A method for manufacturing children's shoes with antioxidant leather uppers

Abstract

This application discloses a method for manufacturing antioxidant leather children's shoes. The method for manufacturing antioxidant leather children's shoes includes the following steps: (1) spraying anhydrous ethanol onto the surface of the leather base layer, then immersing it in water, stirring at a temperature of 80-90℃, and drying to obtain a treated leather base layer; (2) coating the surface of the leather base layer treated in step (1) with an adhesive, then bonding an anti-tear layer, and drying at a temperature of 90-95℃ to obtain a composite layer; (3) spraying a treatment agent onto the surface of the composite layer obtained in step (2), drying, and then bonding and sewing the leather upper to the sole together, followed by heat bonding and shaping treatment to obtain antioxidant leather children's shoes; the treatment agent includes the following raw materials: polyether glycol, isopropanol, antioxidant, organosilicon, ethyl acetate, modified montmorillonite, zinc stearate, and paraffin. The antioxidant leather children's shoes prepared in this application have good mechanical properties, wear resistance, and softness.

Description

Technical Field

[0001] This application relates to the technical field of leather, and in particular to a method for manufacturing children's shoes with an antioxidant leather upper. Background Technology

[0002] Children's shoes are specifically designed for children aged 0-16, emphasizing lightweight, breathability, comfort, and durability. They are broadly categorized into three types: children's leather shoes, sneakers, and sandals. Among these, children's leather shoes are popular due to their excellent shock absorption, increased stability while walking, and prevention of ankle sprains during running and jumping.

[0003] Children's leather shoes are typically made using processes such as gluing, sewing, molding, vulcanization, injection molding, and casting, with natural leather, artificial leather, and synthetic leather as the upper material. Currently, leather is the most common material for children's shoe uppers. It is made of tightly woven collagen fibers, but collagen fibers have low mechanical strength and poor abrasion resistance, resulting in leather with poor abrasion resistance and low strength. This makes them prone to damage after prolonged use, thus affecting the lifespan of the children's shoes. Summary of the Invention

[0004] In order to improve the problem of poor abrasion resistance and low strength of children's leather shoes, which are prone to damage after long-term use, this application provides a method for manufacturing children's shoes with antioxidant leather uppers.

[0005] This application provides a method for manufacturing children's shoes with antioxidant leather uppers, using the following technical solution:

[0006] A method for manufacturing children's shoes with antioxidant leather uppers includes the following steps:

[0007] (1) Spray anhydrous ethanol onto the surface of the leather base material, then soak it in water, stir it at 80-90℃ for 20-25 minutes, and dry it to obtain the treated leather base material.

[0008] (2) Apply adhesive to the surface of the leather base layer treated in step (1), then bond the tear-resistant layer, and dry it at a temperature of 90-95℃ to obtain the composite layer;

[0009] (3) Spray the composite layer surface treatment agent obtained in step (2) and dry it at a temperature of 85-90℃. For the leather upper, glue and sew the leather upper and the sole together, and perform heat bonding and shaping treatment to obtain antioxidant leather children's shoes.

[0010] The treatment agent comprises the following raw materials: polyether glycol, isopropanol, antioxidant, organosilicon, ethyl acetate, modified montmorillonite, zinc stearate, and paraffin.

[0011] By adopting the above technical solution, anhydrous ethanol is first sprayed on the surface of the leather to remove grease and dirt. Then, the leather is soaked in water at a temperature of 80-90℃ to soften it. Next, an adhesive is applied, and an anti-tear layer is applied to the surface of the adhesive to improve the tear resistance of the leather. Finally, a treatment agent is sprayed on the surface of the composite layer to obtain a surface layer with wear resistance and oxidation resistance.

[0012] Polyether glycols possess good heat resistance, chemical corrosion resistance, and excellent flexibility and elasticity. Isopropanol improves the adhesion and flowability of the system, making the prepared treatment agent easier to apply and bond. Antioxidants protect the system from oxidation and mitigate the effects of high temperature, light, and chemical corrosion, thereby effectively extending the service life of the adhesive. Organosilicones have good thermal stability, antioxidant properties, and lubricity, increasing the adhesion, flexibility, and elasticity of the system. Ethyl acetate improves the viscosity of the system, enhances the coatability and drying properties of the treatment agent, and does not affect the color and transparency of the treatment agent.

[0013] Modified montmorillonite possesses excellent mechanical properties, wear resistance, weather resistance, and chemical resistance. Adding modified montmorillonite enhances the wear resistance and mechanical strength of the treatment agent, resulting in a composite layer with superior wear resistance and mechanical properties. Zinc stearate significantly reduces the viscosity of the treatment agent and improves its plasticity. Paraffin wax acts as a lubricant in the treatment agent, reducing friction and lowering the system viscosity, making the treatment agent easier to apply. The various raw material components work together to improve the wear resistance and oxidation resistance of the treatment agent, providing better protection for leather children's shoes.

[0014] Preferably, the tear-resistant layer comprises, by weight, the following raw materials: 30-50 parts polyurethane resin, 14-18 parts nano-ceramic adhesive powder, 2-5 parts zinc stearate, 12-16 parts lauroyl diethanolamine, 16-20 parts modified sepiolite fiber, 8-12 parts activated clay, 6-10 parts chitosan, 3-6 parts nonylphenol polyoxyethylene ether, and 0.5-1 parts plasticizer.

[0015] By adopting the above technical solutions, polyurethane resin exhibits high strength, tear resistance, and abrasion resistance; nano-ceramic powder possesses good mechanical strength and abrasion resistance; its addition to the system can improve the system's hardness and toughness; zinc stearate serves as a heat stabilizer and lubricant, ensuring uniform mixing of all components and improving the system's dispersibility; lauroyl diethanolamine possesses good stability, thickening, permeability, rust prevention, and detergency, and exhibits good biocompatibility; when mixed with other components, it improves the system's viscosity; modified sepiolite fiber possesses good thermal stability, corrosion resistance, friction resistance, and impermeability, thereby enhancing the system's overall performance.

[0016] Activated clay possesses strong adsorption and viscosity properties. Nano-ceramic adhesive powder can be loaded onto the surface of modified sepiolite fibers. Activated clay enhances the adhesion between the nano-ceramic adhesive powder and the modified sepiolite fibers, thereby improving the mechanical properties, wear resistance, and tear resistance of the system. Chitosan can coat the nano-ceramic adhesive powder, modified sepiolite fibers, and activated clay, further improving the mechanical properties of the system and ensuring tight bonding among the raw materials. Nonylphenol polyoxyethylene ether has good dispersibility and emulsifying properties, enabling uniform mixing of the raw materials. Plasticizers can adjust the viscosity and flowability of the system, improve its flexibility and extensibility, and thus enhance the corresponding properties of the system.

[0017] Preferably, the method for preparing the modified sepiolite fiber includes the following steps:

[0018] (1) Soak the sepiolite fiber in hydrochloric acid solution for 10-20 min, wash with water, then disperse it in silane coupling agent aqueous solution, stir at 90-95℃ for 2-4 h, filter, dry, and obtain the treated sepiolite fiber.

[0019] (2) Crush the loofah sponge, disperse it in sodium hydroxide solution, stir it at 75-80℃ for 1-3 hours, wash it with water, disperse it in anhydrous ethanol, add nano titanium dioxide, sonicate it for 2-3 hours, and dry it to obtain the treated loofah sponge.

[0020] (3) Disperse the sepiolite fiber treated in step (1) in deionized water, add the loofah sponge treated in step (2), stir at 80-90℃ for 1-2 hours, then add sodium alginate and continue stirring to obtain modified sepiolite fiber.

[0021] By adopting the above technical solution, sepiolite fiber has high specific surface area and porosity. Hydrochloric acid solution removes organic impurities from sepiolite fiber, further improving its porosity. Silane coupling agent organically modifies sepiolite fiber. The silane coupling agent adsorbs or intercalates into sepiolite, increasing the interlayer spacing of sepiolite and facilitating the intercalation of subsequent components.

[0022] Sodium hydroxide treatment of loofah sponge causes partial swelling, altering its surface properties and facilitating the loading of nano-titanium dioxide onto the surface and within the pores of the loofah sponge. This increases the mechanical properties and weather resistance of the loofah sponge. When sepiolite fibers and loofah sponge are mixed, they cross-link to form a network structure, further improving the mechanical properties of the sepiolite fibers. Sodium alginate coating of the sepiolite fibers and loofah sponge increases the adhesion between them, further enhancing the structural stability of the sepiolite fibers and thus contributing to the subsequent improvement of their tear resistance and other mechanical properties.

[0023] Preferably, the mass ratio of sepiolite fiber, loofah sponge and sodium alginate is 1:0.6-0.9:0.03-0.08.

[0024] By adopting the above technical solution, the mass ratio of sepiolite fiber, loofah sponge, and sodium alginate is further limited within a certain range to obtain modified sepiolite fiber with better mechanical properties. The sepiolite fiber and loofah sponge are cross-linked to form a network structure. Sodium alginate coats the sepiolite fiber and loofah sponge, which increases the connectivity between the sepiolite fiber and loofah sponge, helps the stability of the system structure, and thus improves the relevant mechanical properties of the tear-resistant layer.

[0025] Preferably, the plasticizer is one or more of diisooctyl phthalate, chlorinated paraffin oil, and dioctyl sebacate.

[0026] By adopting the above technical solution, plasticizers help improve the fluidity of the system, adjust the viscosity between the components in the system, and enable the components to mix better, thereby improving the fluidity and flexibility of the system and facilitating the preparation of subsequent layers.

[0027] Preferably, the treatment agent comprises, by weight, the following raw materials: 15-30 parts of polyether glycol, 8-12 parts of isopropanol, 0.5-0.8 parts of antioxidant, 3-5 parts of organosilicon, 8-12 parts of ethyl acetate, 13-24 parts of modified montmorillonite, 6-10 parts of zinc stearate, and 5-8 parts of paraffin wax.

[0028] By adopting the above technical solution, the dosage of each component is further limited, which improves the wear resistance and oxidation resistance of the treatment agent. Each component has better performance within a certain mass ratio range, making the treatment agent easy to apply. The treatment agent obtained after drying has better wear resistance and mechanical properties.

[0029] Preferably, the preparation method of the modified montmorillonite includes the following steps:

[0030] (1) Disperse montmorillonite in deionized water, stir for 1-2 hours, dry, and then calcine at 300-350℃ for 2-3 hours to obtain treated montmorillonite;

[0031] (2) Disperse glass fiber in sodium hydroxide solution, stir at 80-90℃ for 1-3 hours, then wash with water, disperse in anhydrous ethanol, add nano silica, stir for 2-3 hours, and dry to obtain treated glass fiber;

[0032] (3) Disperse the montmorillonite treated in step (1) in a polyvinyl alcohol solution, add the glass fiber treated in step (2), stir at 60-70℃ for 1-3 hours, filter, and dry to obtain modified montmorillonite.

[0033] By adopting the above technical solution, montmorillonite has superior mechanical properties, impact resistance, fatigue resistance, and dimensional stability. Calcination of montmorillonite removes organic impurities, thereby increasing its porosity and facilitating the loading of subsequent components.

[0034] Glass fiber has good heat resistance, corrosion resistance and mechanical strength, but poor wear resistance. Sodium hydroxide solution erodes the surface of glass fiber to a certain extent, making the surface rough and increasing the surface roughness of glass fiber. Nano-silica can be loaded on the surface and pores of glass fiber, thereby improving the mechanical properties and wear resistance of glass fiber.

[0035] Montmorillonite is dispersed in a polyvinyl alcohol solution, and then treated glass fibers are added. The glass fibers can be loaded onto the surface of the montmorillonite. Polyvinyl alcohol has a certain viscosity, which can increase the adhesion between the glass fibers and montmorillonite, so that the glass fibers are firmly loaded on the surface of the montmorillonite, thereby improving the mechanical properties and wear resistance of the montmorillonite. When used in subsequent treatment agents, it can improve the mechanical properties of the treatment agents.

[0036] Preferably, the mass ratio of montmorillonite, glass fiber and nano-silica is 1:0.3-0.6:0.07-0.09.

[0037] By adopting the above technical solution, the mass ratio of montmorillonite, glass fiber, and nano-silica is further limited within a certain range, resulting in modified montmorillonite with better mechanical properties and wear resistance. Nano-silica is loaded on the surface of glass fiber, and glass fiber is loaded on the surface of montmorillonite, thereby improving the corresponding properties of montmorillonite. When subsequently applied to treatment agents, it further improves the relevant properties of the treatment agents.

[0038] Preferably, the antioxidant is antioxidant 168 and / or antioxidant 1076.

[0039] By adopting the above technical solution, antioxidants are used to capture active free radicals, thereby interrupting the chain reaction, slowing down the oxidation process and speed of the treatment agent, and thus protecting the leather children's shoes from oxidation.

[0040] Preferably, the adhesive is made by mixing styrene, neoprene rubber and PVC resin in a mass ratio of 6-10:1:3-5.

[0041] By adopting the above technical solutions, styrene has the characteristics of high temperature resistance and chemical corrosion resistance, and can maintain the bonding effect in harsh environments; neoprene rubber has high adhesion and good corrosion resistance, and PVC resin has superior durability, anti-aging ability and adhesion; the mixture of styrene, neoprene rubber and PVC resin not only improves the adhesion of the adhesive, but also makes the adhesive have good heat resistance, cold resistance and durability, so that the adhesive has good long-term use.

[0042] In summary, this application has the following beneficial effects:

[0043] 1. In this application, anhydrous ethanol is sprayed onto the surface of the leather to remove grease and dirt. Then, the leather is soaked in water at a temperature of 80-90°C to soften it. Then, an adhesive is applied, and an anti-tear layer is applied to the adhesive surface to improve the tear resistance of the leather. Finally, a treatment agent is sprayed onto the surface of the composite layer to obtain a surface layer with wear resistance and oxidation resistance.

[0044] 2. In this application, polyether glycol has good heat resistance, chemical corrosion resistance, good flexibility and elasticity; isopropanol can improve the adhesion and flowability of the system, making the prepared treatment agent easier to apply and stick; antioxidants protect the system from oxidation and can also reduce the effects of high temperature, light and chemical corrosion, thereby effectively extending the service life of the adhesive; organosilicon increases the adhesion, flexibility and elasticity of the system; ethyl acetate can improve the viscosity of the system, improve the coatability and drying properties of the treatment agent, and does not affect the color and transparency of the treatment agent.

[0045] 3. The modified montmorillonite in this application has good mechanical properties, wear resistance, weather resistance, and chemical resistance. Adding modified montmorillonite improves the wear resistance and mechanical strength of the treatment agent, resulting in a composite layer surface with good wear resistance and mechanical properties. Zinc stearate can significantly reduce the viscosity of the treatment agent and improve its plasticity. Paraffin wax has a lubricating effect in the treatment agent, reducing friction and lowering the viscosity of the system, making the treatment agent easier to apply. The various raw material components work together to improve the wear resistance and oxidation resistance of the treatment agent, providing better protection for leather children's shoes. Detailed Implementation

[0046] The present application will be further described in detail below with reference to the embodiments.

[0047] The raw materials used in the examples and comparative examples are all commercially available. The silane coupling agent is silane coupling agent KH570, the plasticizer is diisooctyl phthalate, and the antioxidant is antioxidant 168.

[0048] Preparation example of modified sepiolite fiber

[0049] Preparation Example 1-1

[0050] The preparation method of modified sepiolite fiber includes the following steps:

[0051] (1) Soak 1.2 kg of sepiolite fiber in 2 L of 18% hydrochloric acid solution for 15 min, wash with water, and then disperse in 3 L of 0.3% silane coupling agent aqueous solution. Stir at 95℃ for 3 h, filter, and dry to obtain treated sepiolite fiber.

[0052] (2) Crush the loofah sponge, disperse it in 1.5L of sodium hydroxide solution with a mass fraction of 8%, stir it at 80℃ for 3h, wash it with water, disperse it in 2.5L of anhydrous ethanol, add 0.2kg of nano titanium dioxide, sonicate it for 3h, and dry it to obtain the treated loofah sponge.

[0053] (3) Disperse the sepiolite fiber treated in step (1) in 3L of deionized water, add the loofah sponge treated in step (2), stir at 85℃ for 2h, then add sodium alginate, and continue stirring for 3L to obtain modified sepiolite fiber; wherein, the mass ratio of sepiolite fiber, loofah sponge and sodium alginate is 1:0.6:0.03.

[0054] Preparation Examples 1-2

[0055] The difference from preparation example 1-1 is that no loofah sponge is added in step (2).

[0056] Preparation Examples 1-3

[0057] The difference from preparation example 1-1 is that nano-titanium dioxide is not added in step (2).

[0058] Preparation Examples 1-4

[0059] The difference from preparation example 1-1 is that sodium alginate is not added in step (3).

[0060] Preparation Examples 1-5

[0061] The difference from Preparation Example 1-1 is that the mass ratio of sepiolite fiber, loofah sponge and sodium alginate is 1:0.9:0.08.

[0062] Preparation Examples 1-6

[0063] The difference from Preparation Example 1-1 is that the mass ratio of sepiolite fiber, loofah sponge and sodium alginate is 1:0.2:0.1.

[0064] Preparation example of modified montmorillonite

[0065] Preparation Example 2-1

[0066] The preparation method of modified montmorillonite includes the following steps:

[0067] (1) Disperse 0.9 kg of montmorillonite in 2 L of deionized water, stir for 2 h, dry, and then calcine at 350 °C for 2 h to obtain the treated montmorillonite;

[0068] (2) Disperse glass fiber in 2L of sodium hydroxide solution with a mass fraction of 12%, stir at 85℃ for 3h, then wash with water, disperse in 2L of anhydrous ethanol, add nano silica, stir for 3h, and dry to obtain treated glass fiber.

[0069] (3) Disperse the montmorillonite treated in step (1) in 2.5L of a 0.3% polyvinyl alcohol solution, add the glass fiber treated in step (2), stir at 65℃ for 3h, filter, and dry to obtain modified montmorillonite; wherein the mass ratio of montmorillonite, glass fiber and nano silica is 1:0.3:0.07.

[0070] Preparation Example 2-2

[0071] The difference from preparation example 2-1 is that glass fiber is not added in step (2).

[0072] Preparation Examples 2-3

[0073] The difference from preparation example 2-1 is that no nano-silica is added in step (2).

[0074] Preparation Examples 2-4

[0075] The difference from Preparation Example 2-1 is that the polyvinyl alcohol solution is replaced with an aqueous solution.

[0076] Preparation Examples 2-5

[0077] The difference from Preparation Example 2-1 is that the mass ratio of montmorillonite, glass fiber and nano-silica is 1:0.6:0.09.

[0078] Preparation Examples 2-6

[0079] The difference from Preparation Example 2-1 is that the mass ratio of montmorillonite, glass fiber and nano-silica is 1:0.1:0.12.

[0080] Example

[0081] Example 1

[0082] A method for manufacturing children's shoes with antioxidant leather uppers includes the following steps:

[0083] (1) Spray anhydrous ethanol onto the surface of the leather base material, then soak it in 2L of water, stir it at 85℃ for 25min, and dry it to obtain the treated leather base material.

[0084] (2) Coat the surface of the leather base layer treated in step (1) with adhesive, then bond the tear-resistant layer, and dry it at 95°C to obtain a composite layer, wherein the thickness of the adhesive is 0.1 mm and the thickness of the tear-resistant layer is 0.2 mm.

[0085] (3) The composite layer obtained in step (2) is sprayed with a treatment agent and dried at a temperature of 90°C. The leather upper is then bonded and sewn together with the sole and subjected to heat bonding and shaping treatment to obtain an antioxidant leather children's shoe. The thickness of the treatment agent is 0.1 mm.

[0086] The treatment agent, by weight, comprises the following raw materials: 15 kg of polyether glycol, 8 kg of isopropanol, 0.5 kg of antioxidant, 3 kg of organosilicon, 12 kg of ethyl acetate, 13 kg of modified montmorillonite, 6 kg of zinc stearate, and 8 kg of paraffin wax.

[0087] The tear-resistant layer, by weight, comprises the following raw materials: 30 kg of polyurethane resin, 14 kg of nano-ceramic adhesive powder, 5 kg of zinc stearate, 12 kg of lauroyl diethanolamine, 20 kg of modified sepiolite fiber, 12 kg of activated clay, 10 kg of chitosan, 3 kg of nonylphenol polyoxyethylene ether, and 1 kg of plasticizer.

[0088] The adhesive is made of a mixture of styrene, neoprene rubber, and PVC resin in a mass ratio of 6:1:3;

[0089] Modified sepiolite fiber was prepared using Preparation Example 1-1; modified montmorillonite was prepared using Preparation Example 2-1.

[0090] Example 2

[0091] A method for manufacturing an antioxidant leather children's shoe differs from Example 1 in that the treatment agent, by weight, includes the following raw materials: 30 kg of polyether glycol, 12 kg of isopropanol, 0.8 kg of antioxidant, 5 kg of organosilicon, 8 kg of ethyl acetate, 24 kg of modified montmorillonite, 10 kg of zinc stearate, and 5 kg of paraffin wax.

[0092] Example 3

[0093] A method for manufacturing an antioxidant leather children's shoe differs from Example 1 in that the tear-resistant layer, by weight, comprises the following raw materials: 50 kg of polyurethane resin, 18 kg of nano-ceramic adhesive powder, 2 kg of zinc stearate, 16 kg of lauroyl diethanolamine, 16 kg of modified sepiolite fiber, 8 kg of activated clay, 6 kg of chitosan, 6 kg of nonylphenol polyoxyethylene ether, and 0.5 kg of plasticizer.

[0094] Example 4

[0095] A method for manufacturing an antioxidant leather children's shoe differs from Example 1 in that the adhesive is made by mixing styrene, neoprene rubber, and PVC resin in a mass ratio of 10:1:5.

[0096] Example 5

[0097] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified sepiolite fiber is prepared using Preparation Examples 1-2.

[0098] Example 6

[0099] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified sepiolite fiber is prepared using Preparation Examples 1-3.

[0100] Example 7

[0101] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified sepiolite fiber is prepared using Preparation Examples 1-4.

[0102] Example 8

[0103] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified sepiolite fiber is prepared using Preparation Examples 1-5.

[0104] Example 9

[0105] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified sepiolite fiber is prepared using Preparation Examples 1-6.

[0106] Example 10

[0107] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified montmorillonite is prepared using Preparation Example 2-2.

[0108] Example 11

[0109] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified montmorillonite is prepared using Preparation Examples 2-3.

[0110] Example 12

[0111] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified montmorillonite is prepared using Preparation Examples 2-4.

[0112] Example 13

[0113] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified montmorillonite is prepared using Preparation Examples 2-5.

[0114] Example 14

[0115] A method for manufacturing antioxidant leather children's shoes, which differs from Example 1 in that the modified montmorillonite is prepared using Preparation Examples 2-6.

[0116] Comparative Example

[0117] Comparative Example 1

[0118] A method for manufacturing an antioxidant leather children's shoe, which differs from Example 1 in that no tear-resistant layer is added.

[0119] Comparative Example 2

[0120] A method for manufacturing antioxidant leather children's shoes differs from Example 1 in that no treatment agent is added.

[0121] Comparative Example 3

[0122] A method for manufacturing antioxidant leather children's shoes differs from Example 1 in that modified montmorillonite is not added to the treatment agent.

[0123] Comparative Example 4

[0124] A method for manufacturing antioxidant leather children's shoes differs from Example 1 in that an equal amount of montmorillonite is used instead of modified montmorillonite.

[0125] The performance testing was conducted on the antioxidant leather children's shoes prepared in Examples 1-14 and Comparative Examples 1-4. The tensile strength was tested according to QB / T 2710, the tear strength was tested according to GBT17928-1999, and the elongation at break was tested according to GB / T 24218.3 2010.

[0126] The softness of leather was tested according to NF G52-033-2012 "Leather Physical and Mechanical Tests - Determination of Softness" using a leather softness tester with a shrinkage ring diameter of 35 mm.

[0127] The abrasion resistance (cycles) of leather was tested according to ASTM D 3885-2007a, "Standard Test Method for Abrasion Resistance of Textiles". The results are shown in Table 1.

[0128] Table 1 Test data for the examples and comparative examples

[0129]

[0130]

[0131] As shown in Table 1, the antioxidant leather children's shoes prepared in Examples 1-4, 8, and 13 of this application exhibit good mechanical properties, softness, and abrasion resistance. Specifically, in Example 1, the tensile strength reached 19 N / mm, the tear strength reached 75.3 N / mm, the elongation at break reached 89.23%, the softness reached 9.45 mm, and the abrasion resistance reached 4956 cycles. This indicates that the various raw material components work together to improve the mechanical properties, abrasion resistance, and antioxidant properties of the treatment agent, thus providing better protection for the leather children's shoes.

[0132] In Example 5, the modified sepiolite fiber was prepared without the addition of loofah sponge. Table 1 shows that the tensile strength reached 10 N / mm, the tear strength reached 64.1 N / mm, the elongation at break reached 78.12%, the softness reached 6.23 mm, and the abrasion resistance reached 4210 cycles. This indicates that the sepiolite fiber and loofah sponge cross-link to form a network structure, thereby improving the mechanical properties, abrasion resistance, and softness of the sepiolite fiber.

[0133] In Example 6, the modified sepiolite fiber was prepared without the addition of nano-titanium dioxide. Table 1 shows that the tensile strength reached 12 N / mm, the tear strength reached 65.5 N / mm, the elongation at break reached 79.23%, the softness reached 6.98 mm, and the abrasion resistance reached 4320 cycles. This indicates that the nano-titanium dioxide loaded on the surface and pores of the loofah sponge increased its mechanical properties and weather resistance. Subsequent mixing of the loofah sponge with sepiolite fiber further enhanced the corresponding properties of the sepiolite fiber.

[0134] In Example 7, the modified sepiolite fiber was prepared without sodium alginate. Table 1 shows that the tensile strength reached 13 N / mm, the tear strength reached 66.4 N / mm, the elongation at break reached 80.23%, the softness reached 7.12 mm, and the abrasion resistance reached 4430 cycles. This indicates that the coating of sepiolite fiber and loofah with sodium alginate increases the adhesion between them, further improving the structural stability of the sepiolite fiber, which in turn helps to improve the tear resistance and other mechanical properties of the sepiolite fiber.

[0135] Example 9 changed the mass ratio of sepiolite fiber, loofah sponge, and sodium alginate. As shown in Table 1, the tensile strength, tear strength, elongation at break, softness, and abrasion resistance of the antioxidant leather children's shoes were higher than those of Examples 5 and 7, but lower than those of Examples 1-4 and Example 8. This indicates that the sepiolite fiber and loofah sponge cross-link to form a network structure, and the sodium alginate coating of the sepiolite fiber and loofah sponge increases the connectivity between them, which helps the stability of the system structure and thus improves the related mechanical properties of the tear-resistant layer.

[0136] In Example 10, the modified montmorillonite was prepared without the addition of glass fiber. Table 1 shows that the tensile strength reached 8 N / mm, the tear strength reached 60.1 N / mm, the elongation at break reached 72.12%, the flexibility reached 6.01 mm, and the abrasion resistance reached 4100 cycles. This indicates that glass fiber has good heat resistance, good corrosion resistance, and high mechanical strength. Glass fiber can be loaded onto the surface of montmorillonite, thereby improving its corresponding properties.

[0137] In Example 11, the modified montmorillonite was prepared without the addition of nano-silica. Table 1 shows that the tensile strength reached 10 N / mm, the tear strength reached 62.1 N / mm, the elongation at break reached 74.21%, the flexibility reached 6.13 mm, and the abrasion resistance reached 4190 cycles. This indicates that nano-silica can be loaded onto the surface and pores of glass fibers, thereby improving the mechanical properties and abrasion resistance of the glass fibers.

[0138] In Example 12, the preparation method of modified montmorillonite involved replacing the polyvinyl alcohol solution with an aqueous solution. Table 1 shows that the tensile strength reached 11 N / mm, the tear strength reached 64.1 N / mm, the elongation at break reached 75.23%, the flexibility reached 6.23 mm, and the abrasion resistance reached 4200 cycles. This indicates that polyvinyl alcohol has a certain viscosity, which can increase the adhesion between glass fiber and montmorillonite, allowing the glass fiber to be firmly loaded on the surface of montmorillonite, thereby improving the mechanical properties and abrasion resistance of montmorillonite. Subsequent application in treatment agents can improve the mechanical properties of the treatment agent.

[0139] Example 14 changed the mass ratio of montmorillonite, glass fiber, and nano-silica. As shown in Table 1, the tensile strength, tear strength, elongation at break, softness, and abrasion resistance of the antioxidant leather children's shoes were higher than those of Examples 10 and 11, but lower than those of Examples 1-4 and 13. This indicates that the nano-silica was loaded on the surface of the glass fiber, and the glass fiber was loaded on the surface of the montmorillonite, thereby improving the corresponding properties of the montmorillonite. When applied to the treatment agent, this improved the relevant properties of the treatment agent.

[0140] In Comparative Example 1, without the addition of an anti-tear layer, Table 1 shows that the tensile strength reached 4 N / mm, the tear strength reached 40.2 N / mm, the elongation at break reached 55.12%, the softness reached 4.12 mm, and the abrasion resistance reached 3840 cycles. This indicates that the anti-tear layer can significantly improve the tensile strength, tear strength, elongation at break, softness, and abrasion resistance of children's shoes with antioxidant leather uppers.

[0141] In Comparative Example 2, without the added treatment agent, Table 1 shows that the tensile strength reached 6 N / mm, the tear strength reached 50.1 N / mm, the elongation at break reached 62.13%, the softness reached 5.64 mm, and the abrasion resistance reached 3900 cycles. This indicates that the treatment agent can significantly improve the tensile strength, tear strength, elongation at break, softness, and abrasion resistance of the antioxidant leather children's shoes.

[0142] Comparative Example 3, without modified montmorillonite, showed the following results in the treatment agent: tensile strength reached 7 N / mm, tear strength reached 55.2 N / mm, elongation at break reached 67.33%, flexibility reached 5.98 mm, and abrasion resistance reached 3970 cycles. This indicates that modified montmorillonite possesses good mechanical properties, abrasion resistance, weather resistance, and chemical resistance. Adding modified montmorillonite improves the abrasion resistance and mechanical strength of the treatment agent, resulting in a composite layer surface with superior abrasion resistance and mechanical properties.

[0143] In Comparative Example 4, an equal amount of montmorillonite was used instead of modified montmorillonite in the treatment agent. Table 1 shows that the tensile strength reached 8 N / mm, the tear strength reached 59.2 N / mm, the elongation at break reached 70.12%, the softness reached 6.23 mm, and the abrasion resistance reached 4000 cycles. This indicates that the montmorillonite prepared in this application has superior abrasion resistance and mechanical strength, which can further improve the corresponding properties of antioxidant leather children's shoes.

[0144] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for manufacturing children's shoes with antioxidant leather uppers, characterized in that, Includes the following steps: (1) Spray anhydrous ethanol onto the surface of the leather base material, then immerse it in water, stir at 80-90℃ for 20-25 minutes, and dry it to obtain the treated leather base material; (2) Apply adhesive to the surface of the leather base layer treated in step (1), then bond the tear-resistant layer, and dry it at a temperature of 90-95℃ to obtain the composite layer; (3) Spray the composite layer surface treatment agent obtained in step (2) and dry it at a temperature of 85-90℃ to obtain leather upper. Adhere and sew the leather upper to the sole together and perform heat bonding and shaping treatment to obtain antioxidant leather children's shoes. The treatment agent, by weight, comprises the following raw materials: 15-30 parts of polyether glycol, 8-12 parts of isopropanol, 0.5-0.8 parts of antioxidant, 3-5 parts of organosilicon, 8-12 parts of ethyl acetate, 13-24 parts of modified montmorillonite, 6-10 parts of zinc stearate, and 5-8 parts of paraffin wax. The preparation method of the modified montmorillonite includes the following steps: (1) Disperse montmorillonite in deionized water, stir for 1-2 hours, dry, and then calcine at 300-350℃ for 2-3 hours to obtain treated montmorillonite; (2) Disperse glass fiber in sodium hydroxide solution, stir at 80-90℃ for 1-3 hours, then wash with water, disperse in anhydrous ethanol, add nano silica, stir for 2-3 hours, and dry to obtain treated glass fiber; (3) Disperse the montmorillonite treated in step (1) in a polyvinyl alcohol solution, add the glass fiber treated in step (2), stir at 60-70℃ for 1-3 hours, filter, and dry to obtain modified montmorillonite; The mass ratio of montmorillonite, glass fiber, and nano-silica is 1:0.3-0.6:0.07-0.

09.

2. The method for manufacturing an antioxidant leather children's shoe according to claim 1, characterized in that, The tear-resistant layer comprises, by weight, the following raw materials: 30-50 parts polyurethane resin, 14-18 parts nano-ceramic adhesive powder, 2-5 parts zinc stearate, 12-16 parts lauroyl diethanolamine, 16-20 parts modified sepiolite fiber, 8-12 parts activated clay, 6-10 parts chitosan, 3-6 parts nonylphenol polyoxyethylene ether, and 0.5-1 parts plasticizer.

3. The method for manufacturing an antioxidant leather children's shoe according to claim 2, characterized in that, The method for preparing the modified sepiolite fiber includes the following steps: (1) Soak the sepiolite fiber in hydrochloric acid solution for 10-20 min, wash with water, then disperse it in silane coupling agent aqueous solution, stir at 90-95℃ for 2-4 h, filter, dry, and obtain the treated sepiolite fiber; (2) Crush the loofah sponge, disperse it in sodium hydroxide solution, stir it at 75-80℃ for 1-3 hours, wash it with water, disperse it in anhydrous ethanol, add nano titanium dioxide, sonicate it for 2-3 hours, and dry it to obtain the treated loofah sponge. (3) Disperse the sepiolite fiber treated in step (1) in deionized water, add the loofah sponge treated in step (2), stir at 80-90℃ for 1-2 hours, then add sodium alginate and continue stirring to obtain modified sepiolite fiber.

4. The manufacturing method of an antioxidant leather children's shoe according to claim 3, characterized in that, The mass ratio of sepiolite fiber, loofah sponge and sodium alginate is 1:0.6-0.9:0.03-0.

08.

5. The method for manufacturing an antioxidant leather children's shoe according to claim 2, characterized in that, The plasticizer is one or more of diisooctyl phthalate, chlorinated paraffin oil, and dioctyl sebacate.

6. The method for manufacturing an antioxidant leather children's shoe according to claim 1, characterized in that, The antioxidant is antioxidant 168 and / or antioxidant 1076.

7. The method for manufacturing an antioxidant leather children's shoe according to claim 1, characterized in that, The adhesive is made by mixing styrene, neoprene rubber and PVC resin in a mass ratio of 6-10:1:3-5.

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