Antiskid and yellowing-resistant composite shoe sole material and preparation method and application thereof

Abstract

The present application relates to a kind of antiskid yellowing-resistant composite shoe sole material and its preparation method and application.The antiskid yellowing-resistant composite shoe sole material includes the following weight parts of components: ethylene-vinyl acetate copolymer 69-83 parts, organic siloxane 5-20 parts, antioxidant 0.1-0.5 parts, crosslinking agent 0.1-1 part, zinc stearate 0.5-2 parts, light stabilizer 1-3 parts, foaming agent 1-2 parts, filler 5-8 parts.The composite shoe sole material provided by the present application has excellent antiskid performance, resilience and yellowing resistance, the friction coefficient on dry interface can reach 0.82, the friction coefficient on wet interface can reach 0.33, the resilience rate can reach 68%, and the yellowing resistance level in room temperature ultraviolet lamp environment and in high temperature sunlight environment can both reach five levels.

Description

Technical Field

[0001] This invention relates to the field of footwear materials technology, and in particular to a non-slip, yellowing-resistant composite sole material, its preparation method, and its application. Background Technology

[0002] In recent years, EVA soles have become widely popular due to their lightweight and comfortable wear. EVA soles are made from ethylene-vinyl acetate copolymer (EVA) material. These EVA soles offer high resilience and tensile strength, good toughness, excellent impact resistance and shock absorption, and can adapt to various climates and environments. Therefore, EVA materials are widely used in athletic shoes. However, existing EVA sole materials have relatively poor slip resistance and resistance to yellowing.

[0003] Chinese patent application CN109181088A discloses a shock-absorbing EVA shoe sole material, composed of the following raw materials in parts by weight: 100-200 parts ethylene-vinyl acetate copolymer, 5-15 parts silica, 2-5 parts magnesium stearate, 3-5 parts foaming agent, 30-50 parts inorganic filler, 0.5-1.5 parts accelerator, and 2-3 parts antioxidant. The EVA shoe sole material prepared by this method has moderate hardness, low specific gravity, excellent dimensional stability, and high compression set, exhibiting high energy absorption and high dimensional stability. Although this material contains one or more of diphenylamine, p-phenylenediamine, 2,6-tributyl-4-methylphenol, and disulfide as antioxidants, these antioxidants are prone to migration and precipitation during material processing and use, resulting in low effective concentrations and poor antioxidant effects, making the prepared EVA shoe sole material prone to yellowing.

[0004] Chinese patent application CN108794877A discloses a high-strength EVA shoe sole material prepared from the following raw materials in parts by weight: 35-40 parts EVA resin, 15-20 parts bisphenol A epoxy resin, 5-10 parts polystyrene-polydiene-polystyrene block copolymer, 20-30 parts solid-phase blend composed of calcium carbonate, barium sulfate, and aluminum hydroxide, 2-4 parts microcrystalline wax, 1-3 parts 2,6-di-tert-butyl-4-methylphenol, 2-5 parts toughening material, 2-3 parts curing agent, and 1-2 parts anti-aging agent. The material prepared by this method has the advantages of being lightweight, wear-resistant, slip-resistant, and having good dimensional stability. This patent uses 2,6-di-tert-butyl-4-methylphenol as an antioxidant and a mixture of titanium dioxide, zinc oxide, and o-hydroxybenzotricarbazole as an anti-aging agent. 2,6-di-tert-butyl-4-methylphenol is easily migrated and precipitated during the production and use of the material and is thus lost. At the same time, the presence of titanium dioxide reduces and affects the antioxidant effect, making the material prepared by this method prone to yellowing. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a non-slip, yellowing-resistant composite shoe sole material, its preparation method, and its application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a non-slip and yellowing-resistant composite shoe sole material, comprising the following components in parts by weight: 69-83 parts of ethylene-vinyl acetate copolymer, 5-20 parts of organosiloxane, 0.1-0.5 parts of antioxidant, 0.1-1 parts of crosslinking agent, 0.5-2 parts of zinc stearate, 1-3 parts of light stabilizer, 1-2 parts of foaming agent, and 5-8 parts of filler.

[0008] In a preferred embodiment of the present invention, the organosiloxane is styrene-ethyltrimethoxysilane.

[0009] The inventors discovered that, under the action of a crosslinking agent, the ethylene-vinyl acetate copolymer undergoes a grafting reaction in the molten state. Simultaneously, the vinyl groups in the organosiloxane undergo a crosslinking reaction with the ethylene-vinyl acetate copolymer. The resulting crosslinked structure effectively prevents the migration and precipitation of antioxidants, light stabilizers, fillers, and other components during the molding and preparation of shoe soles. This not only effectively improves the anti-slip properties of the composite material but also introduces the conjugated structure contained in the organosiloxane, effectively enhancing the yellowing resistance of the composite shoe sole material.

[0010] In a preferred embodiment of the present invention, the organosiloxane in the anti-slip and yellowing-resistant composite sole material is no more than 20% by weight, for example, it can be 5%, 8%, 10%, 12%, 15%, 18%, 20% or any two of these values.

[0011] The ethylene-vinyl acetate copolymer in the anti-slip and yellowing-resistant composite sole material shall be no less than 65% by weight, for example, it may be 65%, 70%, 72%, 75%, 78%, 80%, 82% or any two of these values.

[0012] Furthermore, the organosiloxane comprises 10-15% by weight in the anti-slip and yellowing-resistant composite sole material, and the ethylene-vinyl acetate copolymer comprises 72-77% by weight in the same material. When the amounts of organosiloxane and ethylene-vinyl acetate copolymer meet the above conditions, the prepared composite sole material can maintain high resilience while significantly improving anti-slip properties and yellowing resistance.

[0013] In a preferred embodiment of the present invention, the antioxidant is 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate.

[0014] In a preferred embodiment of the present invention, the crosslinking agent is at least one of dicumyl peroxide, 1,4-di-tert-butylperoxyisopropylbenzene, benzoyl peroxide, and dicumyl peroxide.

[0015] The inventors discovered that, under the action of a crosslinking agent, the ethylene-vinyl acetate copolymer undergoes a grafting reaction in the molten state. Simultaneously with the crosslinking reaction, the carbon-carbon double bond groups of the antioxidant react with the ethylene-vinyl acetate copolymer, causing small antioxidant molecules to graft onto the molecular chain of the crosslinked ethylene-vinyl acetate copolymer. This makes it less likely for the antioxidant to migrate and precipitate during the molding and preparation of the shoe sole, thereby significantly improving the yellowing resistance of the composite shoe sole material.

[0016] In a preferred embodiment of the present invention, the light stabilizer is zinc oxide.

[0017] This invention uses zinc oxide as a light stabilizer, which can effectively shield ultraviolet light. The combination of light stabilizer, antioxidant and organosiloxane can effectively improve the photo-oxidation resistance of composite materials, thereby improving the yellowing resistance of composite materials.

[0018] In a preferred embodiment of the present invention, the foaming agent is at least one of azodicarbonamide and azobisisobutyronitrile.

[0019] In a preferred embodiment of the present invention, the filler includes at least one of mica, talc, and titanium dioxide.

[0020] Secondly, the present invention provides a method for preparing a non-slip, yellowing-resistant composite shoe sole material as described in the first aspect, comprising the following steps:

[0021] S1. Antioxidant, a portion of ethylene-vinyl acetate copolymer and a portion of crosslinking agent are mixed and then cooled and granulated to obtain mixed masterbatch;

[0022] S2. The organosiloxane, filler, light stabilizer, zinc stearate and the remaining ethylene-vinyl acetate copolymer are mixed to obtain a compound;

[0023] S3. Add the mixing masterbatch, foaming agent and remaining crosslinking agent obtained in step S1 to the mixture obtained in step S2 and mix them. After cooling and granulation, the anti-slip and yellowing resistant composite shoe sole material is obtained.

[0024] In a preferred embodiment of the present invention, the weight ratio of antioxidant, ethylene-vinyl acetate copolymer and crosslinking agent in step S1 is antioxidant: crosslinking agent: ethylene-vinyl acetate copolymer = (0.1~0.5): (0.1~0.2): 10.

[0025] In a preferred embodiment of the present invention, in step S1, the mixing temperature is 100-120°C and the time is 25-40 min.

[0026] In a preferred embodiment of the present invention, in step S2, the mixing temperature is 90-100°C and the time is 5-15 minutes.

[0027] In a preferred embodiment of the present invention, in step S3, the mixing temperature is 110-120°C and the time is 20-40 min.

[0028] Thirdly, the present invention provides the application of a non-slip and yellowing-resistant composite sole material as described in the first aspect in the preparation of soles.

[0029] The application includes the following steps: the composite sole material is injected through an injection molding machine and then placed in an oven for baking. The temperature parameters of the injection molding machine are as follows: the temperature of the first stage is 85°C, the temperature of the second stage is 88°C, the temperature of the third stage is 90°C, the temperature of the fourth stage is 92°C, the temperature of the molding die is 175°C, the vulcanization time is 10 minutes, the baking temperature is 70-80°C, and the baking time is 30 minutes.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] (1) This invention utilizes the cross-linking reaction between vinyl groups in organosiloxanes and ethylene-vinyl acetate copolymers under the action of a cross-linking agent, which not only effectively improves the anti-slip properties of composite materials, but also introduces the conjugated structure contained in organosiloxanes, effectively improving the yellowing resistance of composite shoe sole materials.

[0032] (2) The present invention also utilizes the grafting reaction of ethylene-vinyl acetate copolymer in the molten state. During the cross-linking reaction, the carbon-carbon double bond groups of the antioxidant react with the ethylene-vinyl acetate copolymer, so that the small molecules of antioxidant are grafted onto the molecular chain of ethylene-vinyl acetate copolymer, making it difficult for the antioxidant to migrate and precipitate during the molding and preparation of shoe soles, thereby significantly improving the yellowing resistance of the composite shoe sole material.

[0033] (3) The composite sole material provided by the present invention has excellent anti-slip performance, resilience and yellowing resistance. The coefficient of friction on the dry interface can reach 0.82, the coefficient of friction on the wet interface can reach 0.33, the resilience rate can reach 68%, and the yellowing resistance level can reach level 5 in both room temperature ultraviolet lamp environment and high temperature sunlight environment. Detailed Implementation

[0034] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0035] To better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art will understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0036] Unless otherwise specified, the methods used in the following embodiments and comparative examples are conventional methods.

[0037] Unless otherwise specified, all materials and reagents used in the following examples and comparative examples are commercially available.

[0038] Example 1

[0039] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0040] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0041] S2. Add 70 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 7 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into an internal mixer and mix at 95°C for 10 minutes to obtain a mixture.

[0042] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0043] Example 2

[0044] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0045] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0046] S2. Add 67 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 10 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into a mixer and mix at 95°C for 10 min to obtain a mixture.

[0047] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0048] Example 3

[0049] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0050] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0051] S2. Add 65 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 12 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into an internal mixer and mix at 95°C for 10 minutes to obtain a mixture.

[0052] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0053] Example 4

[0054] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0055] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0056] S2. Add 62 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 15 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into a mixer and mix at 95°C for 10 minutes to obtain a mixture.

[0057] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0058] Example 5

[0059] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0060] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0061] S2. Add 59 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 18 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into a mixer and mix at 95°C for 10 min to obtain a mixture.

[0062] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0063] Example 6

[0064] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0065] S1. 0.1 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 100°C for 40 min. After cooling and granulation, the mixed masterbatch is obtained.

[0066] S2. 73 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 5 parts by weight of styrene ethyltrimethoxysilane, 0.5 parts by weight of zinc stearate, 3 parts by weight of zinc oxide, 4 parts by weight of mica and 4 parts by weight of talc are added to an internal mixer and mixed at 100°C for 5 minutes to obtain a mixture.

[0067] S3. Add the mixing masterbatch obtained in step S1, 2 parts by weight of azodicarbonamide and 0.4 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 120°C for 20 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0068] Example 7

[0069] This embodiment provides a non-slip and yellowing-resistant composite shoe sole material, the preparation method of which includes the following steps:

[0070] S1. 0.5 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.2 parts by weight of dicumyl peroxide are added to a mixer and mixed at 120°C for 25 minutes. After cooling and granulation, the mixed masterbatch is obtained.

[0071] S2. Add 60 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 20 parts by weight of styrene ethyltrimethoxysilane, 2 parts by weight of zinc stearate, 1 part by weight of zinc oxide, 2 parts by weight of mica and 3 parts by weight of talc into an internal mixer and mix at 90°C for 15 minutes to obtain a mixture.

[0072] S3. Add the mixing masterbatch obtained in step S1, 1 part by weight of azodicarbonamide and 1.3 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 110°C for 40 minutes, cool and granulate to obtain the anti-slip and yellowing resistant composite shoe sole material.

[0073] Comparative Example 1

[0074] This comparative example provides a composite shoe sole material, the preparation method of which includes the following steps:

[0075] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0076] S2. Add 77 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into a mixer and mix at 95°C for 10 minutes to obtain a mixture.

[0077] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the composite shoe sole material.

[0078] Comparative Example 2

[0079] This comparative example provides a composite shoe sole material, the preparation method of which includes the following steps:

[0080] S1. 75 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 12 parts by weight of styrene ethyltrimethoxysilane, 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc are added to an internal mixer and mixed at 95°C for 10 min to obtain a compound.

[0081] S2. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.2 parts by weight of dicumyl peroxide to the mixture obtained in step S1, mix at 115°C for 30 minutes, cool and granulate to obtain the composite shoe sole material.

[0082] Comparative Example 3

[0083] This comparative example provides a composite shoe sole material, the preparation method of which includes the following steps:

[0084] S1. 0.3 parts by weight of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, 10 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVA V5110J) and 0.1 parts by weight of dicumyl peroxide are added to a mixer and mixed at 110°C for 45 min. After cooling and granulation, the mixed masterbatch is obtained.

[0085] S2. Add 52 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 25 parts by weight of styrene ethyltrimethoxysilane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc into a mixer and mix at 95°C for 10 minutes to obtain a mixture.

[0086] S3. Add the mixing masterbatch obtained in step S1, 1.5 parts by weight of azodicarbonamide and 1.1 parts by weight of dicumyl peroxide to the mixture obtained in step S2, mix at 115°C for 30 minutes, cool and granulate to obtain the composite shoe sole material.

[0087] Comparative Example 4

[0088] This comparative example provides a composite shoe sole material. The preparation method of this material differs from that of Example 2 in that, in step S2 of this comparative example, 10 parts by weight of styrene ethyltrimethoxysilane were not added to the internal mixer. Step S2 of this comparative example is as follows: 67 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), hexamethyldisiloxane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica, and 3 parts by weight of talc are added to the internal mixer and mixed at 95°C for 10 minutes to obtain a compound.

[0089] Comparative Example 5

[0090] This comparative example provides a composite shoe sole material. The preparation method of this material differs from that of Example 2 in that, in step S2 of this comparative example, 10 parts by weight of styrene ethyltrimethoxysilane were not added to the internal mixer. Step S2 of this comparative example is as follows: 67 parts by weight of ethylene-vinyl acetate copolymer (from BASF Yangzi, model EVAV5110J), 10 parts by weight of vinyltrimethylsiloxane, 1 part by weight of zinc stearate, 2 parts by weight of zinc oxide, 4 parts by weight of mica and 3 parts by weight of talc are added to the internal mixer and mixed at 95°C for 10 minutes to obtain a compound.

[0091] Example of effect 1

[0092] Shoe soles were prepared using the materials obtained in the examples and comparative examples as raw materials. The preparation method of the shoe soles was as follows: the composite shoe sole material was injected through an injection molding machine, and then baked in an oven. The temperature parameters of the injection molding machine were as follows: the temperature of the first stage was 85°C, the temperature of the second stage was 88°C, the temperature of the third stage was 90°C, the temperature of the fourth stage was 92°C, the temperature of the molding die was 175°C, the vulcanization time was 10 min, the baking temperature was 70-80°C, and the baking time was 30 min. The prepared shoe soles were subjected to the following performance tests:

[0093] (1) Rebound rate: The rebound rate of each shoe sole was tested using a GT-7042-RE impact elasticity testing machine;

[0094] (2) Yellowing resistance: The yellowing resistance of each shoe sole was tested according to Method A and Method B in HG / T 3689-2014 "Test for Yellowing Resistance of Footwear";

[0095] (3) Anti-slip performance: The anti-slip performance of dry interface and wet interface was tested in accordance with the standard GB / T3903.6-2017 "General Test Methods for Footwear Anti-slip Performance".

[0096] The test results are shown in Table 1.

[0097] Table 1

[0098]

[0099] As can be seen from Examples 1-5 and Comparative Example 3, the weight percentage of the ethylene-vinyl acetate copolymer in the composite sole material of the present invention should not be less than 65%, and the weight percentage of the styrene-ethyltrimethoxysilane in the composite sole material of the present invention should not exceed 20%. When the weight percentage of the organosiloxane in the anti-slip and yellowing-resistant composite sole material is 10-15%, and the weight percentage of the ethylene-vinyl acetate copolymer in the anti-slip and yellowing-resistant composite sole material is 72-77%, the prepared composite sole material exhibits the best comprehensive performance in terms of resilience, yellowing resistance, and anti-slip properties. The coefficient of friction on the dry interface is 0.78-0.82, the coefficient of friction on the wet interface is 0.28-0.33, the resilience rate is 65-68%, and the yellowing resistance level can reach level five in both room temperature ultraviolet lamp environment and high temperature (50±2℃) sun lamp environment. Compared to Examples 1-5, in Comparative Example 3, the ethylene-vinyl acetate copolymer accounted for 62% of the composite sole material by weight, and styrene-ethyltrimethoxysilane accounted for 25%. The resulting composite sole material exhibited significantly worse resilience and slip resistance, with a resilience of only 48% and a slight decrease in yellowing resistance. The inventors believe that the reduced resilience and slip resistance may be due to the excessive cross-linking of the three-dimensional cross-linked network structure formed by the reaction of styrene-ethyltrimethoxysilane and the ethylene-vinyl acetate copolymer in Comparative Example 1. This excessive cross-linking made the composite sole material too dense, thus reducing its resilience and coefficient of friction.

[0100] As can be seen from Examples 3, 1, and 4-5, the composite sole material prepared in Example 3 exhibits significantly better overall performance in terms of resilience, yellowing resistance, and slip resistance compared to Comparative Examples 1 and 4-5. This may be because the styrene-ethyltrimethoxysilane used in Example 3 contains double bond and conjugated structures, which can undergo cross-linking reactions with the ethylene-vinyl acetate copolymer under the action of a cross-linking agent during the mixing and melting process. The resulting cross-linked structure can significantly improve the slip resistance of the composite sole material and, to some extent, improve its resilience. At the same time, the conjugated structure remaining after the reaction, together with antioxidants and light stabilizers, can improve the yellowing resistance of the composite sole material to some extent.

[0101] As can be seen from Example 3 and Comparative Example 2, the yellowing resistance of the composite sole material prepared in Example 3 is significantly better than that of the material obtained in Comparative Example 2. This indicates that pre-mixing the antioxidant, ethylene-vinyl acetate copolymer, and crosslinking agent can promote the reaction between the carbon-carbon double bond groups of the antioxidant and the ethylene-vinyl acetate copolymer, allowing small antioxidant molecules to be grafted onto the molecular chain of the crosslinked ethylene-vinyl acetate copolymer. This makes it less likely for the antioxidant to migrate and precipitate during the molding and preparation of the sole, thereby significantly improving the yellowing resistance of the composite sole material.

[0102] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A non-slip, yellowing-resistant composite shoe sole material, characterized in that, It includes the following components in parts by weight: 69-83 parts of ethylene-vinyl acetate copolymer, 5-20 parts of organosiloxane, 0.1-0.5 parts of antioxidant, 0.1-1 parts of crosslinking agent, 0.5-2 parts of zinc stearate, 1-3 parts of light stabilizer, 1-2 parts of foaming agent, and 5-8 parts of filler; The organosiloxane is styrene ethyltrimethoxysilane; The antioxidant is 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate; The preparation method of the anti-slip and yellowing-resistant composite shoe sole material includes the following steps: S1. Antioxidant, a portion of ethylene-vinyl acetate copolymer and a portion of crosslinking agent are mixed and then cooled and granulated to obtain mixed masterbatch; S2. The organosiloxane, filler, light stabilizer, zinc stearate and the remaining ethylene-vinyl acetate copolymer are mixed to obtain a compound; S3. Add the mixing masterbatch, foaming agent and remaining crosslinking agent obtained in step S1 to the mixture obtained in step S2 and mix them. After cooling and granulation, the anti-slip and yellowing resistant composite shoe sole material is obtained.

2. The anti-slip and yellowing-resistant composite shoe sole material as described in claim 1, characterized in that, The organosiloxane in the anti-slip and yellowing-resistant composite sole material shall not exceed 20% by weight.

3. The anti-slip and yellowing-resistant composite shoe sole material as described in claim 1, characterized in that, The crosslinking agent is at least one of dicumyl peroxide, 1,4-di-tert-butylperoxyisopropylbenzene, benzoyl peroxide, and dicumyl peroxide.

4. The anti-slip and yellowing-resistant composite shoe sole material as described in claim 1, characterized in that, The light stabilizer is zinc oxide.

5. The anti-slip and yellowing-resistant composite shoe sole material as described in claim 1, characterized in that, The foaming agent is at least one of azodicarbonamide and azobisisobutyronitrile.

6. The anti-slip and yellowing-resistant composite shoe sole material as described in claim 1, characterized in that, The filler includes at least one of mica, talc, and titanium dioxide.

7. The application of the anti-slip and yellowing-resistant composite sole material as described in any one of claims 1 to 6 in the preparation of shoe soles.

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