High-resilience anti-aging TPU sports shoe sole and preparation method thereof

Abstract

The invention relates to the technical field of sole production, in particular to a high-resilience anti-aging TPU sports shoe sole and a preparation method thereof. The TPU sports shoe bottom piece comprises a TPU composite film and a TPU insole arranged on the surface of the TPU composite film, and the TPU composite film is a double-layer co-extrusion film prepared from TPU particles and TPU hot melt colloidal particles through a casting co-extrusion process. The TPU composite film and the TPU midsole are integrally formed, so that the weight of the sole can be remarkably reduced, meanwhile, the production process is effectively simplified, the TPU sports shoe bottom piece is endowed with good rebound resilience, wear resistance and slip resistance, the sole is stressed more uniformly in all directions, and the service life of the sole is prolonged. Therefore, the comfort of the TPU sports shoe bottom piece is improved, and the foot is stably protected.

Description

Technical Field

[0001] The invention relates to the technical field of sole production, and in particular to a high-resilience and aging-resistant TPU sports shoe sole and a preparation method thereof. Background Art

[0002] With the improvement of living standards, people have put forward higher requirements for the comfort and functionality of shoes. Foam soles are used in various sports soles due to their remarkable characteristics of lightness, comfort and high elasticity. At present, the common foam materials for shoes in the industry are mainly EVA, SBS, PVC, TPU, etc., but they all have some disadvantages, such as low skid resistance and obvious low-temperature hardening of EVA; poor heat resistance and wear resistance of SBS; poor wear resistance and cold resistance of PVC; and TPU has problems such as high cost, easy yellowing of appearance, and non-slip. However, compared with other types of foam materials, it shows obvious advantages in comfort, resilience, wear resistance and other aspects. The use of TPU materials to make shoe materials has the characteristics of simple process and superior performance. Therefore, it is urgent to conduct in-depth research on TPU sports shoe sole materials to provide more and better choices for the high-quality sole manufacturing industry. Summary of the invention

[0003] The purpose of the present invention is to provide a high-resilience and aging-resistant TPU sports shoe bottom sheet and a preparation method thereof in order to solve the above-mentioned deficiencies in the prior art.

[0004] The objective of the present invention is achieved through the following technical scheme: The present invention provides a high-resilience and aging-resistant TPU sports shoe sole, comprising a TPU composite film and a TPU midsole arranged on the surface of the TPU composite film, wherein the TPU composite film is a double-layer co-extruded film made of TPU particles and TPU hot-melt adhesive particles through a cast co-extrusion process.

[0005] Furthermore, the TPU particles include the following raw materials in parts by weight: 60-80 parts of TPU elastomer, 3-8 parts of plasticizer, 0.5-6 parts of anti-yellowing agent, 0.1-1.5 parts of lubricant and 0-10 parts of colorant.

[0006] Furthermore, the preparation method of the TPU elastomer includes the following steps: heating and melting polycaprolactone diol and vacuum dehydrating it, then transferring it to a reaction kettle, raising the temperature to 90-100°C, adding 4,4-dicyclohexyltoluene diisocyanate in batches under a nitrogen atmosphere, adding a small amount of organic tin catalyst to carry out a prepolymerization reaction after the temperature stabilizes, and then adding a chain extender and carbodiimide to carry out a chain extension reaction after completion, and then transferring it to a mold for curing and demolding to obtain the TPU elastomer.

[0007] Furthermore, the R value of the prepolymerization reaction system is 2.0, the chain extender is at least one of 1,4-hexanediol, TDMA-G55, and 3,3'-dichloro-4,4'-diphenylmethanediamine, the amount of the chain extender is 8-10% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate, and the amount of the carbodiimide is 0.05-0.2% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate.

[0008] Furthermore, the plasticizer is at least one of dioctyl oxalate, dioctyl sebacate, epoxy fatty acid methyl ester, and propylene glycol adipate polyester.

[0009] Furthermore, the lubricant is at least one of amino silicone oil, zinc stearate, and stearamide.

[0010] Furthermore, the anti-yellowing agent is at least one of a hindered amine light stabilizer, an ultraviolet light absorber, and an antioxidant. The hindered amine light stabilizer is preferably a light stabilizer 783, the ultraviolet light absorber is preferably GSSORB UV-571 or UV-1130, and the antioxidant is at least one of GSINOX DHOP, GSINOX 5057, and GSINOX 1135.

[0011] Furthermore, the colorant can be an organic pigment, such as phthalocyanine blue, or an inorganic pigment such as titanium dioxide, carbon black, etc. The choice of colorant is determined by the application scenario requirements, giving the TPU particles an optional color.

[0012] Furthermore, the TPU particles also include foamed particles. The preparation method of the foamed particles is specifically as follows: 5-8 parts of polyborosiloxane and 0.3-1 parts of a compatibilizer are evenly mixed and added to an internal mixer; 50-60 parts of ethylene-vinyl acetate copolymer, 30-40 parts of a polyolefin elastomer, 0.1-0.5 parts of a coupling agent and 0.5-3 parts of a filler are added thereto, the temperature is first raised to 80°C for preheating and stirring, and then the temperature is raised to 120-125°C, 0.5-1 parts of a cross-linking agent and 2-4 parts of a foaming agent are added and continued to stir to obtain an internal mixing rubber material; the mixture is transferred to an open mixer at 80-90°C for mixing, and the mixed rubber material is granulated by an extruder; the granulated rubber particles are placed in a foaming device, and the rubber particles are foamed by heating to obtain the foamed particles.

[0013] Among them, the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene, the coupling agent is terminal hydroxyl polydimethylsiloxane, the filler is one or more of white carbon black, calcium carbonate, and zinc stearate, the crosslinking agent is di-tert-butyl peroxide, and the foaming agent is azodicarbonamide.

[0014] Furthermore, the preparation method of the TPU hot melt rubber particles comprises the following steps: S1, placing polyester polyol, inorganic filler, tackifying resin, and thermoplastic resin in a reaction container, heating and stirring to 120-140° C., controlling the vacuum pressure at 50-100 Pa, and maintaining for 1-1.5 hours;

[0015] S2, heating the aromatic polyisocyanate to a molten state, and then placing it in the reaction vessel of step S1 to react at a temperature of 80-120° C., and stopping the reaction when the -NCO group content in the reaction system reaches a theoretical calculated value;

[0016] S3, add silane coupling agent and stir for 10-20 minutes, then add dimorpholinyl diethyl ether and thermoplastic resin and continue stirring for 10-20 minutes, and mix well;

[0017] S4. Control the pressure of the reaction container to be less than 100 Pa, perform degassing treatment, and granulate the obtained product through an extruder or a granulator to obtain the TPU hot melt rubber particles.

[0018] Furthermore, the polyester polyol is compounded by amorphous polyester polyol and crystalline polyester polyol in a mass ratio of 1:1-1.5, wherein the amorphous polyester polyol is polybutylene adipate diol or polyethylene adipate diol, and the crystalline polyester polyol is preferably crystalline polybutylene adipate or polyethylene terephthalate polyol.

[0019] Furthermore, the aromatic polyisocyanate is preferably 4,4'-diphenylmethane diisocyanate, diphenylmethane 2,4"-diisocyanate or toluene diisocyanate. In the above reaction system, the isocyanate index is preferably 1.8.

[0020] Furthermore, the inorganic filler is at least one of fumed silica, talc and kaolin, and the amount of the inorganic filler is 0.3-0.6wt% of the total amount of polyester polyol and aromatic polyisocyanate. The tackifying resin is at least one of terpene phenol resin, tert-butylphenol resin or natural rosin resin, and the amount of the tackifying resin is 12-18% of the total amount of polyester polyol and aromatic polyisocyanate. The thermoplastic resin is a semi-crystalline linear polycaprolactone-based thermoplastic polyurethane resin, and the amount of the thermoplastic resin is 18-20wt% of the total amount of polyester polyol and aromatic polyisocyanate. The silane coupling agent is KH550 or KH560, and the amount of the silane coupling agent is 0.1-1% of the total amount of polyester polyol and aromatic polyisocyanate.

[0021] The present invention also provides a method for preparing the above-mentioned sole sheet for sports shoes, comprising the following preparation steps:

[0022] (1) taking a TPU composite film and pressing it into a desired shape through a mold to obtain a TPU outsole;

[0023] (2) placing the TPU outsole obtained in step (1) into the reserved TPU outsole position in the secondary hot pressing mold, and then placing the TPU midsole;

[0024] (3) The TPU outsole and the TPU midsole are formed into one piece by first performing hot pressing treatment on the secondary hot pressing mold and then performing cold pressing treatment, thereby obtaining the TPU sports shoe bottom sheet.

[0025] Furthermore, in step (3), the temperature of the hot pressing treatment is 150-160°C, and the time is 300-500s; the temperature of the cold pressing treatment is 35-37°C, and the time is 400-600s.

[0026] The beneficial effects of the present invention are:

[0027] (1) The present invention can significantly reduce the weight of the sole by integrally forming the TPU composite film and the TPU midsole, while effectively simplifying the production process, and giving the TPU sports shoe sole good resilience, wear resistance and anti-slip properties, so that the sole is subjected to more uniform force in all directions, thereby improving the comfort of the TPU sports shoe sole and the stable protection of the foot;

[0028] (2) The present invention uses a cast co-extrusion process to form TPU particles and TPU hot-melt adhesive particles into a double-layer composite film, so that one side of the TPU hot-melt adhesive particles can be better bonded and pressed with the TPU midsole. The TPU hot-melt adhesive particles prepared by the above method have high adhesive strength, good weather resistance and temperature resistance, thereby improving the structural strength of the TPU sports shoe bottom sheet and preventing delamination;

[0029] (3) The TPU particles prepared by the present invention using raw materials such as TPU elastomer, plasticizer, anti-yellowing agent and lubricant have the characteristics of high strength and high elasticity, yellowing and aging resistance, hydrolysis resistance and easy processing, thereby giving the TPU sports shoe bottom sheet good advantages such as good yellowing and aging resistance, hydrolysis resistance and high tensile strength;

[0030] (4) The present invention further adds foamed particles in the preparation of TPU particles, thereby improving the resilience and shock absorption of the TPU composite film, thereby significantly improving the comfort and rebound of the TPU sports shoe bottom sheet, and also improving the anti-slip property of the TPU sports shoe bottom sheet. DETAILED DESCRIPTION

[0031] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0032] Example 1

[0033] This embodiment provides a high-resilience and aging-resistant TPU sports shoe sole, including a TPU composite film and a TPU midsole arranged on the surface of the TPU composite film. The TPU composite film is a double-layer co-extruded film made of TPU particles and TPU hot-melt adhesive particles through a cast co-extrusion process.

[0034] Furthermore, the TPU particles include the following raw materials in parts by weight: 62 parts of TPU elastomer, 3 parts of plasticizer, 0.8 parts of anti-yellowing agent, and 0.4 parts of lubricant.

[0035] Furthermore, the preparation method of the TPU elastomer comprises the following steps: the preparation method of the TPU elastomer comprises the following steps: heating and melting polycaprolactone diol at 110°C and a vacuum degree of 90Pa and vacuum dehydrating for 2 hours, then transferring it to a reactor, raising the temperature to 90°C, adding 4,4-dicyclohexyltoluene diisocyanate in batches under a nitrogen atmosphere and stirring rapidly, adding 1 drop of stannous octoate for prepolymerization after the temperature stabilizes, and the reaction ends after the isocyanate group content reaches the theoretical value, and then vacuum degassing the obtained polyurethane prepolymer for 10 minutes, and after completion, adding a chain extender and carbodiimide for chain extension reaction, and then transferring it to a preheated mold for curing and demolding to obtain the TPU elastomer.

[0036] Furthermore, the R value of the prepolymerization reaction system is 2.0, the chain extender is 3,3'-dichloro-4,4'-diphenylmethanediamine, the amount of the chain extender is 8% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate, and the amount of the carbodiimide is 0.08% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate.

[0037] Furthermore, the plasticizer is dioctyl oxalate.

[0038] Furthermore, the lubricant is zinc stearate.

[0039] Furthermore, the anti-yellowing agent is compounded with a hindered amine light stabilizer, an ultraviolet absorber, and an antioxidant in a mass ratio of 2:1:1. The hindered amine light stabilizer is light stabilizer 783, the ultraviolet absorber is GSSORB UV-571, and the antioxidant is GSINOX 1135.

[0040] Furthermore, the preparation method of the TPU hot melt rubber particles comprises the following steps: S1, placing polyester polyol, inorganic filler, tackifying resin, and thermoplastic resin in a reaction container, heating and stirring to 125° C., controlling the vacuum pressure at 90 Pa, and maintaining for 1.5 hours;

[0041] S2, heating the aromatic polyisocyanate to a molten state, and then placing it in the reaction vessel of step S1 to react at a reaction temperature of 90° C., and stopping the reaction when the -NCO group content in the reaction system reaches a theoretical calculated value;

[0042] S3, adding silane coupling agent and stirring for 15 minutes, then adding dimorpholinyl diethyl ether and thermoplastic resin and stirring for 15 minutes, and mixing evenly;

[0043] S4. Control the pressure of the reaction container to be less than 100 Pa, perform degassing treatment, and granulate the obtained product through an extruder or a granulator to obtain the TPU hot melt rubber particles.

[0044] Furthermore, the polyester polyol is compounded by amorphous polyester polyol and crystalline polyester polyol in a mass ratio of 1:1.2, wherein the amorphous polyester polyol is polybutylene adipate diol, and the crystalline polyester polyol is crystalline polybutylene adipate diol.

[0045] Furthermore, the aromatic polyisocyanate is diphenylmethane 2,4'-diisocyanate. In the above reaction system, the isocyanate index is preferably 1.8.

[0046] Furthermore, the inorganic filler is compounded by fumed silica and kaolin in a mass ratio of 1.3:1, and the amount of the inorganic filler is 0.3wt% of the total amount of polyester polyol and aromatic polyisocyanate. The tackifying resin is terpene phenol resin, and the amount of the tackifying resin is 13% of the total amount of polyester polyol and aromatic polyisocyanate. The thermoplastic resin is a semi-crystalline linear polycaprolactone-based thermoplastic polyurethane resin, and the amount of the thermoplastic resin is 18wt% of the total amount of polyester polyol and aromatic polyisocyanate. The silane coupling agent is KH550, and the amount of the silane coupling agent is 0.2% of the total amount of polyester polyol and aromatic polyisocyanate.

[0047] The present invention also provides a method for preparing the above-mentioned sole sheet for sports shoes, comprising the following preparation steps:

[0048] (1) taking a TPU composite film and pressing it into a desired shape through a mold to obtain a TPU outsole;

[0049] (2) placing the TPU outsole obtained in step (1) into the reserved TPU outsole position in the secondary hot pressing mold, and then placing the TPU midsole;

[0050] (3) The TPU outsole and the TPU midsole are formed into one piece by first performing hot pressing treatment on the secondary hot pressing mold and then performing cold pressing treatment, thereby obtaining the TPU sports shoe bottom sheet.

[0051] Furthermore, in step (3), the temperature of the hot pressing treatment is 150° C. and the time is 400 s; the temperature of the cold pressing treatment is 36° C. and the time is 500 s.

[0052] Example 2

[0053] This embodiment provides a high-resilience and aging-resistant TPU sports shoe sole, including a TPU composite film and a TPU midsole arranged on the surface of the TPU composite film. The TPU composite film is a double-layer co-extruded film made of TPU particles and TPU hot-melt adhesive particles through a cast co-extrusion process.

[0054] Furthermore, the TPU particles include the following raw materials in parts by weight: 70 parts of TPU elastomer, 5 parts of plasticizer, 3 parts of anti-yellowing agent, and 0.7 parts of lubricant.

[0055] Furthermore, the preparation method of the TPU elastomer comprises the following steps: the preparation method of the TPU elastomer comprises the following steps: heating and melting polycaprolactone diol at 110°C and a vacuum degree of 90Pa and vacuum dehydrating for 2 hours, then transferring it to a reactor, raising the temperature to 95°C, adding 4,4-dicyclohexyltoluene diisocyanate in batches under a nitrogen atmosphere and stirring rapidly, adding 1 drop of stannous octoate for prepolymerization after the temperature stabilizes, and the reaction ends after the isocyanate group content reaches the theoretical value, and then vacuum degassing the obtained polyurethane prepolymer for 10 minutes, and after completion, adding a chain extender and carbodiimide for chain extension reaction, and then transferring it to a preheated mold for curing and demolding to obtain the TPU elastomer.

[0056] Furthermore, the R value of the prepolymerization reaction system is 2.0, the chain extender is TDMA-G55, the amount of the chain extender is 9% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate, and the amount of the carbodiimide is 0.1% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate.

[0057] Furthermore, the plasticizer is propylene glycol adipate polyester.

[0058] Furthermore, the lubricant is amino silicone oil.

[0059] Furthermore, the anti-yellowing agent is compounded with a hindered amine light stabilizer, an ultraviolet absorber, and an antioxidant in a mass ratio of 2:1:1, wherein the hindered amine light stabilizer is light stabilizer 783, the ultraviolet absorber is GSSORB UV-571, and the antioxidant is GSINOX DHOP.

[0060] Furthermore, the TPU particles also include foamed particles. The preparation method of the foamed particles is specifically as follows: 6 parts of polyborosiloxane and 0.6 parts of a compatibilizer are mixed evenly and added to an internal mixer; 55 parts of ethylene-vinyl acetate copolymer, 32 parts of a polyolefin elastomer, 0.3 parts of a coupling agent and 1.2 parts of a filler are added thereto, first heated to 80°C for preheating and stirring, then heated to 120°C, 0.5 parts of a cross-linking agent and 3 parts of a foaming agent are added and continued to stir to obtain an internal mixing rubber compound; the mixture is transferred to an open mixer at 85°C for mixing, and the mixed rubber compound is granulated by an extruder; the granulated rubber particles are placed in a foaming device, and the rubber particles are foamed by heating to obtain the foamed particles.

[0061] Wherein, the compatibilizer is maleic anhydride grafted polypropylene, the coupling agent is hydroxy-terminated polydimethylsiloxane, the filler is zinc stearate, the cross-linking agent is di-tert-butyl peroxide, and the foaming agent is azodicarbonamide.

[0062] Furthermore, the preparation method of the TPU hot melt rubber particles comprises the following steps: S1, placing polyester polyol, inorganic filler, tackifying resin, and thermoplastic resin in a reaction container, heating and stirring to 130° C., controlling the vacuum pressure at 90 Pa, and maintaining for 1.5 hours;

[0063] S2, heating the aromatic polyisocyanate to a molten state, and then placing it in the reaction vessel of step S1 to react at a temperature of 95° C., and stopping the reaction when the -NCO group content in the reaction system reaches a theoretical calculated value;

[0064] S3, adding silane coupling agent and stirring for 15 minutes, then adding dimorpholinyl diethyl ether and thermoplastic resin and stirring for 15 minutes, and mixing evenly;

[0065] S4. Control the pressure of the reaction container to be less than 100 Pa, perform degassing treatment, and granulate the obtained product through an extruder or a granulator to obtain the TPU hot melt rubber particles.

[0066] Furthermore, the polyester polyol is compounded by amorphous polyester polyol and crystalline polyester polyol in a mass ratio of 1:1-1.5, wherein the amorphous polyester polyol is polybutylene adipate diol, and the crystalline polyester polyol is crystalline polybutylene adipate or polyethylene terephthalate polyol.

[0067] Furthermore, the aromatic polyisocyanate is preferably 4,4'-diphenylmethane diisocyanate. In the above reaction system, the isocyanate index is 1.8.

[0068] Furthermore, the inorganic filler is compounded by fumed silica and kaolin in a mass ratio of 1.3:1, and the amount of the inorganic filler is 0.4wt% of the total amount of polyester polyol and aromatic polyisocyanate. The tackifying resin is tert-butylphenolic resin, and the amount of the tackifying resin is 14% of the total amount of polyester polyol and aromatic polyisocyanate. The thermoplastic resin is a semi-crystalline linear polycaprolactone-based thermoplastic polyurethane resin, and the amount of the thermoplastic resin is 19wt% of the total amount of polyester polyol and aromatic polyisocyanate. The silane coupling agent is KH550, and the amount of the silane coupling agent is 0.4% of the total amount of polyester polyol and aromatic polyisocyanate.

[0069] Example 3

[0070] This embodiment provides a high-resilience and aging-resistant TPU sports shoe sole, including a TPU composite film and a TPU midsole arranged on the surface of the TPU composite film. The TPU composite film is a double-layer co-extruded film made of TPU particles and TPU hot-melt adhesive particles through a cast co-extrusion process.

[0071] Furthermore, the TPU particles include the following raw materials in parts by weight: 75 parts of TPU elastomer, 6 parts of plasticizer, 5 parts of anti-yellowing agent, 1.3 parts of lubricant and 3 parts of colorant.

[0072] Furthermore, the preparation method of the TPU elastomer comprises the following steps: the preparation method of the TPU elastomer comprises the following steps: heating and melting polycaprolactone diol at 110°C and a vacuum degree of 90Pa and vacuum dehydrating for 2 hours, then transferring it to a reactor, raising the temperature to 95°C, adding 4,4-dicyclohexyltoluene diisocyanate in batches under a nitrogen atmosphere and stirring rapidly, adding 1 drop of stannous octoate for prepolymerization after the temperature stabilizes, and the reaction ends after the isocyanate group content reaches the theoretical value, and then vacuum degassing the obtained polyurethane prepolymer for 10 minutes, and after completion, adding a chain extender and carbodiimide for chain extension reaction, and then transferring it to a preheated mold for curing and demolding to obtain the TPU elastomer.

[0073] Furthermore, the R value of the prepolymerization reaction system is 2.0, the chain extender is 3,3'-dichloro-4,4'-diphenylmethanediamine, the amount of the chain extender is 10% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate, and the amount of the carbodiimide is 0.15% of the total amount of polycaprolactone diol and 4,4-dicyclohexyltoluene diisocyanate.

[0074] Furthermore, the plasticizer is epoxy fatty acid methyl ester.

[0075] Furthermore, the lubricant is stearamide.

[0076] Furthermore, the anti-yellowing agent is compounded with a hindered amine light stabilizer, an ultraviolet absorber, and an antioxidant in a mass ratio of 2:1:1. The hindered amine light stabilizer is light stabilizer 783, the ultraviolet absorber is UV-1130, and the antioxidant is GSINOX 5057.

[0077] Furthermore, the TPU particles also include foamed particles. The preparation method of the foamed particles is specifically as follows: 7 parts of polyborosiloxane and 0.8 parts of a compatibilizer are mixed evenly and added to an internal mixer; then 60 parts of ethylene-vinyl acetate copolymer, 38 parts of a polyolefin elastomer, 0.4 parts of a coupling agent and 2 parts of a filler are added thereto, first heated to 80°C for preheating and stirring, then heated to 125°C, 1 part of a cross-linking agent and 3 parts of a foaming agent are added and continued to stir to obtain an internal mixing rubber compound; transferred to an open mixer at 85°C for mixing, and the mixed rubber compound is granulated by an extruder; the granulated rubber particles are placed in a foaming device, and the rubber particles are foamed by heating to obtain the foamed particles.

[0078] Wherein, the compatibilizer is maleic anhydride grafted polyethylene, the coupling agent is hydroxy-terminated polydimethylsiloxane, the filler is calcium carbonate, the cross-linking agent is di-tert-butyl peroxide, and the foaming agent is azodicarbonamide.

[0079] Furthermore, the preparation method of the TPU hot melt rubber particles comprises the following steps: S1, placing polyester polyol, inorganic filler, tackifying resin, and thermoplastic resin in a reaction container, heating and stirring to 135° C., controlling the vacuum pressure at 100 Pa, and maintaining for 1.5 hours;

[0080] S2, heating the aromatic polyisocyanate to a molten state, and then placing it in the reaction vessel of step S1 to react at a reaction temperature of 105° C., and stopping the reaction when the -NCO group content in the reaction system reaches a theoretical calculated value;

[0081] S3, adding silane coupling agent and stirring for 15 minutes, then adding dimorpholinyl diethyl ether and thermoplastic resin and stirring for 15 minutes, and mixing evenly;

[0082] S4. Control the pressure of the reaction container to be less than 100 Pa, perform degassing treatment, and granulate the obtained product through an extruder or a granulator to obtain the TPU hot melt rubber particles.

[0083] Furthermore, the polyester polyol is compounded by amorphous polyester polyol and crystalline polyester polyol in a mass ratio of 1:1-1.5, wherein the amorphous polyester polyol is polybutylene adipate diol, and the crystalline polyester polyol is crystalline polybutylene adipate or polyethylene terephthalate polyol.

[0084] Furthermore, the aromatic polyisocyanate is toluene diisocyanate. In the above reaction system, the isocyanate index is 1.8.

[0085] Furthermore, the inorganic filler is compounded by fumed silica and kaolin in a mass ratio of 1.3:1, and the amount of the inorganic filler is 0.3-0.6wt% of the total amount of polyester polyol and aromatic polyisocyanate. The tackifying resin is a natural rosin resin, and the amount of the tackifying resin is 16% of the total amount of polyester polyol and aromatic polyisocyanate. The thermoplastic resin is a semi-crystalline linear polycaprolactone-based thermoplastic polyurethane resin, and the amount of the thermoplastic resin is 18wt% of the total amount of polyester polyol and aromatic polyisocyanate. The silane coupling agent is KH560, and the amount of the silane coupling agent is 0.7% of the total amount of polyester polyol and aromatic polyisocyanate.

[0086] The present invention also provides a method for preparing the above-mentioned sole sheet for sports shoes, comprising the following preparation steps:

[0087] (1) taking a TPU composite film and pressing it into a desired shape through a mold to obtain a TPU outsole;

[0088] (2) placing the TPU outsole obtained in step (1) into the reserved TPU outsole position in the secondary hot pressing mold, and then placing the TPU midsole;

[0089] (3) The TPU outsole and the TPU midsole are formed into one piece by first performing hot pressing treatment on the secondary hot pressing mold and then performing cold pressing treatment, thereby obtaining the TPU sports shoe bottom sheet.

[0090] Furthermore, in step (3), the temperature of the hot pressing treatment is 155°C and the time is 400s; the temperature of the cold pressing treatment is 36°C and the time is 500s.

[0091] Comparative Example 1

[0092] The difference between this comparative example and Example 2 is that a commercially available TPU elastomer (Taiwan Risheng 1730-60) is used to replace the TPU elastomer in Example 2.

[0093] Comparative Example 2

[0094] The difference between this comparative example and Example 2 is that this comparative example uses antioxidant 1010 to replace the anti-yellowing agent in Example 2.

[0095] Comparative Example 3

[0096] The difference between this comparative example and Example 3 is that commercially available EVA foamed particles (Beijing Yanshan EVA 18J3) are used to replace the foamed particles in Example 3.

[0097] The present invention tests the tensile strength, resilience, aging resistance, bending resistance and anti-slip force of the TPU sports shoe bottom sheets prepared in the above Examples 1-3 and Comparative Examples 1-3. The tensile strength is measured according to GB / T1040.3-2006 standard;

[0098] The rebound rate is measured using the ASTM D2632-2001 standard; the aging resistance is measured using QUV340nm for 1000h, with a light intensity of 800W / cm2; the bending resistance is measured using the GB / T 3903.1-2017 standard (bending angle 50°, bending frequency 230 times / min); the anti-slip force is measured using the GB / T28287-2012 standard. The test results are shown in the following table:

[0099]

[0100] From the above results, it can be seen that the TPU sports shoe soles prepared by Examples 1-3 of the present invention have balanced and excellent performance in mechanical strength, aging resistance and bending resistance, among which the tensile strength is above 40MPa, the resilience is greater than 46%, the bending resistance is greater than 120,000 times, and the tensile strength of the sole changes slightly after 1000h UV aging, indicating that it has good aging resistance and UV resistance stability. On the other hand, the TPU sports shoe sole prepared by Example 1 is slightly inferior to that of Examples 2 and 3 in terms of anti-slip properties, which is mainly because the introduction of the foamed particles plays an important role in improving the dry / wet anti-slip properties of the TPU sports shoe sole.

[0101] The above specific embodiments are further explanations of the technical solutions and beneficial effects of the present invention, and are not limitations of the implementation methods. For those skilled in the art, any obvious replacements that do not depart from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A high-resilience and aging-resistant TPU sports shoe sole, characterized by: The invention comprises a TPU composite film and a TPU midsole arranged on the surface of the TPU composite film. The TPU composite film is a double-layer co-extruded film made of TPU particles and TPU hot-melt adhesive particles through a casting co-extrusion process.

2. The high-resilience and aging-resistant TPU sports shoe sole according to claim 1, characterized in that: The TPU particles include the following raw materials in parts by weight: 60-80 parts of TPU elastomer, 3-8 parts of plasticizer, 0.5-6 parts of anti-yellowing agent, 0.1-1.5 parts of lubricant and 0-10 parts of colorant.

3. The high-resilience and anti-aging TPU sports shoe sole according to claim 2, characterized in that: The preparation method of the TPU elastomer comprises the following steps: heating and melting polycaprolactone diol and vacuum dehydrating it, then transferring it to a reaction kettle, raising the temperature to 90-100° C., adding 4,4-dicyclohexyltoluene diisocyanate in batches under a nitrogen atmosphere, adding a small amount of an organic tin catalyst to carry out a prepolymerization reaction after the temperature stabilizes, adding a chain extender and carbodiimide to carry out a chain extension reaction after completion, and then transferring it to a mold for curing and demolding to obtain the TPU elastomer.

4. The high-resilience and anti-aging TPU sports shoe sole according to claim 2, characterized in that: The plasticizer is at least one of dioctyl oxalate, dioctyl sebacate, epoxy fatty acid methyl ester, and propylene glycol adipate polyester.

5. The high-resilience and anti-aging TPU sports shoe sole according to claim 2, characterized in that: The lubricant is at least one of amino silicone oil, zinc stearate and stearamide.

6. The high-resilience and anti-aging TPU sports shoe sole according to claim 1, characterized in that: The anti-yellowing agent is at least one of a hindered amine light stabilizer, an ultraviolet absorber, and an antioxidant.

7. The high-resilience and anti-aging TPU sports shoe sole according to claim 1, characterized in that: The TPU particles also include 12-20 parts of foamed particles.

8. The high-resilience and anti-aging TPU sports shoe sole according to claim 7, characterized in that: The preparation method of the foamed beads is specifically as follows: 5-8 parts of polyborosiloxane and 0.3-1 parts of a compatibilizer are uniformly mixed and added into an internal mixer; 50-60 parts of ethylene-vinyl acetate copolymer, 30-40 parts of a polyolefin elastomer, 0.1-0.5 parts of a coupling agent and 0.5-3 parts of a filler are added thereto, the temperature is first raised to 80° C. for preheating and stirring, and then the temperature is raised to 120-125° C., 0.5-1 parts of a cross-linking agent and 2-4 parts of a foaming agent are added and stirred continuously to obtain an internal mixing rubber material; the mixture is transferred to an open mixer at 80-90° C. for mixing, and the mixed rubber material is granulated by an extruder; the granulated rubber particles are placed in a foaming device, and the rubber particles are foamed by heating to obtain the foamed beads.

9. The method for preparing the high-resilience and aging-resistant TPU sports shoe bottom sheet according to claim 1, characterized in that: The method comprises the following preparation steps: (1) taking a TPU composite film and pressing it into a desired shape through a mold to obtain a TPU outsole; (2) placing the TPU outsole obtained in step (1) into the reserved TPU outsole position in the secondary hot pressing mold, and then placing the TPU midsole; (3) The TPU outsole and the TPU midsole are formed into one piece by first performing hot pressing treatment on the secondary hot pressing mold and then performing cold pressing treatment, thereby obtaining the TPU sports shoe bottom sheet.

10. The method for preparing the high-resilience and aging-resistant TPU sports shoe bottom sheet according to claim 1, characterized in that: In step (3), the temperature of the hot pressing treatment is 150-160°C, and the time is 300-500s; the temperature of the cold pressing treatment is 35-37°C, and the time is 400-600s.

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