A wear-resistant leather fabric and a preparation method thereof

Abstract

This invention discloses a wear-resistant leather fabric and its preparation method. The method involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of ricinoleic acid-modified polyurethane, polyhedral oligomeric silsesquioxane, fibrous soybean protein, and zirconium oxide composite graphene oxide. The leather fabric obtained by this invention exhibits excellent wear resistance, extends the service life of the leather fabric, maintains good softness, and provides superior comfort.

Description

Technical Field

[0001] This invention belongs to the field of fabric preparation technology, specifically relating to a wear-resistant leather fabric and its preparation method. Background Technology

[0002] Leather fabric is made by bonding animal hides to a base fabric after degreasing, tanning, and other treatments. Raw hides such as cowhide, pigskin, and sheepskin undergo a series of physical and chemical treatments, including degreasing, liming, softening, pickling, tanning, neutralization, retanning, filling, fatliquoring, and dyeing. These processes destroy and remove most of the other components in the raw hides, retaining only the essential parts for leather manufacturing: collagen fibers and the basic tissue structure composed of collagen fibers. Leather fabrics are widely used in many industries, including clothing, footwear, bags, and daily necessities. Compared to synthetic leather, animal leather has advantages such as high strength, durability, waterproofness, breathability, and aesthetic appeal.

[0003] With the improvement of the national economic level, people's demand for animal leather products is increasing. However, animal leather products usually require careful care. With long-term use, small molecules in animal leather migrate, and the original texture and elasticity are lost, resulting in brittleness, aging, and surface cracking. Given the increasingly fast pace of life, people have limited time and energy for caring for animal leather products. Therefore, improving the abrasion resistance of animal leather can play a certain protective role and extend the service life of animal leather products.

[0004] Patent CN103525957B discloses a method for producing wear-resistant leather. The method involves taking plump hides and sequentially applying a base coat, embossing, intermediate coat, top coat, tumbling, and color correction to obtain the finished leather. This patented technology uses different coatings for layered protection. After the base coat process, embossing effectively increases the density of the hide. Special processes for the intermediate and top coats further improve peel strength and abrasion resistance. However, this patented technology has a cumbersome coating process, and each coating layer requires baking at 100°C or near 100°C. The high baking temperature leads to poor mechanical properties and reduced softness in the product. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a wear-resistant leather fabric and its preparation method.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of castor oil-modified polyurethane, polyhedral oligomeric silsesquioxane, fibrous soybean protein, and zirconium oxide composite graphene oxide in a mass ratio of 1:0.1–0.2:0.2–0.3:0.1–0.2.

[0008] Preferably, the animal hide is selected from any one of cowhide, pigskin, or sheepskin.

[0009] Preferably, the ricinoleic acid-modified polyurethane is prepared by the following method: First, under nitrogen protection, toluene diisocyanate and polytetrahydrofuran diether alcohol are mixed uniformly at 70-80°C. Then, dibutyltin dilaurate is added, and polymerization is maintained at this temperature for 2-3 hours. The mixture is then heated to 90-100°C, and 2,2-dimethylolpropionic acid and N-methyldiethanolamine are added. The reaction is maintained at this temperature for 2-3 hours. Next, ricinoleic acid is added, and the reaction is maintained at this temperature for 2-3 hours. The mixture is then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35-40% by mass. The mass ratio of toluene diisocyanate, polytetrahydrofuran diether alcohol, dibutyltin dilaurate, 2,2-dimethylolpropionic acid, N-methyldiethanolamine, and ricinoleic acid is 16:5:0.5-0.8:3-4:3-4:2-3.

[0010] Preferably, the polyhedral oligomeric silsesquioxane is prepared by the following method: first, γ-aminopropyltriethoxysilane and cyclohexane are mixed evenly, then a 30-40% hydrochloric acid solution is added, the mixture is heated to 60-70°C, and the reaction is maintained at this temperature for 55-60 hours. The solvent is then removed by vacuum evaporation to obtain the final product. The ratio of γ-aminopropyltriethoxysilane, cyclohexane, and hydrochloric acid solution is 5-6 g: 20-30 mL: 3-4 mL.

[0011] Preferably, the fibrous soy protein is prepared by the following method: first, soy protein is ultrasonically dispersed in 25-30 times its weight of water, the pH is adjusted to 11-12 using 1-2 mol / L sodium hydroxide solution, heated at 80-90°C for 10-12 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.6-1 mol / L tartaric acid solution, stirred at 60-70°C for 40-50 minutes, irradiated with microwave at 300-500W for 2-3 minutes, the pH is adjusted to neutral using 1-2 mol / L sodium hydroxide solution, dialyzed using a 10000-12000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibrous soy protein.

[0012] Preferably, the zirconium oxide composite graphene oxide is prepared by the following method: first, zirconium oxide, graphene oxide, and sodium bromide are pulverized to 500 mesh and mixed in a mass ratio of 30-40:170-180:9-10 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature is raised to 1200-1300℃ at 3-5℃ / min, and calcined for 6-7 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder is mixed with an equal mass of water, ultrasonically oscillated at 500-600W for 30-40 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0013] Preferably, the specific method for degreasing is as follows: after cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12 to 15 times, let it stand for 2 to 3 hours, adjust the pH to 2 to 3 using a 20 to 30% formic acid aqueous solution, rotate the drum for 2 to 3 hours, and then drain the liquid.

[0014] More preferably, the degreasing agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12-15:100; wherein the animal fur waste extract is prepared by the following method: first, the animal fur waste is added to a 1-2 mol / L sodium hydroxide solution, stirred and heated at 95-100°C for 6-8 hours, filtered while hot, and the filtrate is naturally cooled to 60-65°C. Lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9-10 using a 1-2 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3-4 hours to obtain the animal fur waste extract; wherein the ratio of animal fur waste, sodium hydroxide solution, and lauroyl chloride is 3-4 kg: 2-3 kg: 0.2-0.3 mL.

[0015] Preferably, the specific method of water washing is as follows: First, wash the degreased leather with 2 to 3 times its weight of water 2 to 3 times to obtain pre-washed leather; then add the pre-washed leather to 2 to 3 times its weight of water, adjust the pH to 7, stir at 35 to 40°C for 1 to 2 hours, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather with 2 to 3 times its weight of water 2 to 3 times.

[0016] Preferably, the process conditions for the first low-temperature plasma treatment are: working atmosphere is oxygen, gas pressure is 20-30 Pa, power is 200-300 W, and treatment time is 30-40 s.

[0017] Preferably, the specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40-50°C water at 2-3 times its weight for 40-50 minutes, add the retanning agent, rotate the drum for 2-3 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8-1.

[0018] Preferably, the process conditions for the second low-temperature plasma treatment are as follows: the working atmosphere is nitrogen and oxygen, with a volume ratio of 1:0.3 to 0.5, the gas pressure is 100 to 120 Pa, the power is 300 to 400 W, and the treatment time is 2 to 3 minutes.

[0019] Preferably, the specific method of fatliquoring is as follows: soak the retanned leather in 2 to 3 times its weight of water at 60 to 65°C for 20 to 30 minutes, add the fatliquoring agent, rotate the drum for 2 to 3 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3 to 0.4.

[0020] More preferably, the fatliquoring agent is obtained by mixing castor oil phosphate, cow hoof oil, animal fur waste extract, and polyethylene glycol 400 dioleate in a mass ratio of 1:1:0.1-0.2:0.3-0.4.

[0021] More preferably, the animal fur waste extract is prepared by the following method: first, the animal fur waste is added to a 1-2 mol / L sodium hydroxide solution, stirred and heated at 95-100°C for 6-8 hours, filtered while hot, and the filtrate is freeze-dried under vacuum to obtain the extract; the mass ratio of animal fur waste to sodium hydroxide solution is 3-4:2-3.

[0022] A wear-resistant leather fabric is obtained by the aforementioned preparation method.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] This invention discloses a leather fabric obtained by sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of ricinoleic acid-modified polyurethane, polyhedral oligomeric silsesquioxane, fibrous soybean protein, and zirconium oxide composite graphene oxide. The leather fabric obtained by this invention exhibits excellent abrasion resistance, extends its service life, maintains good softness, and provides superior comfort.

[0025] This invention does not improve abrasion resistance by forming an abrasion-resistant coating. On the one hand, it avoids affecting the softness of the leather fabric, and on the other hand, it avoids the loss of abrasion resistance after the coating peels off.

[0026] The key technology of this invention lies in the selection of the retanning agent, which uses ricinoleic acid-modified polyurethane as the main component, supplemented by polyhedral oligomeric silsesquioxanes, fibrous soybean protein, and zirconium oxide composite graphene oxide. The hydroxyl groups and double bonds in ricinoleic acid are introduced into the polyurethane to improve the retanning effect; the polyhedral oligomeric silsesquioxanes, fibrous soybean protein, and zirconium oxide composite graphene oxide further enhance the retanning effect and fully penetrate the interior of the leather fabric, improving the product's abrasion resistance.

[0027] Low-temperature plasma treatment was performed before retanning and fatliquoring, which improved the retanning and fatliquoring effects, ensured the softness of the leather fabric, and enhanced its abrasion resistance.

[0028] The fatliquoring agent of the present invention is made by mixing castor oil phosphate, cow hoof oil, animal fur waste extract, and polyethylene glycol 400 dioleate. Through the synergistic effect of the components, the softness is improved. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] Unless otherwise specified, all products in this invention were purchased through market channels.

[0031] For ease of comparison, the animal hides used in the examples and comparative examples are all from the same source of cowhide.

[0032] Example 1

[0033] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.1 kg of polyhedral oligomeric silsesquioxane, 0.2 kg of fibrous soybean protein, and 0.1 kg of zirconium oxide composite graphene oxide.

[0034] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 70°C under nitrogen protection. 0.05 kg of dibutyltin dilaurate was added, and polymerization was maintained at this temperature for 2 hours. The mixture was then heated to 90°C, and 0.3 kg of 2,2-dimethylolpropionic acid and 0.3 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2 hours. 0.2 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35%.

[0035] Polyhedral oligomeric silsesquioxanes are prepared by the following method: 0.5 kg of γ-aminopropyltriethoxysilane is mixed with 2 L of cyclohexane until homogeneous, then 0.3 L of 30% hydrochloric acid solution is added, the mixture is heated to 60 °C and kept at that temperature for 55 hours, and the solvent is removed by vacuum evaporation to obtain the product.

[0036] Fibrinized soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 25 times its weight of water, the pH is adjusted to 11 using 1 mol / L sodium hydroxide solution, heated at 80℃ for 10 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.6 mol / L tartaric acid solution, stirred at 60℃ for 40 minutes, irradiated with 300W microwave for 2 minutes, the pH is adjusted to neutral using 1 mol / L sodium hydroxide solution, dialyzed using a 10000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibroinized soy protein.

[0037] Zirconia-graphene oxide composite was prepared by the following method: Zirconia, graphene oxide and sodium bromide were first pulverized to 500 mesh and mixed in a mass ratio of 30:170:9 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature was raised to 1200℃ at 3℃ / min and calcined for 6 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder was mixed with water by an equal mass, ultrasonically oscillated at 500W for 30 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0038] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12, let it stand for 2 hours, adjust the pH to 2 using a 20% formic acid aqueous solution, rotate the drum for 2 hours, and then drain the liquid.

[0039] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12:100. The animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is naturally cooled to 60°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0040] The specific method for washing is as follows: First, wash the degreased leather twice with twice its weight of water to obtain pre-washed leather; then add the pre-washed leather to twice its weight of water, adjust the pH to 7, stir at 35℃ for 1 hour, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with twice its weight of water.

[0041] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20 Pa, power was 200 W, and treatment time was 30 s.

[0042] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40°C water at twice its weight for 40 minutes, add the retanning agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8.

[0043] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.3, the pressure was 100 Pa, the power was 300 W, and the treatment time was 2 minutes.

[0044] The specific method for fatliquoring is as follows: Soak the retanned leather in 60°C water at twice its weight for 20 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0045] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0046] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0047] Example 2

[0048] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.2 kg of polyhedral oligomeric silsesquioxane, 0.3 kg of fibrous soybean protein, and 0.2 kg of zirconium oxide composite graphene oxide.

[0049] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed evenly at 80°C under nitrogen protection. 0.08 kg of dibutyltin dilaurate was added, and the mixture was kept at this temperature for 3 hours to polymerize. The mixture was then heated to 100°C, and 0.4 kg of 2,2-dimethylolpropionic acid and 0.4 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 3 hours to react. 0.3 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 3 hours to react. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 40% by mass.

[0050] Polyhedral oligomeric silsesquioxanes are prepared by the following method: 0.6 kg of γ-aminopropyltriethoxysilane is mixed with 3 L of cyclohexane, then 0.4 L of 40% hydrochloric acid solution is added, the mixture is heated to 70 °C, and the reaction is maintained at this temperature for 60 hours. The solvent is then removed by vacuum evaporation to obtain the final product.

[0051] Fibrinized soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 30 times its weight of water, the pH is adjusted to 12 using 2 mol / L sodium hydroxide solution, heated at 90℃ for 12 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 1 mol / L tartaric acid solution, stirred at 70℃ for 50 minutes, irradiated with 500W microwave for 3 minutes, the pH is adjusted to neutral using 2 mol / L sodium hydroxide solution, dialyzed using a 12000Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibroinized soy protein.

[0052] Zirconia-graphene oxide composite was prepared by the following method: Zirconia, graphene oxide and sodium bromide were first pulverized to 500 mesh and mixed in a mass ratio of 40:180:10 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature was raised to 1300℃ at 5℃ / min and calcined for 7 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder was mixed with water by an equal mass, ultrasonically oscillated at 600W for 40 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0053] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 15, let it stand for 3 hours, adjust the pH to 3 using a 30% formic acid aqueous solution, rotate the drum for 3 hours, and then drain the liquid.

[0054] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 15:100. The animal fur waste extract is prepared by the following method: 4 kg of animal fur waste is added to 3 kg of 2 mol / L sodium hydroxide solution, stirred and heated at 100°C for 8 hours, filtered while hot, and the filtrate is naturally cooled to 65°C. 0.3 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 10 using 2 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 4 hours to obtain the animal fur waste extract.

[0055] The specific method for washing is as follows: First, wash the degreased leather three times with three times its weight of water to obtain pre-washed leather; then add the pre-washed leather to three times its weight of water, adjust the pH to 7, stir at 40℃ for 2 hours, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather three times with three times its weight of water.

[0056] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 30 Pa, power was 300 W, and treatment time was 40 s.

[0057] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 50°C water at 3 times its weight for 50 minutes, add the retanning agent, rotate the drum for 3 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:1.

[0058] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.5, the pressure was 120 Pa, the power was 400 W, and the treatment time was 3 minutes.

[0059] The specific method for fatliquoring is as follows: Soak the retanned leather in 65°C water at 3 times its weight for 30 minutes, add the fatliquoring agent, rotate the drum for 3 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.4.

[0060] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.2 kg of animal hide and fur waste extract, and 0.4 kg of polyethylene glycol 400 dioleate.

[0061] Animal fur waste extract is prepared by the following method: 4 kg of animal fur waste is added to 3 kg of 2 mol / L sodium hydroxide solution, stirred and heated at 100°C for 8 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0062] Example 3

[0063] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.15 kg of polyhedral oligomeric silsesquioxane, 0.25 kg of fibrous soybean protein, and 0.15 kg of zirconium oxide composite graphene oxide.

[0064] The ricinoleic acid-modified polyurethane was prepared by the following method: First, under nitrogen protection, 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 75°C. Then, 0.07 kg of dibutyltin dilaurate was added, and the mixture was kept at this temperature for 2.5 hours. The mixture was then heated to 95°C, and 0.35 kg of 2,2-dimethylolpropionic acid and 0.35 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2.5 hours. Finally, 0.25 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2.5 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 37%.

[0065] Polyhedral oligomeric silsesquioxanes are prepared by the following method: 0.55 kg of γ-aminopropyltriethoxysilane is mixed with 2.5 L of cyclohexane, then 0.35 L of 35% hydrochloric acid solution is added, the mixture is heated to 65 °C and kept at that temperature for 57 hours, and the solvent is removed by vacuum evaporation to obtain the product.

[0066] Fibrinized soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 28 times its weight of water, the pH is adjusted to 11 using 1.5 mol / L sodium hydroxide solution, heated at 85°C for 11 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.8 mol / L tartaric acid solution, stirred at 65°C for 45 minutes, irradiated with a 450W microwave for 2 minutes, the pH is adjusted to neutral using 1 mol / L sodium hydroxide solution, dialyzed using a 12000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibroinized soy protein.

[0067] Zirconia-graphene oxide composite was prepared by the following method: Zirconia, graphene oxide and sodium bromide were first pulverized to 500 mesh and mixed in a mass ratio of 35:175:9 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature was raised to 1250℃ at 4℃ / min and calcined for 6 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder was mixed with water by an equal mass, ultrasonically oscillated at 600W for 35 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0068] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 13 times its weight, let it stand for 2 hours, adjust the pH to 2 using a 25% formic acid aqueous solution, rotate the drum for 3 hours, and then drain the liquid.

[0069] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 13:100. The animal fur waste extract is prepared by the following method: 3.5 kg of animal fur waste is added to 2.5 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 98°C for 7 hours, filtered while hot, and the filtrate is naturally cooled to 62°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 10 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0070] The specific method for washing is as follows: First, wash the degreased leather twice with three times its weight of water to obtain pre-washed leather; then add the pre-washed leather to two times its weight of water, adjust the pH to 7, stir at 38℃ for 1.5 hours, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with 2.5 times its weight of water.

[0071] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 25 Pa, power was 300 W, and treatment time was 40 s.

[0072] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 50°C water at twice its weight for 45 minutes, add the retanning agent, rotate the drum for 2.5 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:1.

[0073] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.5, the pressure was 120 Pa, the power was 400 W, and the treatment time was 2 minutes.

[0074] The specific method for fatliquoring is as follows: Soak the retanned leather in 65°C water at 3 times its weight for 30 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0075] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0076] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 100°C for 7 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0077] Comparative Example 1

[0078] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.1 kg of polyhedral oligomeric silsesquioxane, and 0.1 kg of zirconium oxide composite graphene oxide.

[0079] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 70°C under nitrogen protection. 0.05 kg of dibutyltin dilaurate was added, and polymerization was maintained at this temperature for 2 hours. The mixture was then heated to 90°C, and 0.3 kg of 2,2-dimethylolpropionic acid and 0.3 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2 hours. 0.2 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35%.

[0080] Polyhedral oligomeric silsesquioxanes are prepared by the following method: 0.5 kg of γ-aminopropyltriethoxysilane is mixed with 2 L of cyclohexane until homogeneous, then 0.3 L of 30% hydrochloric acid solution is added, the mixture is heated to 60 °C and kept at that temperature for 55 hours, and the solvent is removed by vacuum evaporation to obtain the product.

[0081] Zirconia-graphene oxide composite was prepared by the following method: Zirconia, graphene oxide and sodium bromide were first pulverized to 500 mesh and mixed in a mass ratio of 30:170:9 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature was raised to 1200℃ at 3℃ / min and calcined for 6 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder was mixed with water by an equal mass, ultrasonically oscillated at 500W for 30 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0082] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12, let it stand for 2 hours, adjust the pH to 2 using a 20% formic acid aqueous solution, rotate the drum for 2 hours, and then drain the liquid.

[0083] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12:100. The animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is naturally cooled to 60°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0084] The specific method for washing is as follows: First, wash the degreased leather twice with twice its weight of water to obtain pre-washed leather; then add the pre-washed leather to twice its weight of water, adjust the pH to 7, stir at 35℃ for 1 hour, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with twice its weight of water.

[0085] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20 Pa, power was 200 W, and treatment time was 30 s.

[0086] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40°C water at twice its weight for 40 minutes, add the retanning agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8.

[0087] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.3, the pressure was 100 Pa, the power was 300 W, and the treatment time was 2 minutes.

[0088] The specific method for fatliquoring is as follows: Soak the retanned leather in 60°C water at twice its weight for 20 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0089] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0090] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0091] Comparative Example 2

[0092] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.2 kg of fibrous soybean protein, and 0.1 kg of zirconium oxide composite graphene oxide.

[0093] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 70°C under nitrogen protection. 0.05 kg of dibutyltin dilaurate was added, and polymerization was maintained at this temperature for 2 hours. The mixture was then heated to 90°C, and 0.3 kg of 2,2-dimethylolpropionic acid and 0.3 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2 hours. 0.2 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35%.

[0094] Fibrinized soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 25 times its weight of water, the pH is adjusted to 11 using 1 mol / L sodium hydroxide solution, heated at 80℃ for 10 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.6 mol / L tartaric acid solution, stirred at 60℃ for 40 minutes, irradiated with 300W microwave for 2 minutes, the pH is adjusted to neutral using 1 mol / L sodium hydroxide solution, dialyzed using a 10000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibroinized soy protein.

[0095] Zirconia-graphene oxide composite was prepared by the following method: Zirconia, graphene oxide and sodium bromide were first pulverized to 500 mesh and mixed in a mass ratio of 30:170:9 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature was raised to 1200℃ at 3℃ / min and calcined for 6 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder was mixed with water by an equal mass, ultrasonically oscillated at 500W for 30 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

[0096] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12, let it stand for 2 hours, adjust the pH to 2 using a 20% formic acid aqueous solution, rotate the drum for 2 hours, and then drain the liquid.

[0097] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12:100. The animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is naturally cooled to 60°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0098] The specific method for washing is as follows: First, wash the degreased leather twice with twice its weight of water to obtain pre-washed leather; then add the pre-washed leather to twice its weight of water, adjust the pH to 7, stir at 35℃ for 1 hour, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with twice its weight of water.

[0099] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20 Pa, power was 200 W, and treatment time was 30 s.

[0100] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40°C water at twice its weight for 40 minutes, add the retanning agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8.

[0101] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.3, the pressure was 100 Pa, the power was 300 W, and the treatment time was 2 minutes.

[0102] The specific method for fatliquoring is as follows: Soak the retanned leather in 60°C water at twice its weight for 20 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0103] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0104] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0105] Comparative Example 3

[0106] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of 1 kg of ricinoleic acid-modified polyurethane, 0.1 kg of polyhedral oligomeric silsesquioxane, and 0.2 kg of fibrous soybean protein.

[0107] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 70°C under nitrogen protection. 0.05 kg of dibutyltin dilaurate was added, and polymerization was maintained at this temperature for 2 hours. The mixture was then heated to 90°C, and 0.3 kg of 2,2-dimethylolpropionic acid and 0.3 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2 hours. 0.2 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35%.

[0108] Polyhedral oligomeric silsesquioxanes are prepared by the following method: 0.5 kg of γ-aminopropyltriethoxysilane is mixed with 2 L of cyclohexane until homogeneous, then 0.3 L of 30% hydrochloric acid solution is added, the mixture is heated to 60 °C and kept at that temperature for 55 hours, and the solvent is removed by vacuum evaporation to obtain the product.

[0109] Fibrinized soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 25 times its weight of water, the pH is adjusted to 11 using 1 mol / L sodium hydroxide solution, heated at 80℃ for 10 minutes, and the supernatant is collected by centrifugation to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.6 mol / L tartaric acid solution, stirred at 60℃ for 40 minutes, irradiated with 300W microwave for 2 minutes, the pH is adjusted to neutral using 1 mol / L sodium hydroxide solution, dialyzed using a 10000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibroinized soy protein.

[0110] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12, let it stand for 2 hours, adjust the pH to 2 using a 20% formic acid aqueous solution, rotate the drum for 2 hours, and then drain the liquid.

[0111] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12:100. The animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is naturally cooled to 60°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0112] The specific method for washing is as follows: First, wash the degreased leather twice with twice its weight of water to obtain pre-washed leather; then add the pre-washed leather to twice its weight of water, adjust the pH to 7, stir at 35℃ for 1 hour, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with twice its weight of water.

[0113] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20 Pa, power was 200 W, and treatment time was 30 s.

[0114] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40°C water at twice its weight for 40 minutes, add the retanning agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8.

[0115] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.3, the pressure was 100 Pa, the power was 300 W, and the treatment time was 2 minutes.

[0116] The specific method for fatliquoring is as follows: Soak the retanned leather in 60°C water at twice its weight for 20 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0117] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0118] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0119] Comparative Example 4

[0120] A method for preparing abrasion-resistant leather fabric involves sequentially subjecting animal raw hides to degreasing, washing, a first low-temperature plasma treatment, retanning, a second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing; wherein the retanning agent used in the retanning process is ricinoleic acid modified polyurethane.

[0121] The ricinoleic acid-modified polyurethane was prepared by the following method: 1.6 kg of toluene diisocyanate and 0.5 kg of polytetrahydrofuran diether alcohol were mixed uniformly at 70°C under nitrogen protection. 0.05 kg of dibutyltin dilaurate was added, and polymerization was maintained at this temperature for 2 hours. The mixture was then heated to 90°C, and 0.3 kg of 2,2-dimethylolpropionic acid and 0.3 kg of N-methyldiethanolamine were added. The mixture was kept at this temperature for 2 hours. 0.2 kg of ricinoleic acid was added, and the mixture was kept at this temperature for 2 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain a ricinoleic acid-modified polyurethane with a solid content of 35%.

[0122] The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12, let it stand for 2 hours, adjust the pH to 2 using a 20% formic acid aqueous solution, rotate the drum for 2 hours, and then drain the liquid.

[0123] The defatting agent solution is obtained by uniformly mixing decyl glucoside and animal fur waste extract at a mass ratio of 12:100. The animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is naturally cooled to 60°C. 0.2 mL of lauroyl chloride is added dropwise to the filtrate, and the pH is controlled at 9 using 1 mol / L sodium hydroxide solution. After the addition is complete, the mixture is stirred for 3 hours to obtain the animal fur waste extract.

[0124] The specific method for washing is as follows: First, wash the degreased leather twice with twice its weight of water to obtain pre-washed leather; then add the pre-washed leather to twice its weight of water, adjust the pH to 7, stir at 35℃ for 1 hour, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather twice with twice its weight of water.

[0125] The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20 Pa, power was 200 W, and treatment time was 30 s.

[0126] The specific method for retanning is as follows: soak the leather after low-temperature plasma treatment in 40°C water at twice its weight for 40 minutes, add the retanning agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the leather after low-temperature plasma treatment to the retanning agent is 1:0.8.

[0127] The process conditions for the second low-temperature plasma treatment were as follows: the working atmosphere was nitrogen and oxygen, with a volume ratio of 1:0.3, the pressure was 100 Pa, the power was 300 W, and the treatment time was 2 minutes.

[0128] The specific method for fatliquoring is as follows: Soak the retanned leather in 60°C water at twice its weight for 20 minutes, add the fatliquoring agent, rotate the drum for 2 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3.

[0129] The fatliquoring agent is obtained by mixing 1 kg of castor oil phosphate, 1 kg of cow hoof oil, 0.1 kg of animal hide waste extract, and 0.3 kg of polyethylene glycol 400 dioleate.

[0130] Animal fur waste extract is prepared by the following method: 3 kg of animal fur waste is added to 2 kg of 1 mol / L sodium hydroxide solution, stirred and heated at 95°C for 6 hours, filtered while hot, and the filtrate is then freeze-dried under vacuum to obtain the extract.

[0131] The performance of the leather fabrics obtained in Examples 1-3 and Comparative Examples 1-4 were tested respectively, and the specific methods are as follows:

[0132] 1. Abrasion resistance: A Martindale abrasion tester was used, referring to QB / T 2726-2005 "Determination of abrasion resistance of leather physical and mechanical tests". Before the test, the mass m1 of the sample was weighed. Then the sample was fixed on the test instrument and the grinding wheel was pressed on. The speed was set to 1000 r / min. After the test, the mass m2 of the sample was weighed again and the mass loss before and after wear was calculated, that is, the difference between m1 and m2.

[0133] 2. Softness: Refer to GB / T 39371-2020 "Determination of Softness in Physical and Mechanical Tests of Leather" to conduct a softness test (the diameter of the round hole is 25mm).

[0134] The performance test results are shown in Table 1.

[0135] Table 1. Performance Test Results

[0136]

[0137] As shown in Table 1, the leather fabrics obtained in Examples 1 to 3 have excellent abrasion resistance and good softness.

[0138] Comparative Example 1 omitted fibrous soy protein, Comparative Example 2 omitted polyhedral oligomeric silsesquioxane, Comparative Example 3 omitted zirconium oxide composite graphene oxide, and Comparative Example 4 omitted polyhedral oligomeric silsesquioxane, fibrous soy protein, and zirconium oxide composite graphene oxide. Both wear resistance and softness were significantly worse, indicating that fibrous soy protein, polyhedral oligomeric silsesquioxane, and zirconium oxide composite graphene oxide work synergistically to improve wear resistance and have good compatibility with animal skin components. They cross-link into a network structure through hydrogen bonding and other interactions, resulting in better product softness.

[0139] The present invention has been illustrated through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of individual raw materials in the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing abrasion-resistant leather fabric, characterized in that, Animal hides are subjected to the following steps in sequence: degreasing, washing, first low-temperature plasma treatment, retanning, second low-temperature plasma treatment, fatliquoring, dyeing, and color fixing. The retanning agent used in the retanning process is a mixture of ricinoleic acid-modified polyurethane, polyhedral oligomeric silsesquioxane, fibrous soybean protein, and zirconium oxide composite graphene oxide in a mass ratio of 1:0.1-0.2:0.2-0.3:0.1-0.

2. The ricinoleic acid-modified polyurethane was prepared by the following method: under nitrogen protection, toluene diisocyanate and polytetrahydrofuran diether alcohol were mixed evenly at 70-80°C, dibutyltin dilaurate was added, and polymerization was carried out at this temperature for 2-3 hours. The mixture was then heated to 90-100°C, 2,2-dimethylolpropionic acid and N-methyldiethanolamine were added, and the reaction was carried out at this temperature for 2-3 hours. Ricinoleic acid was added, and the reaction was carried out at this temperature for 2-3 hours. The mixture was then naturally cooled to below 45°C, neutralized with triethylamine, and emulsified with distilled water to obtain ricinoleic acid-modified polyurethane with a solid content of 35-40% by mass. The polyhedral oligomeric silsesquioxane is prepared by the following method: first, γ-aminopropyltriethoxysilane is mixed evenly with cyclohexane, then a 30-40% hydrochloric acid solution is added, the mixture is heated to 60-70°C, and the reaction is maintained at this temperature for 55-60 hours. The solvent is then removed by vacuum evaporation to obtain the final product. The fibrous soy protein is prepared by the following method: First, soy protein is ultrasonically dispersed in 25-30 times its weight of water, the pH is adjusted to 11-12 using 1-2 mol / L sodium hydroxide solution, heated at 80-90℃ for 10-12 minutes, centrifuged and the supernatant is collected to obtain a soy protein solution; then, the soy protein solution is mixed with an equal volume of 0.6-1 mol / L tartaric acid solution, stirred at 60-70℃ for 40-50 minutes, irradiated with microwave at 300-500W for 2-3 minutes, the pH is adjusted to neutral using 1-2 mol / L sodium hydroxide solution, dialyzed using a 10000-12000 Da dialysis bag, dried, and pulverized to below 500 mesh to obtain fibrous soy protein; The zirconia composite graphene oxide is prepared by the following method: First, zirconia, graphene oxide, and sodium bromide are pulverized to 500 mesh and mixed in a mass ratio of 30-40:170-180:9-10 to obtain a mixed powder; then, under a nitrogen atmosphere, the temperature is raised to 1200-1300℃ at 3-5℃ / min, and calcined for 6-7 hours, and then naturally cooled to room temperature to obtain calcined powder; finally, the calcined powder is mixed with an equal mass of water, ultrasonically oscillated at 500-600W for 30-40 minutes, centrifuged to collect the precipitate, dried, and pulverized to below 500 mesh to obtain the final product.

2. The preparation method according to claim 1, characterized in that, The animal hide is selected from any one of cowhide, pigskin, or sheepskin.

3. The preparation method according to claim 1, characterized in that, The mass ratio of toluene diisocyanate, polytetrahydrofuran diether alcohol, dibutyltin dilaurate, 2,2-dimethylolpropionic acid, N-methyldiethanolamine, and ricinoleic acid is 16:5:0.5-0.8:3-4:3-4:2-3.

4. The preparation method according to claim 1, characterized in that, The ratio of γ-aminopropyltriethoxysilane, cyclohexane, and hydrochloric acid solution is 5-6 g: 20-30 mL: 3-4 mL.

5. The preparation method according to claim 1, characterized in that, The specific method for degreasing is as follows: After cleaning the animal hide, completely immerse it in a degreasing agent solution with a weight of 12 to 15 times. Let it stand for 2 to 3 hours, adjust the pH to 2 to 3 using a 20 to 30% formic acid aqueous solution, rotate the drum for 2 to 3 hours, and then drain the liquid.

6. The preparation method according to claim 1, characterized in that, The specific method for washing is as follows: First, wash the degreased leather with 2 to 3 times its weight of water 2 to 3 times to obtain pre-washed leather; then add the pre-washed leather to 2 to 3 times its weight of water, adjust the pH to 7, stir at 35 to 40°C for 1 to 2 hours, drain the water, and obtain neutralized washed leather; finally, wash the neutralized washed leather with 2 to 3 times its weight of water 2 to 3 times.

7. The preparation method according to claim 1, characterized in that, The process conditions for the first low-temperature plasma treatment were: working atmosphere was oxygen, gas pressure was 20-30 Pa, power was 200-300 W, and treatment time was 30-40 s; The specific method for retanning is as follows: soak the leather treated with low-temperature plasma in 40-50°C water at 2-3 times its weight for 40-50 minutes, add the retanning agent, rotate the drum for 2-3 hours, and then drain the liquid; the mass ratio of the leather treated with low-temperature plasma to the retanning agent is 1:0.8-1. The process conditions for the second low-temperature plasma treatment are as follows: the working atmosphere is nitrogen and oxygen, with a volume ratio of 1:0.3 to 0.5, the gas pressure is 100 to 120 Pa, the power is 300 to 400 W, and the treatment time is 2 to 3 minutes; The specific method for fatliquoring is as follows: Soak the retanned leather in 2 to 3 times its weight of water at 60 to 65°C for 20 to 30 minutes, add the fatliquoring agent, rotate the drum for 2 to 3 hours, and then drain the liquid; the mass ratio of the retanned leather to the fatliquoring agent is 100:0.3 to 0.

4.

8. A wear-resistant leather fabric, characterized in that, It is obtained by the preparation method described in any one of claims 1 to 7.

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