WO2025161569A1 - Injection-molded high-wear-resistance high-slip-resistance tpu shoe sole - Google Patents

Abstract

The present invention relates to the technical field of TPU shoe soles. Disclosed in the present invention is an injection-molded high-wear-resistance high-slip-resistance TPU shoe sole, specifically comprising the following raw materials in parts by weight: 10-20 parts of a modified molecular sieve, 5-10 parts of white carbon black, 60-90 parts of a TPU-NBR composite material, and 0.6-1 part of an auxiliary additive. According to the injection-molded high-wear-resistance high-slip-resistance TPU shoe sole, the addition of white carbon black improves the wear resistance and thermal stability of a TPU material; the addition of an antioxidant delays the oxidation process of the TPU material, thereby prolonging the service life of the TPU material; and the addition of the modified molecular sieve can reduce the thermoplastic and viscosity of the TPU material, making processing of the TPU material easier. In addition, the modified molecular sieve can also control the size and distribution of pores in the TPU material, improve the interfacial adhesion, wettability, and surface flatness of the TPU material, and enhance the mechanical properties of the TPU material, thereby improving the hardness, strength, toughness, and durability of the TPU material.

Description

A high wear-resistant and high anti-slip TPU sole for injection molding Technical Field

The invention relates to the technical field of TPU soles, in particular to a high-wear-resistant and high-slip TPU sole that can be used for injection molding.

Background Art

Referring to a Chinese patent for a TPU sole material, its manufacturing process and heel-type sole (Announcement No.: CN115746256A), the TPU sole material is composed of the following components by weight: polyol: 65-75 parts; diphenylmethane diisocyanate: 15-25 parts; 1,4-butanediol: 3-7 parts; antioxidant: 0.2-0.5 parts; and lubricant: 0.2-0.5 parts; the manufacturing process includes the following steps: the first step, the polyol 65g- 75g of propylene glycol, 15g-25g of diphenylmethane diisocyanate, 3g-7g of 1,4-butanediol, 0.2g-0.5g of an antioxidant, and 0.2g-0.5g of a lubricant are added to an internal mixer to prepare a mixture. Secondly, the mixture prepared in the first step is transferred to a mold for foaming, and then naturally cooled after foaming to obtain a semi-finished product. Thirdly, the semi-finished product obtained in the second step is sprayed with a desired color paint on the heel, and then allowed to dry naturally to form the TPU sole material. However, the TPU sole materials prepared in the above-mentioned prior art have poor heat resistance. Therefore, the present invention provides a highly wear-resistant and anti-slip TPU sole that can be injection molded to address the above-mentioned problems.

Technical issues

In view of the shortcomings of the prior art, the present invention provides a high-wear-resistant and high-slip TPU sole that can be injection molded, which solves the problems mentioned in the above background technology.

Technical Solutions

To achieve the above objectives, the present invention is implemented through the following technical scheme: a high-wear-resistant and high-anti-slip TPU sole that can be used for injection molding, specifically comprising the following raw materials in parts by weight: 10 to 20 parts of modified molecular sieve, 5 to 10 parts of white carbon black, 60 to 90 parts of TPU-NBR composite material, and 0.6 to 1 part of auxiliary additives.

Preferably, the auxiliary additives are an anti-yellowing agent and an antioxidant, wherein the mass ratio of the anti-yellowing agent to the antioxidant is 1:(0.7-1); the anti-yellowing agent is selected from a mixture of one or more of UV-P, UV-327, UV-328 and UV-765, and the antioxidant is selected from a mixture of one or more of 168 antioxidants, 1010 antioxidants, 1076 antioxidants and 1098 antioxidants.

Preferably, the specific modification steps of the modified molecular sieve are:

1) Put the molecular sieve into a ball mill for grinding to make the molecular sieve into powder;

2) Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it with distilled water;

3) Mix the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate in a pure DMF solution, and heat in a water bath to obtain a modified molecular sieve solution;

4) Filter and wash the modified molecular sieve solution, and place the filter residue in a drying oven for drying to obtain a dry modified molecular sieve.

Preferably, in step 1), the grinding time is 15 to 20 minutes and the rotation speed is 1100 to 1300 rpm.

Preferably, in step 2), washing with distilled water is performed 2 to 3 times.

Preferably, in step 3), the mixing mass ratio of the molecular sieve, 1-ethyl acetate-3-methylimidazolium hexafluorophosphate and the pure DMF solution is 5:1.

Preferably, the water bath temperature in step 3) is 65-75° C., the water bath time is 10-14 hours, and the stirring speed is 90-110 rpm.

Preferably, the temperature in the drying oven is 110-130°C.

Preferably, the preparation method of the TPU-NBR composite material is: pouring TPU into a torque rheometer under constant temperature conditions, and after melting, first increasing and then decreasing the torque, and when the torque is stable, adding NBR rubber compound to obtain the TPU-NBR composite material.

Preferably, the TPU is a polyether polyurethane with a Shore hardness of 60A to 45D.

Preferably, the mass ratio of TPU to NBR rubber mixture is 1:0.4. When the TPU is poured in, the constant temperature in the moment rheometer is 170-175° C. and the rotation speed is 75-85 r/min.

Beneficial effects

The present invention provides a highly wear-resistant and highly anti-slip TPU sole that can be injection molded. Compared with the prior art, the invention has the following beneficial effects: the injection moldable highly wear-resistant and highly anti-slip TPU sole improves the wear resistance and thermal stability of the TPU material by adding white carbon black; the addition of an antioxidant delays the oxidation process of the TPU material, thereby extending its service life; the addition of a modified molecular sieve reduces the thermoplasticity and viscosity of the TPU material, making it easier to process; in addition, the modified molecular sieve can control the size and distribution of pores in the TPU material, improving the interfacial adhesion, wettability, and surface smoothness of the TPU material, while enhancing the mechanical properties of the TPU material, increasing its hardness, strength, toughness, and durability. By using a TPU-NBR composite material, the wear resistance and heat resistance of the sole are improved, thereby extending its service life.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a water contact angle test diagram of a high wear-resistant and high anti-slip TPU sole for injection molding according to the present invention.

Best Mode for Carrying Out the Invention

The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

TPU is a polyether polyurethane with a Shore hardness of 60A to 45D;

The preparation method of the TPU-NBR composite material is as follows: under a constant temperature condition of 170°C, pouring TPU into a torque rheometer at a rotation speed of 80r/min, and after melting, first increasing and then decreasing the torque. When the torque is stable, adding NBR rubber compound to obtain the TPU-NBR composite material, wherein the mass ratio of TPU to NBR rubber compound is 1:0.4.

The embodiments of the present invention provide the following technical solutions:

Example 1

S1, put the molecular sieve into a ball mill for grinding, the grinding time is 15 minutes, the rotation speed is 1100 rpm, and the molecular sieve is ground into powder;

S2. Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it twice with distilled water;

S3, the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate were placed in pure DMF solution and mixed at a mixing mass ratio of 5:1, a stirring speed of 90 rpm, and heated in a water bath at a water bath temperature of 65 ° C. for 10 hours to obtain a modified molecular sieve solution;

S4, filtering and washing the modified molecular sieve solution, and placing the filter residue in a drying oven for drying to obtain a dry modified molecular sieve for standby use;

S5, the components are weighed in proportion and set aside;

S6. Pour 60 g of TPU-NBR composite material, 0.3 g of anti-yellowing agent and 0.3 g of antioxidant into a blender;

S7, add 5g of white carbon black and 10g of modified molecular sieve, and continue stirring until the mixture is evenly mixed;

S8. The mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a herringbone pattern. After cooling and shaping, a TPU tennis shoe sole with a VVVV repeated pattern is obtained.

Modes for Carrying Out the Invention

Example 2

S1, put the molecular sieve into a ball mill for grinding, the grinding time is 18 minutes, the rotation speed is 1200 rpm, and the molecular sieve is ground into powder;

S2. Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it three times with distilled water;

S3, the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate were placed in a pure DMF solution and mixed at a mixing mass ratio of 5:1, a stirring speed of 100 rpm, and heated in a water bath at a water bath temperature of 70 ° C. for 12 hours to obtain a modified molecular sieve solution;

S4, filtering and washing the modified molecular sieve solution, and placing the filter residue in a drying oven for drying to obtain a dry modified molecular sieve for standby use;

S5, the components are weighed in proportion and set aside;

S6. Pour 75 g of TPU-NBR composite material, 0.4 g of anti-yellowing agent and 0.3 g of antioxidant into a blender;

S7, add 8g of white carbon black and 15g of modified molecular sieve, and continue stirring until the mixture is evenly mixed;

S8. The mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a wavy pattern. After cooling and shaping, a TPU sports shoe sole with a wavy pattern is obtained.

Example 3

S1, put the molecular sieve into a ball mill for grinding, the grinding time is 20 minutes, the rotation speed is 1300 rpm, and the molecular sieve is ground into powder;

S2. Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it three times with distilled water;

S3, the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate were placed in pure DMF solution and mixed at a mixing mass ratio of 5:1, a stirring speed of 110 rpm, and heated in a water bath at a water bath temperature of 75 ° C. for 14 hours to obtain a modified molecular sieve solution;

S4, filtering and washing the modified molecular sieve solution, and placing the filter residue in a drying oven for drying to obtain a dry modified molecular sieve for standby use;

S5, the components are weighed in proportion and set aside;

S6. Pour 80 g of TPU-NBR composite material, 0.5 g of anti-yellowing agent and 0.4 g of antioxidant into a blender;

S7, add 10g of white carbon black and 20g of modified molecular sieve, and continue stirring until the mixture is uniform;

S8. The mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a continuous block-like shading. After cooling and shaping, a TPU running shoe sole with a continuous block-like shading is obtained.

Comparative Example 1

S1. Pour 60g of TPU-NBR composite material, 0.3g of anti-yellowing agent and 0.3g of antioxidant into a blender;

S2. Then pour the mixed material into an injection molding machine and perform injection molding to obtain a TPU sole.

Comparative Example 2

S1, put the molecular sieve into a ball mill for grinding, the grinding time is 15 minutes, the rotation speed is 1100 rpm, and the molecular sieve is ground into powder;

S2. Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it twice with distilled water;

S3, the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate were placed in pure DMF solution and mixed at a mixing mass ratio of 5:1, a stirring speed of 90 rpm, and heated in a water bath at a water bath temperature of 65 ° C. for 10 hours to obtain a modified molecular sieve solution;

S4, filtering and washing the modified molecular sieve solution, and placing the filter residue in a drying oven for drying to obtain a dry modified molecular sieve for standby use;

S5, the components are weighed in proportion and set aside;

S6. Pour 60 g of pure TPU, 0.3 g of anti-yellowing agent, and 0.3 g of antioxidant into a blender;

S7, add 10g of modified molecular sieve and continue stirring until the mixture is evenly mixed;

S8. Then pour the mixed material into an injection molding machine and perform injection molding to obtain a TPU sole.

Damping factor tanδ test: The samples were tested using a damping tester. Each sample was tested 3 times and the average value was taken. The results are shown in Table 1:

Table 1

As can be seen from Table 1, the glass transition temperature of Comparative Example 2 is lower than 0°C, so the damping factor tanδ value corresponding to it at 0°C is very low, which reflects that its anti-slip performance is poor; the damping factor tanδ corresponding to Comparative Example 1 at 0°C is also low; while Examples 1, 2, and 3 increase the glass transition temperature (above 0°C) by adding NBR compound to pure TPU, so that the damping factor tanδ peak is obtained at 0°C, and therefore their anti-slip performance is better.

As can be seen from Figure 1, the water contact angle on the sample surface is measured by vertically dripping water droplets. The water contact angle θ in Example 1 is 104.1°, which is greater than 90°; the water contact angle θ of the TPU in Comparative Example 1 is 86.5°, which has a certain hydrophilicity. Therefore, the TPU sole prepared by this technical solution has better hydrolysis resistance and can maintain good mechanical properties even in a high temperature and high humidity environment.

Meanwhile, the contents not described in detail in this specification belong to the prior art known to those skilled in the art.

It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims (10)

A high-wear-resistant and high-anti-slip TPU sole for injection molding is characterized in that it specifically comprises the following raw materials in parts by weight: 10-20 parts of modified molecular sieve, 5-10 parts of white carbon black, 60-90 parts of TPU-NBR composite material, and 0.6-1 part of auxiliary additives. The high-wear-resistant and high-anti-slip TPU sole for injection molding according to claim 1 is characterized in that: the auxiliary additives are an anti-yellowing agent and an antioxidant, wherein the mass ratio of the anti-yellowing agent to the antioxidant is 1:(0.7-1); the anti-yellowing agent is selected from a mixture of one or more of UV-P, UV-327, UV-328 and UV-765, and the antioxidant is selected from a mixture of one or more of 168 antioxidants, 1010 antioxidants, 1076 antioxidants and 1098 antioxidants. The high wear-resistant and high anti-slip TPU sole for injection molding according to claim 1 is characterized in that the specific modification steps of the modified molecular sieve are: 1) Put the molecular sieve into a ball mill for grinding to make the molecular sieve into powder; 2) Place the molecular sieve powder in a sodium dodecyl sulfate solution, wash it clean, filter the washed molecular sieve, and then wash it with distilled water; 3) Mix the dried molecular sieve and 1-ethyl acetate-3-methylimidazolium hexafluorophosphate in a pure DMF solution, and heat in a water bath to obtain a modified molecular sieve solution; 4) Filter and wash the modified molecular sieve solution, and place the filter residue in a drying oven for drying to obtain a dry modified molecular sieve. The high-wear-resistant and high-anti-slip TPU sole for injection molding according to claim 3 is characterized in that: in the step 1), the grinding time is 15 to 20 minutes and the rotation speed is 1100 to 1300 rpm. The high wear-resistant and high anti-slip TPU sole for injection molding according to claim 3, characterized in that: in the step 2), the distilled water washing is performed 2 to 3 times. The injection-molded, high-wear-resistant, high-anti-slip TPU sole according to claim 3, wherein in step 3), the molecular sieve, 1-ethyl acetate-3-methylimidazolium hexafluorophosphate, and pure DMF solution are mixed in a mass ratio of 5:1. The injection-molded, high-wear-resistant, high-anti-slip TPU sole according to claim 3, wherein the water bath temperature in step 3) is 65-75° C., the water bath time is 10-14 hours, and the stirring speed is 90-110 rpm. The high wear-resistant and high anti-slip TPU sole for injection molding according to claim 3 is characterized in that the temperature in the drying oven is 110-130°C. The injection-molded, high-wear-resistant, high-anti-slip TPU sole according to claim 1 is characterized in that the TPU is a polyether polyurethane having a Shore hardness of 60A to 45D, and the TPU-NBR composite material is prepared by pouring the TPU into a torque rheometer under constant temperature conditions, melting the TPU, first increasing and then decreasing the torque, and adding the NBR rubber compound when the torque stabilizes, thereby obtaining the TPU-NBR composite material. The high-wear-resistant and high-anti-slip TPU sole for injection molding according to claim 9 is characterized in that: the mass ratio of TPU to NBR rubber mixture is 1:0.4, and when pouring TPU, the constant temperature in the moment rheometer is 170-175°C and the rotation speed is 75-85 r/min.