbonate, 24mL of isopropanol and 258mL of deionized water for 25 hours to remove impurities, wash them 5 times with distilled water, and air dry them to obtain pretreated cowhide; S2: Take pretreated cowhide, add distilled water at a material-to-liquid ratio of 1:25, then add acetic acid to make the concentration 1.2 mol / L, and add 3g of pepsin to dissolve the cowhide. After magnetic stirring at 37℃ for 72h, filter the reaction solution and centrifuge at 3000rpm for 30min at 4℃. Collect the supernatant, transfer the supernatant to a dialysis bag and seal it. Place it in a large beaker containing distilled water and dialyze at 4℃. During the dialysis process, keep magnetic stirring and change the distilled water every 6h. Continue dialysis for 3 days to obtain a collagen solution. Pre-freeze the collagen solution for 12h, transfer it to a freeze dryer and freeze-dry for 48h to obtain collagen. S3: Weigh 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in a mass ratio of 3:1, dissolve them in 0.5 mol / L glacial acetic acid solution to prepare a crosslinking agent with a mass concentration of 15%; take 45g of collagen, add 300mL of crosslinking agent, stir and react at 4℃ for 11h to obtain a modified spinning solution; inject the modified spinning solution into a syringe and install it on an injection pump, set the spinning voltage to 16kV, the spinning feed speed to 2mL / h, and the receiving distance to 16cm, and perform electrospinning to obtain modified collagen fibers; The preparation steps of the modified waterborne polyurethane finishing agent are as follows: Step a: Take 15g of mesoporous nano silica and dry it at 120℃ for 50min. Add anhydrous ethanol and stir to prepare a nanoparticle suspension with a mass concentration of 4.8%. Add 2.25g of dichlorodimethylsilane and 12mL of deionized water in sequence. Heat to 130℃ and reflux for 55min. After the reaction is completed, a high-concentration nano dispersion is obtained. Wash it three times with anhydrous ethanol by centrifugation, dry it in an oven at 105℃, and grind it to obtain modified nano silica. Step b: Weigh out waterborne polyurethane and dilute it with deionized water. Stir with a glass rod for 15 minutes to ensure uniform dispersion of the emulsion, and prepare 900 mL of waterborne polyurethane emulsion with a concentration of 10 g / L. Transfer the waterborne polyurethane emulsion to a constant temperature water bath, adjust the water bath temperature to 52℃, and stir magnetically. Add 13.5 g of modified mesoporous nano silica to the emulsion within 1 minute to fully mix the nanoparticles with the emulsion. Add 0.9 g of defoamer and continue stirring for 55 minutes. After the reaction is complete, lower the water bath temperature to 23℃ and continue stirring for 22 minutes to obtain the modified waterborne polyurethane finishing agent.
[0019] Comparative Example 1: Compared with Example 3, the mesoporous nano-silica used was not modified, and the remaining steps were the same as in Example 3.
[0020] Comparative Example 2: Compared with Example 3, no mesoporous nano-silica was added to the modified waterborne polyurethane finishing agent, and the remaining steps were the same as in Example 3.
[0021] Comparative Example 3: Compared with Example 3, the extracted collagen was not modified, and the remaining steps were the same as in Example 3.
[0022] Performance testing: The collagen fiber-based shoe lining leathers prepared in Examples 1-3 and Comparative Examples 1-3 were used as samples for performance testing; Tear strength test: Refer to the method in standard GB / T 45711.2-2025. The sample size is a rectangle with a length of 50 mm and a width of 25 mm. There is a hole with a length of 20 mm and a width of 5 mm in the middle. The speed of the tensile testing machine is 100 mm / min. Abrasion resistance test: Refer to the method in standard GB / T 39507-2020, use Martindale abrasion tester for testing, pressure is 9 kPa, friction cycle is 50,000 revolutions, abrasive is felt, sample size is circle with diameter of 150 mm, observe whether the sample is damaged, if damaged, it is unqualified, if undamaged, it is qualified; Moisture absorption rate test: Refer to the method in standard GB / T 24218.6-2010, immerse the sample in water for 60s, take it out and hang it vertically for 30s to drain, weigh the sample before and after water absorption, and calculate the moisture absorption rate. Air permeability test: Refer to the method in standard GB / T 5453-1997, with a sample area of 20 cm². 2 Pressure drop of 100 Pa; Therefore, the test results are shown in Table 1.
[0023] Table 1
[0024] Conclusion: As shown in Table 1, the moisture-wicking and breathable collagen fiber-based shoe lining leathers prepared in Examples 1-3 are superior to the comparative examples in all aspects. Example 3 showed the best performance, with a tear strength of 49.6 N, a moisture absorption rate of 1260%, a breathability of 6.25 mm / s, and passed the abrasion resistance test. In contrast, the tear strength, moisture absorption rate, and breathability of Comparative Examples 1-3 were significantly reduced, and all failed the abrasion resistance test, showing signs of damage. This indicates that the present invention effectively improves the mechanical strength, moisture absorption, breathability, and abrasion resistance of shoe lining leather through collagen cross-linking modification and hydrophobic modification of mesoporous nano-silica / waterborne polyurethane composite finishing.
[0025] It will be apparent to those skilled in the art that the present invention is not limited to the specific details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit and core features of the invention. Therefore, the above embodiments should be considered exemplary rather than restrictive in any respect. The scope of protection of the present invention is defined by the appended claims, not by the foregoing description, and is therefore intended to encompass all variations in the meaning and scope of the equivalents of the claims within the scope of the present invention.
Claims
1. A method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather, characterized in that: Includes the following steps: Step 1: The modified collagen fibers are laid in a two-horizontal-one-vertical cross-laying method to obtain a collagen fiber web; the collagen fiber web is pre-wetted, subjected to high-pressure hydroentangling, and squeezed dry to obtain the base fabric; Step 2: Grind the surface of the base fabric to obtain the pretreated base fabric; The pretreated base fabric is dyed to obtain the dyed base fabric; Step 3: The dyed base fabric is immersed in a modified waterborne polyurethane finishing agent prepared by mixing modified mesoporous nano silica and waterborne polyurethane. After two dips and two rolls in a rolling mill, it is dried, cured and shaped to obtain a semi-finished product. Step 4: Use a pattern roller to emboss the semi-finished product to obtain moisture-wicking and breathable collagen fiber-based shoe lining leather.
2. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 1, characterized in that: The working conditions for the pre-wetting treatment in step 1 are: pressure of 10~12MPa and time of 1~3s; the working conditions for the high-pressure hydroentangling treatment are: pressure of 150~250MPa; the dyeing temperature in step 2 is 95~105℃.
3. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 1, characterized in that: The immersion time in step 3 is 10~12 min, and the drying, curing and shaping conditions are: temperature 95~105℃, time 5~10 min; the embossing temperature in step 4 is 140~150℃.
4. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 1, characterized in that: The preparation steps of the modified collagen fiber are as follows: S1: Under 4℃ conditions, take cowhide scraps, immerse them in sodium chloride solution for 3-4 hours, rinse them with distilled water 3-5 times and filter them, then soak them in degreasing agent for 23-25 hours, wash them with distilled water 3-5 times, and air dry them to obtain pre-treated cowhide. S2: Add distilled water to pretreated cowhide, then add acetic acid to make the concentration 1.2 mol / L, and add pepsin. Stir magnetically at 36-37℃ for 70-72 h, filter the reaction solution and centrifuge at 3000 rpm at 2-4℃ for 25-30 min. Collect the supernatant and dialyze it at 4℃ to obtain a collagen solution. Pre-freeze the collagen solution for 10-12 h, then freeze-dry it for 46-48 h to obtain collagen. S3: Weigh 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, dissolve them in 0.5 mol / L glacial acetic acid solution to prepare a crosslinking agent; add collagen to the crosslinking agent, stir and react at 2~4℃ for 10~11 h to obtain a modified spinning solution; inject the modified spinning solution into a syringe, set the spinning voltage to 14~16 kV, the spinning feed speed to 1~2 mL / h, and the receiving distance to 14~16 cm, and perform electrospinning to obtain modified collagen fibers.
5. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 4, characterized in that: The sodium chloride solution in S1 has a mass concentration of 12%, and the degreasing agent is prepared by mixing sodium carbonate, isopropanol, and deionized water in a mass ratio of 6:8:86; the pre-treated cowhide and distilled water in S2 have a material-to-liquid ratio of 1:25, and the amount of pepsin added is 1% of the mass of the cowhide scraps; the mass ratio of 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride to N-hydroxysuccinimide in S3 is 3:1, the mass concentration of the crosslinking agent is 15%, and the mass ratio of collagen to the crosslinking agent is 3:
20.
6. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 4, characterized in that: The dialysis working conditions described in S2 are magnetic stirring, changing the distilled water every 6 hours, and continuous dialysis for 3 days.
7. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 1, characterized in that: The preparation steps of the modified waterborne polyurethane finishing agent are as follows: Step a: Dry mesoporous nano-silica at 115~120℃ for 40~50min, add anhydrous ethanol and stir to obtain a nanoparticle suspension, add dichlorodimethylsilane and deionized water in sequence, heat to 130℃ and reflux for 45~55min to obtain a high-concentration nano-dispersion, centrifuge and wash 2~3 times with anhydrous ethanol, dry at 95~105℃, grind to obtain modified mesoporous nano-silica; Step b: Weigh the waterborne polyurethane and dilute it with deionized water. Stir for 10-15 minutes to prepare a waterborne polyurethane emulsion. Transfer the waterborne polyurethane emulsion to a water bath, adjust the temperature to 48-52℃, and stir magnetically. Add modified mesoporous nano silica to the emulsion within 1 minute, add defoamer, and stir for 45-55 minutes. Reduce the water bath temperature to 20-23℃ and maintain stirring for 18-22 minutes to obtain the modified waterborne polyurethane finishing agent.
8. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 7, characterized in that: The mass concentration of the nanoparticle suspension in step a is 4.8%, and the amount of dichlorodimethylsilane added is 15% of the mass of the mesoporous nano silica.
9. The method for preparing a moisture-wicking and breathable collagen fiber-based shoe lining leather according to claim 7, characterized in that: The concentration of the aqueous polyurethane emulsion in step b is 10 g / L, and the mass ratio of the aqueous polyurethane emulsion, modified mesoporous nano silica and defoamer is 100:1.5:0.
1.
10. A moisture-wicking and breathable collagen fiber-based shoe lining leather is prepared by the preparation method according to any one of claims 1-9.