Wear-resistant and stain-resistant leather and preparation method thereof

Abstract

The invention relates to wear-resistant and stain-resistant leather and a preparation method thereof, and belongs to the technical field of leather.The preparation method comprises the steps that A1, leather finishing liquid is prepared; a2, the leather blank is subjected to surface dust removal, cleaning, air drying and grinding in sequence, then leather coating liquid is sprayed, drying, polishing and waxing are conducted, and the wear-resistant and stain-resistant leather finished product is obtained. In the process of preparing the leather finishing liquid, methyl methacrylate, butyl acrylate and acrylic acid are selected as main base materials, alkyd resin and sodium p-styrenesulfonate are used as functional auxiliary materials, and phenyltrimethoxysilane is used as an enhanced raw material, so that the finished product has wear resistance; in addition, the carboxyl carbon nanotube-zinc oxide composite material is also prepared, so that the waterproofness of the finished product is improved; gallic acid and octadecyl dimethyl trimethylsilyl propyl ammonium chloride are added to achieve a synergistic antibacterial effect; the leather finishing liquid provided by the invention has wear-resistant, hydrophobic and antibacterial effects, and a leather finished product prepared by using the leather finishing liquid has stain resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of leather, and specifically relates to a wear-resistant and stain-resistant leather and a preparation method thereof. Background Art

[0002] As an important material, leather is widely used in many fields such as shoes, clothing, luggage, furniture, and automotive interiors. With the continuous improvement of consumers' requirements for product quality and usage experience, the wear resistance and stain resistance of leather have become key indicators for measuring its quality. The wear resistance determines the service life of leather products, while the stain resistance directly affects the aesthetics and practicality of the products. Traditional leather products have many deficiencies in terms of wear resistance and stain resistance. During actual use, the surface of traditional leather is extremely prone to wear due to friction, especially in high-frequency use scenarios, such as the soles of shoes and the corners of luggage, where the wear phenomenon is more serious. This not only damages the appearance of leather products but also greatly shortens their service life. In addition, traditional leather has weak stain resistance. Due to the presence of a large number of tiny pores on its surface, when it comes into contact with stains such as water stains, oil stains, and ink, the stain molecules will quickly penetrate into the leather interior and adhere, resulting in a significant increase in the cleaning difficulty. Moreover, when the leather is in a humid environment or contaminated with stains, it is prone to become a breeding ground for bacteria. Once the stains cannot be removed in time, it will not only affect the aesthetics of leather products but also may cause unpleasant odors and reduce the product quality.

[0003] Therefore, how to prepare a leather with excellent wear resistance and stain resistance and achieve the synergistic effect of various properties has become an urgent problem to be solved in the current leather preparation field. Summary of the Invention

[0004] The purpose of the present invention is to provide a wear-resistant and stain-resistant leather and a preparation method thereof, which solves the problem of poor wear resistance and stain resistance of leather in the prior art.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A preparation method of a wear-resistant and stain-resistant leather includes the following steps:

[0007] A1. Prepare a leather finishing solution;

[0008] A2. The leather blank is successively subjected to surface dust removal, cleaning, air drying, and grinding, then sprayed with the leather finishing solution, and then dried, polished, and waxed to obtain the finished wear-resistant and stain-resistant leather.

[0009] As a preferred technical solution of the present invention, the preparation method of the leather finishing solution in step A1 includes the following steps:

[0010] S1. Prepare a carboxylated carbon nanotube zinc oxide composite material;

[0011] S2. Pre-treat part of the raw materials to obtain premix A, premix B, initiating solution, emulsion, and mixture A;

[0012] S3. Add sodium bicarbonate, emulsion, premix A, and alkyd resin to the carboxylated carbon nanotube-zinc oxide composite material, heat up and dropwise add the initiating solution, and then stir to obtain mixture B;

[0013] S4. Dropwise add premix B and the initiating solution to mixture B simultaneously. After dropping, control the temperature and let it stand still. Then add mixture A and phenyltrimethoxysilane, control the temperature and let it stand still again. Add gallic acid and let it stand still, adjust the pH, and stir to obtain the leather finishing solution.

[0014] As a preferred technical solution of the present invention, step S1 specifically includes the following steps:

[0015] Mix zinc acetate, diethylene glycol monomethyl ether, and deionized water evenly, control the temperature and stir for the first time, let it stand still, add carboxylated carbon nanotubes and dopamine hydrochloride, disperse them by ultrasonic wave, control the temperature and stir for the second time, centrifuge, wash, and control the temperature for drying to obtain the carboxylated carbon nanotube-zinc oxide composite material.

[0016] Furthermore, the zinc acetate, brand: Qianyao, is purchased from Langfang Qianyao Technology Co., Ltd.; the carboxylated carbon nanotubes, product number: HQNANO-CNTs-006-3H, brand: Beike Nano, are purchased from Suzhou Kaifa New Materials Technology Co., Ltd.

[0017] As a preferred technical solution of the present invention, the dosage ratio of zinc acetate, diethylene glycol monomethyl ether, deionized water, carboxylated carbon nanotubes, and dopamine hydrochloride in step S1 is 1 - 1.1 g: 245 - 250 mL: 10 - 12 mL: 1.1 - 1.2 g: 3 - 5 g;

[0018] Zinc particles can significantly increase the surface roughness of the material, thereby enhancing the waterproof performance of the system; due to its excellent mechanical strength and elastic modulus, carbon nanotubes can provide a strong supporting structure for the coating layer, ensuring that the coating layer can still maintain the structural integrity to a certain extent when subjected to external forces. However, the interfacial interaction between carbon nanotubes and polymers is relatively weak. In view of this, the present invention selects carboxylated carbon nanotubes treated by carboxylation as the base material to prepare carboxylated carbon nanotube-zinc oxide composites, and adds them as key raw materials to the system, which can greatly improve the waterproof property of the system and thus increase the anti-fouling performance.

[0019] As a preferred technical solution of the present invention, the temperature of the first temperature-controlled stirring in step S1 is 170-180°C, and the time is 5-8 min; the standing is carried out at room temperature for 1.5-2 h; the time of ultrasonic dispersion is 30-35 min; the temperature of the second temperature-controlled stirring is 170-175°C, and the time is 1-1.5 h; the washing is carried out by washing with absolute ethanol and distilled water in sequence for 2-3 times; the temperature of the temperature-controlled drying is 100-110°C, and the time is 10-12 h.

[0020] As a preferred technical solution of the present invention, step S2 specifically includes:

[0021] Mix methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate and carry out temperature-controlled pre-stirring to obtain premix A; mix methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate and carry out temperature-controlled pre-stirring to obtain premix B; mix the initiator and distilled water evenly to obtain an initiator solution; mix the emulsifier evenly to obtain an emulsion; carry out temperature-controlled stirring on the silane coupling agent, octadecyl dimethyl trimethylsilylpropyl ammonium chloride, deionized water, and absolute ethanol to obtain mixture A.

[0022] Further, the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate in premix A and premix B is 8-11:10.5-12:0.7-1:0.7-0.75; the mass ratio of the initiator and distilled water is 0.4-0.5:40-45; the emulsifier includes a mixture of an anionic emulsifier and a non-ionic emulsifier in a mass ratio of 0.5-0.6:1.

[0023] Further, the brands of acrylic acid and butyl acrylate are both: Kejian, and they are both purchased from Shandong Kejian Chemical Co., Ltd.; the brand of methyl methacrylate is: Chuangying, and it is purchased from Shandong Chuangying Chemical Co., Ltd.; the brand of sodium styrene sulfonate is: Jiyesheng, and it is purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0024] Still further, the temperature of the temperature-controlled pre-stirring is 70-75°C, and the time is 20-25 min for both.

[0025] Still further, the initiator includes ammonium persulfate.

[0026] Still further, the anionic emulsifier includes sodium dodecyl sulfate or sodium dodecylbenzenesulfonate; the non-ionic emulsifier includes Span 80 or Tween 80.

[0027] Further, the mass ratio of the silane coupling agent, octadecyl dimethyl trimethylsilylpropyl ammonium chloride, deionized water, and absolute ethanol is 10-11:1:10-15:10-15.

[0028] Furthermore, the silane coupling agent includes KH-550; the temperature of the temperature-controlled stirring is 55-60°C, and the time is 2-3h.

[0029] As a preferred technical solution of the present invention, the mass ratio of the carboxylated carbon nanotube zinc oxide composite, sodium bicarbonate, emulsion, premix A, and alkyd resin in step S3 is 2.5-5:0.8-1:0.65-0.7:10-12:7-8; the addition amount of the initiator solution is 0.8-0.82 times the mass of acrylic acid in premix A.

[0030] Furthermore, the alkyd resin model includes SM3230, purchased from Jiangsu Sanmu Chemical Co., Ltd.

[0031] As a preferred technical solution of the present invention, the temperature increase in step S3 is to increase the temperature to 75-80°C; the initiator solution is added dropwise within 1h.

[0032] As a preferred technical solution of the present invention, the addition amount of premix B in step S4 includes 2-2.2 times the mass of premix A; the addition amount of the initiator solution is 0.8-0.82 of the mass of acrylic acid in premix B.

[0033] As a preferred technical solution of the present invention, the mass ratio of mixture B, mixture A, phenyltrimethoxysilane, and gallic acid in step S4 is 18-20:1.8-2:0.8-1:1.5-2.

[0034] As a preferred technical solution of the present invention, the temperature of the temperature-controlled standing in step S4 is 70-85°C, and the time is 1-2h; the temperature of the re-temperature-controlled standing is 80-85°C, and the time is 1.5-2h; the standing time after adding gallic acid is 1-2h; the pH is adjusted to pH = 6 at room temperature using sodium bicarbonate; the stirring time is 10-15min.

[0035] The beneficial effects of the present invention:

[0036] (1) In this invention, methyl methacrylate, butyl acrylate and acrylic acid are selected as the main base materials, alkyd resin and sodium styrene sulfonate are used as functional auxiliary materials, and phenyltrimethoxysilane is used as an enhanced raw material. The strong interaction generated between the molecular chains formed by alkyd resin and the main base materials increases the compactness of the system. Meanwhile, phenyltrimethoxysilane will hydrolyze in the system, and the generated silanol groups will undergo polycondensation, thus forming a network structure in the system. In this way, when the system is subjected to external frictional force, the movement of the internal molecular chains is restricted, enhancing the abrasion resistance of the leather produced. In addition, to consolidate the stability of the system performance, the sodium styrene sulfonate added in this invention is to introduce sulfonic acid groups, increase the electrostatic repulsion between particles in the system, reduce the probability of gel formation, and further effectively make the produced finished product more stable, that is, further enhancing the abrasion resistance of the system.

[0037] (2) The carboxyl carbon nanotube-zinc oxide composite material prepared in this invention can coordinate with the carboxyl groups in the system to form stable chemical bonds, further improving the water resistance of the material. In addition, during the preparation of the carboxyl carbon nanotube-zinc oxide composite material in this invention, hydrochloric acid dopamine is also added to enhance the stability of the crosslinked network of the system, thereby indirectly further improving the water resistance.

[0038] (3) This invention adds gallic acid, and the phenolic hydroxyl groups containing strong oxidizing properties in it can damage the integrity of the cell membrane; octadecyl dimethyl trimethylsilylpropyl ammonium chloride is added to adsorb on the surface of bacteria through electrostatic interaction to further assist in damaging the bacterial cell membrane; that is, gallic acid and octadecyl dimethyl trimethylsilylpropyl ammonium chloride can cooperate to cause bacterial death, increasing the antibacterial effect of the system.

[0039] (4) The leather finishing agent provided by this invention has the functions of wear resistance, hydrophobicity and antibacterial property. Taking water resistance as the basic property for anti-fouling, supplemented by wear resistance to resist external physical abrasion, to a certain extent reducing the chance of stain attachment. In addition, it also effectively inhibits the growth of microorganisms with antibacterial property, starting from three aspects to jointly reduce the accumulation of stains on the leather surface. In this way, it can effectively make the leather finished product prepared with the leather finishing agent of this invention have an excellent anti-fouling effect. Specific embodiments

[0040] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than 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 making creative efforts belong to the scope of protection of the present invention.

[0041] For the zinc acetate used in the examples, comparative examples and test examples of the present invention, the brand is Qianyao, purchased from Langfang Qianyao Technology Co., Ltd.; for the carboxylated carbon nanotubes used, the product number is HQNANO-CNTs-006-3H, the brand is Beike Nano, purchased from Suzhou Kaifa New Materials Technology Co., Ltd.; for the acrylic acid and butyl acrylate used, the brands are both Kejian, both purchased from Shandong Kejian Chemical Industry Co., Ltd.; for the methyl methacrylate used, the brand is Chuangying, purchased from Shandong Chuangying Chemical Industry Co., Ltd.; for the sodium styrene sulfonate used, the brand is Jiyesheng, purchased from Wuhan Jiyesheng Chemical Industry Co., Ltd.; the alkyd resin models used include SM3230, purchased from Jiangsu Sanmu Chemical Co., Ltd.

[0042] Example 1

[0043] A method for preparing wear-resistant and stain-resistant leather, comprising the following steps:

[0044] A1. Prepare a leather finishing solution;

[0045] A2. The leather blank is sequentially subjected to surface dust removal, cleaning, air drying and polishing, then sprayed with the leather finishing solution, and then dried, polished and waxed to obtain the wear-resistant and stain-resistant leather finished product;

[0046] The method for preparing the leather finishing solution described in step A1 comprises the following steps:

[0047] S1. Mix zinc acetate, diethylene glycol monoethyl ether and deionized water evenly, control the temperature at 170 °C and stir for 8 min, let stand at room temperature for 1.5 h, add carboxylated carbon nanotubes and hydrochloric acid dopamine, and ultrasonically disperse for 30 min. Control the temperature at 170 °C and stir for 1 h, centrifuge, wash twice with anhydrous ethanol and distilled water respectively, and dry at 105 °C for 11 h to obtain the carboxylated carbon nanotube zinc oxide composite;

[0048] The dosage ratio of the zinc acetate, diethylene glycol monoethyl ether, deionized water, carboxylated carbon nanotubes and hydrochloric acid dopamine is 1 g: 250 mL: 11 mL: 1.1 g: 3 g;

[0049] S2. Mix methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate in a mass ratio of 8:10.5:0.7:0.73, then control the temperature at 70 °C and pre-stir for 20 min to obtain premix A; mix methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate in a mass ratio of 8:10.5:0.7:0.73, then control the temperature at 70 °C and pre-stir for 23 min to obtain premix B; mix ammonium persulfate and distilled water in a mass ratio of 0.45:40 evenly to obtain an initiator solution; mix sodium dodecyl sulfate and Tween 80 in a mass ratio of 0.6:1 evenly to obtain an emulsion; mix silane coupling agent KH-550, octadecyl dimethyl trimethylsilylpropyl ammonium chloride, deionized water, and absolute ethanol in a mass ratio of 10:1:10:15, control the temperature at 55 °C and stir for 2 h to obtain mixture A;

[0050] S3. Add sodium bicarbonate, the emulsion, premix A, and alkyd resin to the carboxylated carbon nanotube zinc oxide composite, heat up to 80 °C, dropwise add the initiator solution, and then stir to obtain mixture B;

[0051] The mass ratio of the carboxylated carbon nanotube zinc oxide composite, sodium bicarbonate, the emulsion, premix A, and alkyd resin is 2.5:0.9:0.65:12:7; the addition amount of the initiator solution is 0.8 times the mass of acrylic acid in premix A; the initiator solution is added dropwise within 1 h;

[0052] S4. Dropwise add premix B and the initiator solution to mixture B simultaneously. After the addition is complete, control the temperature at 70 °C and let it stand for 1 h. Then add mixture A and phenyltrimethoxysilane, control the temperature at 82.5 °C and let it stand for 1.5 h. Add gallic acid and let it stand for 1 h. Adjust the pH = 6 at room temperature using sodium bicarbonate and stir for 10 min to obtain the leather finishing liquid;

[0053] The addition amount of premix B is 2 times the mass of premix A; the addition amount of the initiator solution is 0.81 of the mass of acrylic acid in premix B; the mass ratio of mixture B, mixture A, phenyltrimethoxysilane, and gallic acid is 20:1.8:1:1.5.

[0054] Example 2

[0055] A method for preparing wear-resistant and stain-resistant leather, comprising the following steps:

[0056] A1. Prepare the leather finishing liquid;

[0057] A2. The leather blank is successively subjected to surface dust removal, cleaning, air drying, and polishing, then sprayed with the leather finishing liquid, and then dried, polished, and waxed to obtain the wear-resistant and stain-resistant leather finished product;

[0058] The method for preparing the leather finishing liquid described in step A1 includes the following steps:

[0059] S1. After uniformly mixing zinc acetate, diethylene glycol monoethyl ether and deionized water, control the temperature at 180 °C and stir for 5 min, let it stand at room temperature for 2 h, add carboxylated carbon nanotubes and dopamine hydrochloride, ultrasonically disperse for 35 min, control the temperature at 173 °C and stir for 1.5 h, centrifuge, wash 3 times with absolute ethanol and distilled water in sequence, control the temperature at 100 °C and dry for 10 h to obtain carboxylated carbon nanotube zinc oxide composite material;

[0060] The dosage ratio of zinc acetate, diethylene glycol monoethyl ether, deionized water, carboxylated carbon nanotubes and dopamine hydrochloride is 1.05 g: 245 mL: 10 mL: 1.2 g: 5 g;

[0061] S2. Mix methyl methacrylate, butyl acrylate, acrylic acid and sodium styrene sulfonate according to the mass ratio of 11: 12: 1: 0.75, control the temperature at 72.5 °C and pre-stir for 25 min to obtain premixed material A; Mix methyl methacrylate, butyl acrylate, acrylic acid and sodium styrene sulfonate according to the mass ratio of 11: 12: 1: 0.75, control the temperature at 75 °C and pre-stir for 20 min to obtain premixed material B; Mix ammonium persulfate and distilled water according to the mass ratio of 0.5: 42.5 uniformly to obtain initiator solution; Mix sodium dodecylbenzenesulfonate and span 80 according to the mass ratio of 0.5: 1 uniformly to obtain emulsion; Mix silane coupling agent KH-550, octadecyldimethyltrimethylsilylpropyl ammonium chloride, deionized water and absolute ethanol according to the mass ratio of 11: 1: 12.5: 10, control the temperature at 57.5 °C and stir for 2.5 h to obtain mixture A;

[0062] S3. Add sodium bicarbonate, emulsion, premixed material A and alkyd resin to the carboxylated carbon nanotube zinc oxide composite material, heat up to 75 °C, dropwise add the initiator solution and then stir to obtain mixture B;

[0063] The mass ratio of the carboxylated carbon nanotube zinc oxide composite material, sodium bicarbonate, emulsion, premixed material A and alkyd resin is 5: 0.8: 0.68: 10: 8; The addition amount of the initiator solution is 0.82 times the mass of acrylic acid in premixed material A; The initiator solution is added dropwise within 1 h;

[0064] S4. Dropwise add premixed material B and the initiator solution to mixture B simultaneously. After dropping, control the temperature at 77.5 °C and let it stand for 2 h, then add mixture A and phenyltrimethoxysilane, control the temperature at 80 °C and let it stand for 2 h, add gallic acid and let it stand for 1 h, adjust the pH = 6 at room temperature with sodium bicarbonate and stir for 15 min to obtain leather finishing agent;

[0065] The addition amount of premixed material B is 2.2 times the mass of premixed material A; The addition amount of the initiator solution is 0.8 of the mass of acrylic acid in premixed material B; The mass ratio of mixture B, mixture A, phenyltrimethoxysilane and gallic acid is 18: 2: 0.9: 1.75.

[0066] Example 3

[0067] A method for preparing wear-resistant and stain-resistant leather comprises the following steps:

[0068] A1. Prepare leather finishing liquid;

[0069] A2. The leather blank is subjected to surface dust removal, cleaning, air drying, and polishing, and then sprayed with leather finishing liquid. The leather blank is then dried, polished, and waxed to obtain a wear-resistant and stain-resistant leather product.

[0070] The method for preparing the leather finishing liquid described in step A1 comprises the following steps:

[0071] S1. After zinc acetate, diethylene glycol and deionized water are uniformly mixed, the mixture is stirred at 175°C for 6 minutes, and the mixture is allowed to stand at room temperature for 2 hours. Carboxylated carbon nanotubes and dopamine hydrochloride are added and ultrasonically dispersed for 32.5 minutes. The mixture is stirred at 175°C for 1 hour, centrifuged, washed with anhydrous ethanol and distilled water three times in sequence, and dried at 110°C for 12 hours to obtain a carboxylated carbon nanotube zinc oxide composite.

[0072] The zinc acetate, diethylene glycol, deionized water, carboxylated carbon nanotubes, and dopamine hydrochloride are used in a ratio of 1.1 g:248 mL:12 mL:1.2 g:4 g;

[0073] S2. Methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate were mixed in a mass ratio of 9.5:11:0.85:0.7, and the mixture was pre-stirred at 75°C for 22 min to obtain premix A; methyl methacrylate, butyl acrylate, acrylic acid, and sodium styrene sulfonate were mixed in a mass ratio of 9.5:111:0.85:0.7, and the mixture was pre-stirred at 72°C for 25 min to obtain premix B; ammonium persulfate and distilled water were mixed in a mass ratio of 0.4:45 to obtain an initiating solution; sodium lauryl sulfate and Tween 80 were mixed in a mass ratio of 0.55:1 to obtain an emulsion; silane coupling agent KH-550, octadecyldimethyltrimethylsilylpropylammonium chloride, deionized water, and anhydrous ethanol were mixed in a mass ratio of 10.5:1:15:12.5 to obtain a mixture A at 60°C for 3 h.

[0074] S3, adding sodium bicarbonate, emulsion, premix A and alkyd resin to the carboxylated carbon nanotube zinc oxide composite, heating to 78° C., adding initiator solution dropwise and stirring to obtain mixture B;

[0075] The mass ratio of the carboxylated carbon nanotube zinc oxide composite, sodium bicarbonate, emulsion, premix A, and alkyd resin is 3.8:1:0.7:11:7.5; the amount of the initiator solution added is 0.81 times the mass of the acrylic acid in the premix A; the initiator solution is dripped in 1 hour;

[0076] S4. Simultaneously dropwise add premix B and the initiating solution into mixture B. After the addition is complete, control the temperature at 85 °C and let it stand for 1.5 h. Then add mixture A and phenyltrimethoxysilane, control the temperature at 85 °C again and let it stand for 2 h. Add gallic acid and let it stand for 2 h. Adjust the pH to 6 at room temperature using sodium bicarbonate and stir for 12.5 min to obtain the leather finishing liquid;

[0077] The addition amount of the premix B is 2.1 times the mass of the premix A; the addition amount of the initiating solution is 0.82 of the mass of acrylic acid in the premix B; the mass ratio of the mixture B, mixture A, phenyltrimethoxysilane and gallic acid is 19:1.9:0.8:2.

[0078] Comparative Example 1

[0079] Compared with Example 3, alkyd resin is not added in Comparative Example 1, and the remaining operation steps and parameters remain unchanged.

[0080] Comparative Example 2

[0081] Compared with Example 3, sodium styrenesulfonate is not added in Comparative Example 2, and the remaining operation steps and parameters remain unchanged.

[0082] Comparative Example 3

[0083] Compared with Example 3, phenyltrimethoxysilane is not added in Comparative Example 3, and the remaining operation steps and parameters remain unchanged.

[0084] Comparative Example 4

[0085] Compared with Example 3, hydrochloric acid dopamine is not added in step S1 of Comparative Example 4, and the remaining operation steps and parameters remain unchanged.

[0086] Comparative Example 5

[0087] Compared with Example 3, the carboxylated carbon nanotube zinc oxide composite is not added in step S3 of Comparative Example 5, and the remaining operation steps and parameters remain unchanged.

[0088] Comparative Example 6

[0089] Compared with Example 3, gallic acid is not added in step S4 of Comparative Example 6, and the remaining operation steps and parameters remain unchanged.

[0090] Comparative Example 7

[0091] Compared with Example 3, mixture A is not added in step S4 of Comparative Example 7, and the remaining operation steps and parameters remain unchanged.

[0092] Test Example 1

[0093] According to QB / T 2726-2005, the leather prepared in Examples 1-3 and Comparative Examples 1-3 was subjected to abrasion resistance testing using a CS-10 grinding wheel under test conditions of a load of 1000 g and a test rotation speed of 1000 revolutions. Evaluation criteria: The test grades are divided into five grades: A, obvious wear; B, relatively obvious wear; C, distinguishable wear; D, difficult to see wear; E, no wear visible; the results are shown in Table 1.

[0094] Table 1

[0095] Wear resistance Example 1 E Example 2 E Example 3 E Comparative Example 1 C Comparative Example 2 C Comparative Example 3 D

[0096] As can be seen from Table 1, the leather prepared by the present invention has excellent abrasion resistance.

[0097] Test Example 2

[0098] (1) Static water-drop waterproof test: The leather prepared in Examples 1-3 and Comparative Examples 4-5 was clamped at both ends and tightened with clips, and water droplets were dropped onto the leather surface at a rate of one drop per second using a dropper, and the surface state of the leather was observed after 100 min; the results are shown in Table 2.

[0099] (2) Static immersion waterproof test: The leather prepared in Examples 1-3 and Comparative Examples 4-5 was immersed in water at room temperature for 24 hours, and the time at which water penetration occurred in each group of leather was observed; the results are shown in Table 2.

[0100] Table 2

[0101]

[0102] As can be seen from Table 2, the leather prepared by the present invention has excellent waterproof effect.

[0103] Test Example 3

[0104] Referring to QB / T 4341-2012, the antibacterial properties of the leather prepared in Examples 1-3 and Comparative Examples 6-7 were tested (Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538P, Candida albicans ATCC10231), and the results are shown in Table 3.

[0105] Table 2

[0106]

[0107] As can be seen from Table 3, the leather prepared by the present invention has excellent antibacterial effect.

[0108] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

[0109] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar ways to substitute, as long as they do not deviate from the concept of the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing wear-resistant and stain-resistant leather, characterized in that, It includes the following steps: A1. Prepare the leather finishing liquid; A2. The leather blank is successively subjected to surface dust removal, cleaning, air drying and sanding, then the leather finishing liquid is sprayed, and then dried, polished and waxed to obtain the finished wear-resistant and stain-resistant leather; The preparation method of the leather finishing liquid described in step A1 includes the following steps: S1. Prepare the carboxylated carbon nanotube zinc oxide composite; S2. Pretreat part of the raw materials to obtain premix A, premix B, initiator solution, emulsion and mixture A; S3. Add sodium bicarbonate, emulsion, premix A and alkyd resin to the carboxylated carbon nanotube zinc oxide composite, heat up and dropwise add the initiator solution, and then stir to obtain mixture B; S4. Dropwise add premix B and the initiator solution to mixture B at the same time. After dropping, control the temperature and let it stand still. Then add mixture A and phenyltrimethoxysilane, control the temperature and let it stand still again. Add gallic acid and let it stand still, adjust the pH, and stir to obtain the leather finishing liquid.

2. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, wherein, Step S1 specifically includes the following steps: Mix zinc acetate, diethylene glycol monomethyl ether and deionized water evenly, stir at a controlled temperature for the first time, let it stand still, add carboxylated carbon nanotubes and dopamine hydrochloride, ultrasonically disperse, stir at a controlled temperature for the second time, centrifuge, wash, and dry at a controlled temperature to obtain the carboxylated carbon nanotube zinc oxide composite.

3. The preparation method of the wear-resistant and stain-resistant leather according to claim 2, wherein, The dosage ratio of zinc acetate, diethylene glycol monomethyl ether, deionized water, carboxylated carbon nanotubes and dopamine hydrochloride described in step S1 is 1 - 1.1 g: 245 - 250 mL: 10 - 12 mL: 1.1 - 1.2 g: 3 - 5 g.

4. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, wherein, Step S2 specifically includes: Mix methyl methacrylate, butyl acrylate, acrylic acid and sodium styrenesulfonate, and pre-stir at a controlled temperature to obtain premix A; Mix methyl methacrylate, butyl acrylate, acrylic acid and sodium styrenesulfonate, and pre-stir at a controlled temperature to obtain premix B; Mix the initiator and distilled water evenly to obtain the initiator solution; Mix the emulsifiers evenly to obtain the emulsion; Control the temperature and stir the silane coupling agent, octadecyl dimethyl trimethylsilylpropyl ammonium chloride, deionized water and absolute ethanol to obtain mixture A.

5. The preparation method of the wear-resistant and stain-resistant leather according to claim 4, characterized in that, The mass ratio of methyl methacrylate, butyl acrylate, acrylic acid and sodium styrenesulfonate in premix A and premix B is 8 - 11: 10.5 - 12: 0.7 - 1: 0.7 - 0.75; The mass ratio of the initiator and distilled water is 0.4 - 0.5: 40 - 45; The emulsifier includes a mixture of an anionic emulsifier and a non-ionic emulsifier in a mass ratio of 0.5 - 0.6:

1.

6. The preparation method of the wear-resistant and stain-resistant leather according to claim 4, characterized in that, The initiator includes ammonium persulfate; The anionic emulsifier includes sodium dodecyl sulfate or sodium dodecylbenzenesulfonate; The non-ionic emulsifier includes span 80 or tween 80; The silane coupling agent includes KH-550.

7. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, wherein The mass ratio of the carboxylated carbon nanotube zinc oxide composite, sodium bicarbonate, emulsion, premix A and alkyd resin described in step S3 is 2.5 - 5: 0.8 - 1: 0.65 - 0.7: 10 - 12: 7 - 8; The addition amount of the initiator solution is 0.8 - 0.82 times the mass of acrylic acid in premix A.

8. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, wherein, The addition amount of premix B described in step S4 includes 2 - 2.2 times the mass of premix A.

9. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, characterized in that, The addition amount of the initiating liquid described in step S4 is 0.8 - 0.82 of the mass of acrylic acid in premix B.

10. The preparation method of the wear-resistant and stain-resistant leather according to claim 1, characterized in that, The mass ratio of premix B, premix A, phenyltrimethoxysilane and gallic acid described in step S4 is 18 - 20:1.8 - 2:0.8 - 1:1.5 - 2.

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