Preparation method of bionic anti-skid sole

Abstract

The invention discloses a preparation method of a bionic anti-slip sole, and belongs to the technical field of shoe material preparation. Nitrile rubber with a reasonable proportion is adopted, and the characteristics of large friction and strong hysteresis between chain segments and fillers of the nitrile rubber are utilized to prepare the bionic anti-slip sole which is resistant to wet and slip on an ice surface; a wet water film on the ice surface is punctured through the flexible convex racks of the bionic thin-line-shaped structure, so that water molecules are adsorbed under the capillary action and the molecular action of the network-shaped grooves, and the bottom, making contact with the interface of the ice surface, of the bionic anti-skid shoe sole does not slip due to the influence of the water film on the surface of the ice surface. Therefore, the wet skid resistance of the prepared bionic anti-skid sole on the ice surface is improved.

Description

TECHNICAL FIELD

[0001] The application discloses a shoe material preparation technology, and particularly relates to a preparation method of a bionic antiskid shoe sole. BACKGROUND

[0002] The structure of a shoe sole is quite complex, and in a broad sense, can include all materials constituting the bottom, such as an outsole, a midsole and a heel. In a narrow sense, only the outsole is referred to, and the common characteristics of a shoe sole material should include wear resistance, water resistance, oil resistance, heat resistance, pressure resistance, impact resistance, good elasticity, easy adaptation to a foot shape, difficulty in shape change after shaping, heat preservation, easy moisture absorption and the like, and the shoe sole material should also be matched with the midsole to have the functions of braking, preventing from slipping and stopping, and the like.

[0003] The existing antiskid shoes have poor skid resistance on wet ground, especially when walking on snow and ice, the surface of ice has a liquid water film, and the heat generated by the pressure and friction of the shoe sole on the ice surface can also melt the surface of the ice to form a wet water film surface, and walking on the wet water film surface is easy to slip and cause the wearer to fall, and therefore, a shoe sole with excellent antiskid performance is needed. SUMMARY

[0004] The application aims to solve the above problems and provides a preparation method of a bionic antiskid shoe sole.

[0005] To achieve the above object, the application provides the following technical scheme: a preparation method of a bionic antiskid shoe sole, comprising the following steps: The following components are calculated by mass parts: S1, 100 parts of nitrile rubber are added to a plastic mixer for plasticizing, 4 parts of zinc oxide and 1 part of stearic acid are added at 75 DEG C, and then 5-25 parts of modified terpene resin, 1 part of rubber accelerator DM, 1 part of rubber accelerator CZ, 1 part of antioxidant 6-di-tert-butyl-p-cresol, 3 parts of coupling agent KH-550 are sequentially added, 20-60 parts of white carbon black, 10 parts of naphthenic oil and 10 parts of plasticizer DOP are added at a temperature of 95 DEG C, and the mixer is turned over after being heated to 130 DEG C to obtain a plasticized rubber material, and the plasticized rubber material is added to a mixing mill and mixed with 2 parts of sulfur, and the obtained base rubber material is cooled after being discharged. S2, mold preparation, an aluminum alloy powder bed selective laser melting deposition modeling is selected, a mold is constructed by using a modular partition laser melting selection, a circular truncated cone-shaped concave pattern of a soft pad area is formed at the center of the heel and metatarsal area of the mold by laser melting, and the mold is processed by laser digital bite flower to form a ring-shaped arrangement of fine line-shaped structure concave patterns along the soft pad area, and a conformal waterway cooling process is formed by additive manufacturing. S3, Injection Molding Preparation: 1 part of silica nanoparticles is deposited onto 15 parts of UVO-treated pre-shrinked polystyrene base material, 5 parts of nano-zirconia particles are added, and cross-linking is promoted using 1H,1H,2H,2H-perfluorooctyl to form a modified zirconia-polydimethylsiloxane compound. 20 parts of the modified zirconia-polydimethylsiloxane compound are coated onto the bottom surface of the mold. 80 parts of the base compound, heated by an injection molding machine, are injected into the mold and vacuumed. After cooling through a conformal water cooling process, the mold is demolded to obtain the biomimetic non-slip shoe sole.

[0006] Preferably, the silica used is 40 parts.

[0007] Preferably, 15 parts of the modified terpene resin are used.

[0008] Preferably, the grooves are provided with a network of protrusions.

[0009] Compared with the prior art, the beneficial effects of the present invention are: This invention uses a reasonable proportion of nitrile rubber and leverages the high friction and strong hysteresis between nitrile rubber segments and fillers to prepare a biomimetic anti-slip sole for use on ice. The flexible, convex toothed structure with a biomimetic fine-line structure pierces the wet water film on the ice surface, causing water molecules to be adsorbed by capillary action and molecular action in the network of grooves. The bottom of the biomimetic anti-slip sole, in contact with the ice surface, is not affected by the water film and therefore does not slip, thus improving the anti-slip performance of the prepared biomimetic anti-slip sole on ice. Attached Figure Description

[0010] Figure 1 This is a schematic diagram of the structure of a biomimetic anti-slip shoe sole; Figure 2 Schematic diagram of a network-like trench structure Figure 1 ; Figure 3 Schematic diagram of a network-like trench structure Figure 2 ; Figure 4 Charts showing the physical properties of biomimetic anti-slip shoe soles with different vinyl cyanide mass fractions; Figure 5 Charts showing the physical properties of biomimetic anti-slip shoe soles with different amounts of modified terpene resin; Figure 6 Charts showing the physical properties of biomimetic anti-slip shoe soles with different amounts of silica. Detailed Implementation

[0011] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. In this description, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0012] A method for preparing a biomimetic anti-slip shoe sole includes the following steps: The following components are listed in parts by mass: S1. Add 100 parts of nitrile rubber to a mixer for plasticizing. Add 4 parts of zinc oxide and 1 part of stearic acid at 75°C. Then add 5-25 parts of modified terpene resin, 1 part of rubber accelerator DM, 1 part of rubber accelerator CZ, 1 part of antioxidant 6-di-tert-butyl-p-cresol, and 3 parts of coupling agent KH-550 in sequence. Heat to 95°C and add 20-60 parts of silica, 10 parts of naphthenic oil, and 10 parts of plasticizer DOP. Heat to 130°C and turn the material over to obtain the mixed rubber compound. Add the mixed rubber compound to a two-roll mill and 2 parts of sulfur for mixing. After cooling the discharged material, obtain the base rubber compound. The physical properties of biomimetic anti-slip shoe soles prepared with nitrile rubber of different vinyl cyanide contents were tested using 40 parts of modified terpene resin and 5 parts of silica. The test scheme is as follows: Option ①: Vinyl cyanide mass fraction is 19%; Option 2: The mass fraction of vinyl cyanide is 29%; Option ③: Vinyl cyanide mass fraction is 33%; Option 4: Vinyl cyanide mass fraction is 41%; like Figure 4 As shown, with the increase of vinyl cyanide mass fraction, the dynamic friction coefficient of the biomimetic anti-slip sole also increases. This is because with the increase of vinyl cyanide content, the interaction force between molecular chains in nitrile rubber increases, reducing the free volume of molecular chains, which increases the friction between chain segments and fillers, enhances hysteresis, and thus improves the anti-slip performance. However, when the vinyl cyanide mass fraction exceeds 29%, the elongation at break begins to decrease, and when the vinyl cyanide mass fraction exceeds 33%, the tear strength begins to decrease. Therefore, while ensuring the anti-slip performance, nitrile rubber with a vinyl cyanide mass fraction of 33% is selected as the material for preparing the biomimetic anti-slip sole. The physical properties of biomimetic anti-slip shoe soles prepared with different mass fractions of modified terpene resin (33% vinyl cyanide and 0 parts silica) were tested according to the following scheme: Option I: 5 parts modified terpene resin; Option II: 10 parts modified terpene resin; Option III: 15 parts of modified terpene resin; Option IV: 20 parts of modified terpene resin; Option V: 25 parts modified terpene resin; like Figure 5 As shown, the anti-slip performance of the biomimetic anti-slip sole gradually improves with the increase of modified terpene resin dosage. This is because the modified terpene resin can be effectively dispersed into the base rubber during processing and gradually migrates to the surface of the biomimetic anti-slip sole, effectively increasing the surface modulus of the biomimetic anti-slip sole. The sole surface is more likely to penetrate the water film, increasing the contact area at the interface of wet and slippery ice surfaces, thereby improving the anti-slip ability. However, with the increase of modified terpene resin dosage, the wear resistance decreases sharply. This is because during the blending process of modified terpene resin with nitrile rubber, its short chains penetrate into the macromolecular chain segments, thereby increasing the glass transition temperature of nitrile rubber, increasing the internal friction of the molecular chains, and thus reducing the wear resistance. Considering the cost and process difficulty of modified terpene resin, in order to reduce the dosage while ensuring anti-slip performance and not reduce the wear resistance too much, a dosage of 15 parts of modified terpene resin was selected, which has both a high wet dynamic friction coefficient and high wear resistance.

[0013] The physical properties of biomimetic anti-slip shoe soles prepared with different mass fractions of silica were tested using a vinyl cyanide content of 33% and a modified terpene resin content of 15 parts. The test scheme is as follows: Option 1: 20 parts of silica; Option 2: 30 parts of silica; Option 3: 40 parts of silica; Option 4: 50 parts of silica; Option 5: 60 parts of silica; like Figure 6As shown, the elongation at break and tear strength of the biomimetic anti-slip sole decrease with increasing silica content. This is because increasing silica content reduces the rubber content in the base rubber compound, leading to a decrease in elongation at break and tear strength. The wet slip resistance of the biomimetic anti-slip sole increases with silica content, reaching its highest level at 40 parts silica. This is because silica filling with nitrile rubber enhances the sole's ability to expel water film from the ice surface, resulting in some dry friction between the sole and the contact surface, thus increasing the coefficient of friction and enhancing wet slip resistance. However, further increasing silica content increases the sole's hardness, reducing deformation upon contact with the ground and decreasing dry friction, ultimately lowering the slip resistance. Therefore, a silica content of 40 parts silica was selected.

[0014] The above physical tests were conducted in accordance with GB / T528—2009 and GB / T3903.6—2017.

[0015] S2, Mold preparation: Selective laser melting deposition modeling of aluminum alloy powder bed, modular partitioned laser melting selective area construction of mold, forming frustum-shaped concave texture of soft pad area in the center of the heel and metatarsal areas of the mold by laser melting, and forming a ring-shaped fine line structure concave texture along the soft pad area of ​​the mold under laser digital texturing, and cooling process of conformal water channel by additive manufacturing. High-energy laser beams are used to scan point by point to achieve powder metallurgy bonding, thereby printing aluminum alloy shoe molds. This technology can also process complex shoe mold textures and patterns, and process the network of raised and fine line structured concave patterns between concave patterns, replacing the chemical reagent etching process. S3, Injection Molding Preparation: 1 part of silica nanoparticles is deposited onto 15 parts of UVO-treated pre-shrinked polystyrene base material. UVO ultraviolet ozone treatment utilizes the synergistic effect of ultraviolet light and ozone to modify the material surface. Specific wavelengths of ultraviolet light, such as 185 nm and 254 nm, excite oxygen in the air to generate ozone and active oxygen. These substances react with target molecules to change their chemical structure. 5 parts of nano-zirconia particles are added, and cross-linking is promoted using 1H,1H,2H,2H-perfluorooctyl to form a modified zirconia-polydimethylsiloxane compound. 20 parts of the modified zirconia-polydimethylsiloxane compound are coated onto the bottom surface of the mold. 80 parts of the base compound, heated by an injection molding machine, are injected into the mold, vacuumed, and then cooled using a conformal water cooling process before demolding to obtain the biomimetic anti-slip shoe sole.

[0016] Silica is reacted with polystyrene base material via vapor deposition to form polydimethylsiloxane adhesive. Then, nano-zirconia particles are added. These nano-zirconia particles are pre-activated with hydroxyl groups and then cross-linked with 1H,1H,2H,2H-perfluorooctyl groups. The hydroxyl groups of the polydimethylsiloxane adhesive combine with the nano-zirconia particles to form a modified zirconia-polydimethylsiloxane adhesive. This modified zirconia-polydimethylsiloxane adhesive is coated onto the bottom surface of a mold to form a 1mm thick layer. The base adhesive is then injected for further lamination. Because the modified zirconia-polydimethylsiloxane adhesive produces a graded textured surface after heat shrinkage, and is activated by vinyl cyanide in the base adhesive, it creates a high 3D effect and low encapsulation density on the inner surface of the mold cavity. This improves the anti-adhesion between the bottom surface of the biomimetic anti-slip shoe sole and the inner surface of the mold cavity, enhancing the integrity and molding rate during demolding. Biomimetic anti-slip shoe soles prepared in this way... Figure 1 As shown, the prepared biomimetic anti-slip sole has a frustum-shaped protrusion at the center of the heel and metatarsal areas, and flexible serrated strips with a fine linear structure are formed outward from the two centers, and as... Figures 2-3 As shown, there are network-like grooves between the flexible convex teeth. In reptiles and amphibians, such as geckos, salamanders and tree frogs, the feet have surface microstructures that have good adsorption and frictional stability on wet and slippery lotus leaves or leaves. The biomimetic anti-slip shoe sole is designed to mimic the surface microstructure of the foot.

[0017] When the biomimetic anti-slip sole is stepped on a slippery ice surface, the pressure on the foot is mainly released in the heel and metatarsal areas located in the cushioned area. The frustum-shaped protrusions are forced to deform and indent, causing the flexible serrated strips and network-like grooves to deform and increase the contact area with the slippery ice surface. Because the surface of the biomimetic anti-slip sole is a modified zirconium oxide-polydimethylsiloxane thin layer, the Si-O-Si silicon-oxygen bonds in polydimethylsiloxane have significant surface hydrophobicity, which can block the penetration of water from the water film on the ice surface. However, when the water film on the slippery ice surface is punctured by the flexible serrated strips and Si-O-Si silicon-oxygen bonds, the increased deformation of the network-like grooves absorbs water molecules from the punctured water film through capillary action. Furthermore, due to the Si-O-Si silicon-oxygen bonds in polydimethylsiloxane... The polarity of Si differs from that of nano-zirconia, causing the nano-zirconia to be predominantly dispersed in the network-like grooves. The hydroxyl groups at the active sites in the nano-zirconia act as molecular interactions, adsorbing water molecules from the punctured water film and temporarily storing them in the network-like grooves. This means that when the bionic anti-slip sole comes into contact with ice, the water film on the ice surface is punctured and adsorbed into the network-like grooves, while the bottom, in contact with the ice surface, is not affected by the water film and thus does not slip. This improves the anti-slip performance of the bionic anti-slip sole on ice. Furthermore, after lifting the foot, the heel and metatarsal areas, which were forced into flexible deformation, recover, and the deformation of the flexible serrations and network-like grooves decreases, disrupting the molecular forces between the water molecules temporarily stored in the network-like grooves and the active sites in the nano-zirconia, causing the water molecules to be expelled.

[0018] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0019] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing a biomimetic anti-slip shoe sole, characterized in that: Includes the following steps: The following components are listed in parts by mass: S1. Add 100 parts of nitrile rubber to a mixer for plasticizing. Add 4 parts of zinc oxide and 1 part of stearic acid at 75°C. Then add 5-25 parts of modified terpene resin, 1 part of rubber accelerator DM, 1 part of rubber accelerator CZ, 1 part of antioxidant 6-di-tert-butyl-p-cresol, and 3 parts of coupling agent KH-550 in sequence. Heat to 95°C and add 20-60 parts of silica, 10 parts of naphthenic oil, and 10 parts of plasticizer DOP. Heat to 130°C and turn the material over to obtain the mixed rubber compound. Add the mixed rubber compound to a two-roll mill and 2 parts of sulfur for mixing. After cooling the discharged material, obtain the base rubber compound. S2, Mold preparation: Selective laser melting deposition modeling of aluminum alloy powder bed, modular partitioned laser melting selective area construction of mold, forming frustum-shaped concave texture of soft pad area in the center of the heel and metatarsal areas of the mold by laser melting, and forming a ring-shaped fine line structure concave texture along the soft pad area of ​​the mold under laser digital texturing, and cooling process of conformal water channel by additive manufacturing. S3, Injection Molding Preparation: 1 part of silica nanoparticles is deposited onto 15 parts of UVO-treated pre-shrinked polystyrene base material, 5 parts of nano-zirconia particles are added, and cross-linking is promoted using 1H,1H,2H,2H-perfluorooctyl to form a modified zirconia-polydimethylsiloxane compound. 20 parts of the modified zirconia-polydimethylsiloxane compound are coated onto the bottom surface of the mold. 80 parts of the base compound, heated by an injection molding machine, are injected into the mold and vacuumed. After cooling through a conformal water cooling process, the mold is demolded to obtain the biomimetic non-slip shoe sole.

2. The method for preparing a biomimetic anti-slip shoe sole according to claim 1, characterized in that: The amount of silica used is 40 parts.

3. The method for preparing a biomimetic anti-slip shoe sole according to claim 1, characterized in that: The modified terpene resin was used in 15 parts.

4. The method for preparing a biomimetic anti-slip shoe sole according to claim 1, characterized in that: The grooves are arranged with a network of protrusions.

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