Wear-resistant rain shoes and production process thereof

Abstract

The invention relates to the technical field of rubber products, and discloses wear-resistant rain shoes and a production process thereof. Comprising the following components in parts by weight: 40-60 parts of nitrile rubber, 30-50 parts of chloroprene rubber, 20-40 parts of natural rubber, 20-35 parts of fumed silica, 15-25 parts of nano calcium carbonate, 8-15 parts of aramid fiber, 8-12 parts of an environment-friendly plasticizer, 2-4 parts of a vulcanization accelerator, 3-6 parts of an active agent, 3-5 parts of an anti-aging agent and 3-6 parts of an anti-ultraviolet stabilizer. The anti-ultraviolet stabilizer is a mixture prepared from a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber according to the mass ratio of (2 to 1) to (3 to 1). The rain shoes have multiple additional functions, the anti-ultraviolet stabilizer can prevent the rain shoes from being degraded under sunlight irradiation, the material performance is maintained, and the appearance color is kept; the antibacterial agent can inhibit bacterium breeding, peculiar smell and bacterial infection are prevented from being generated in the rain shoes, foot health is guaranteed, wearing safety and comfort are improved, and the use scene and function range of the rain shoes are remarkably expanded.

Description

Technical Field

[0001] The invention relates to the technical field of rubber products, in particular to wear-resistant rain boots and a production process thereof. Background Art

[0002] In modern life, wear-resistant rain boots are key equipment for dealing with wet and complex terrain.

[0003] The wear-resistant rain boots currently on the market generally have some defects. After long-term use, the uppers of many rain boots are easily worn, resulting in reduced waterproof performance and shortening the service life. Some rain boots lack effective antibacterial functions, which easily breed bacteria in humid environments, produce odors, and endanger foot health. Moreover, general rain boots have poor visibility in low light or night environments, increasing the safety risks of users.

[0004] Based on this, a wear-resistant rain boot and a production process thereof are proposed. Summary of the invention

[0005] The purpose of the present invention is to solve the above problems and to provide a wear-resistant rain boot and a production process thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The invention discloses wear-resistant rain boots, comprising the following ingredients in parts by weight: 40-60 parts of nitrile rubber, 30-50 parts of chloroprene rubber, 20-40 parts of natural rubber, 20-35 parts of fumed silica, 15-25 parts of nano calcium carbonate, 8-15 parts of aramid fiber, 8-12 parts of environmentally friendly plasticizer, 2-4 parts of vulcanization accelerator, 3-6 parts of active agent and 3-5 parts of antioxidant.

[0008] Preferably, 3-6 parts of an anti-ultraviolet stabilizer are further included, wherein the anti-ultraviolet stabilizer is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in a mass ratio of 2:1-3:1, wherein the molecular weight of the hindered amine light stabilizer is 1000-3000, and the maximum absorption wavelength of the benzotriazole ultraviolet absorber is in the range of 300-380nm.

[0009] Preferably, it also includes 2-5 parts of an antibacterial agent, and the preparation method of the antibacterial agent is:

[0010] The nano silver particles and the quaternary ammonium salt antibacterial agent are mixed in a mass ratio of 1:3-1:5, and 5%-10% of the mass of the nano silver particles of the dispersant polyvinyl pyrrolidone are added, and the mixture is dispersed for 30-60 minutes under high-speed stirring at a rotation speed of 1000-1500 rpm.

[0011] Preferably, it also includes 3-8 parts of a fluorescent tracer, and the preparation method of the fluorescent tracer is:

[0012] Sodium fluorescein and polyurethane microspheres are mixed in an organic solvent at a mass ratio of 1:2-1:4, wherein the organic solvent is toluene or xylene, dispersed for 30-60 minutes under an ultrasonic environment with a frequency of 20-40 kHz, and then the organic solvent is removed by a rotary evaporator at 50-70° C. and a vacuum degree of 0.08-0.1 MPa to obtain the product.

[0013] Preferably, the invention further comprises 5-10 parts of graphene nanosheets, wherein the graphene nanosheets have 3-10 layers, a sheet diameter of 1-5 μm, and a surface thereof is carboxylated and modified by using chloroacetic acid as a modifier, with a modification degree of 5%-10%.

[0014] A production process for wear-resistant rain boots comprises the following steps:

[0015] S1: premixing nitrile rubber, chloroprene rubber and natural rubber in an internal mixer at 80-100° C. for 5-10 minutes to obtain a premix A;

[0016] S2: Add fumed silica, nano calcium carbonate and aramid fiber to premix A, raise the temperature to 120-140° C., and knead for 15-20 minutes to obtain mixture B;

[0017] S3: adding an anti-ultraviolet stabilizer, graphene nanosheets, an environmentally friendly plasticizer, a vulcanization accelerator, and an active agent to the mixture B, and continuing to knead at 150-170° C. for 10-15 minutes to obtain a mixture C;

[0018] S4: adding an antimicrobial agent and a fluorescent tracer to the mixture C, and kneading at 160-180° C. for 8-12 minutes to obtain a mixture D;

[0019] S5: adding an antioxidant to the mixture D, discharging the mixture after mixing for 5-8 minutes, and leaving the rubber material at room temperature for 12-24 hours to obtain a wear-resistant rain boot material.

[0020] Preferably, the production process of the wear-resistant rain boots includes:

[0021] The obtained wear-resistant rain boots material is vulcanized on a flat vulcanizer at a vulcanization temperature of 140-160° C., a vulcanization pressure of 10-15 MPa, and a vulcanization time of 30-60 minutes. After demolding, secondary vulcanization is performed in an oven at 80-100° C. for 1-3 hours to obtain finished wear-resistant rain boots.

[0022] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0023] 1. This application adopts a non-single rubber formula, which combines nitrile rubber, chloroprene rubber and natural rubber. Nitrile rubber gives it excellent oil resistance, which can effectively resist oil erosion and maintain the stability of the upper material performance in complex environments; chloroprene rubber brings excellent weather resistance, whether it is exposed to the sun or washed by rain, it is not easy to age or crack, which greatly extends the service life of rain boots; natural rubber enhances the elasticity and flexibility of rain boots, making them more comfortable to wear, and can better fit the foot movements when walking, reducing fatigue.

[0024] 2. This application adopts reinforcing filling materials by adding fumed silica, nano calcium carbonate and aramid fiber. The high specific surface area of ​​fumed silica greatly improves the material strength, nano calcium carbonate optimizes cost-effectiveness while strengthening, and the high strength and high modulus characteristics of aramid fiber provide strong wear resistance for rain boots, effectively resisting the loss caused by daily walking and friction, ensuring that the upper remains intact for a long time, and maintaining good waterproof and protective effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A schematic diagram of the production process of wear-resistant rain boots provided according to an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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 creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] Wear-resistant rain boots were prepared according to the following formula: 40 parts of nitrile rubber, 30 parts of chloroprene rubber, and 20 parts of natural rubber were weighed, placed in an internal mixer, and premixed at 80°C for 5 minutes to obtain premix A. 20 parts of fumed silica, 15 parts of nano calcium carbonate, and 8 parts of aramid fiber were added to premix A, the temperature was raised to 120°C, and the mixture was mixed for 15 minutes to obtain mixture B. 3 parts of anti-ultraviolet stabilizer (the hindered amine light stabilizer and the benzotriazole ultraviolet absorber were composed of a mass ratio of 2:1, the hindered amine light stabilizer molecular weight was 1000, and the benzotriazole ultraviolet absorber had a maximum absorption wavelength of 300nm), 5 parts of graphene nanosheets (3 layers, sheet diameter 1μm, surface modified by chloroacetic acid carboxylation, modification degree 5%), 8 parts of environmentally friendly plasticizer, 2 parts of vulcanization accelerator, and 3 parts of activator were added to mixture B, and the mixture was further mixed at 150°C for 10 minutes to obtain mixture C. Add 2 parts of antibacterial agent (nanosilver particles and quaternary ammonium salt antibacterial agent are mixed in a mass ratio of 1:3, and polyvinyl pyrrolidone, a dispersant of 5% of the mass of nanosilver particles, is added, and dispersed for 30 minutes under stirring at a speed of 1000rpm) and 3 parts of fluorescent tracer (fluorescein sodium and polyurethane microspheres are mixed in toluene in a mass ratio of 1:2, dispersed in an ultrasonic environment at a frequency of 20kHz for 30 minutes, and then the organic solvent is removed by a rotary evaporator at 50°C and a vacuum degree of 0.08MPa) to the mixture C, and knead at 160°C for 8 minutes to obtain a mixture D. Add 3 parts of antioxidant to the mixture D, mix for 5 minutes and then discharge the material, and leave the rubber material at room temperature for 12 hours to obtain a high-performance wear-resistant rain boots material. The obtained material is vulcanized and molded on a flat vulcanizer, the vulcanization temperature is 140°C, the vulcanization pressure is 10MPa, the vulcanization time is 30 minutes, and after demolding, secondary vulcanization is performed in an oven at 80°C for 1 hour to obtain a finished high-performance wear-resistant rain boots.

[0029] Example 2

[0030] Change the formula to prepare wear-resistant rain boots: weigh 50 parts of nitrile rubber, 40 parts of chloroprene rubber, and 30 parts of natural rubber, put them into a mixer, and premix them at 90°C for 8 minutes to obtain premix A. Add 25 parts of fumed silica, 20 parts of nano calcium carbonate, and 12 parts of aramid fiber to premix A, heat to 130°C, and mix for 18 minutes to obtain mixture B. Add 4 parts of anti-ultraviolet stabilizer (the hindered amine light stabilizer and the benzotriazole ultraviolet absorber are composed of a mass ratio of 2.5:1, the hindered amine light stabilizer has a molecular weight of 2000, and the benzotriazole ultraviolet absorber has a maximum absorption wavelength of 340nm) to mixture B, 8 parts of graphene nanosheets (6 layers, sheet diameter 3μm, surface modified by chloroacetic acid carboxylation, modification degree 8%), 10 parts of environmentally friendly plasticizer, 3 parts of vulcanization accelerator, and 4 parts of activator, and continue to mix at 160°C for 12 minutes to obtain mixture C. Add 3 parts of antibacterial agent (nanosilver particles and quaternary ammonium salt antibacterial agent are mixed in a mass ratio of 1:4, and polyvinyl pyrrolidone, a dispersant of 8% of the mass of nanosilver particles, is added, and dispersed for 45 minutes under stirring at a speed of 1200rpm) and 5 parts of fluorescent tracer (fluorescein sodium and polyurethane microspheres are mixed in xylene in a mass ratio of 1:3, dispersed in an ultrasonic environment at a frequency of 30kHz for 45 minutes, and then the organic solvent is removed by a rotary evaporator at 60°C and a vacuum degree of 0.09MPa) to the mixture C, and knead at 170°C for 10 minutes to obtain a mixture D. Add 4 parts of antioxidant to the mixture D, mix for 6 minutes and then discharge the material, and leave the rubber material at room temperature for 18 hours to obtain a high-performance wear-resistant rain boots material. The obtained material is vulcanized and molded on a flat vulcanizer, the vulcanization temperature is 150°C, the vulcanization pressure is 13MPa, the vulcanization time is 45 minutes, and after demolding, secondary vulcanization is performed in an oven at 90°C for 2 hours to obtain a finished high-performance wear-resistant rain boots.

[0031] Example 3

[0032] Adjust the formula again to prepare wear-resistant rain boots: weigh 60 parts of nitrile rubber, 50 parts of chloroprene rubber, and 40 parts of natural rubber, put them into a mixer, and premix them at 100°C for 10 minutes to obtain premix A. Add 35 parts of fumed silica, 25 parts of nano calcium carbonate, and 15 parts of aramid fiber to premix A, heat to 140°C, and mix for 20 minutes to obtain mixture B. Add 6 parts of anti-ultraviolet stabilizer (the hindered amine light stabilizer and the benzotriazole ultraviolet absorber are composed of a mass ratio of 3:1, the hindered amine light stabilizer has a molecular weight of 3000, and the benzotriazole ultraviolet absorber has a maximum absorption wavelength of 380nm) to mixture B, 10 parts of graphene nanosheets (10 layers, 5 μm in diameter, the surface is modified by chloroacetic acid carboxylation, and the degree of modification is 10%), 12 parts of environmentally friendly plasticizer, 4 parts of vulcanization accelerator, and 6 parts of activator, and continue to mix at 170°C for 15 minutes to obtain mixture C. Add 5 parts of antibacterial agent (nanosilver particles and quaternary ammonium salt antibacterial agent are mixed in a mass ratio of 1:5, and polyvinyl pyrrolidone, a dispersant of 10% of the mass of nanosilver particles, is added, and dispersed for 60 minutes at a speed of 1500rpm and stirred) and 8 parts of fluorescent tracer (fluorescein sodium and polyurethane microspheres are mixed in toluene in a mass ratio of 1:4, dispersed in an ultrasonic environment of a frequency of 40kHz for 60 minutes, and then the organic solvent is removed by a rotary evaporator at 70°C and a vacuum degree of 0.1MPa) to the mixture C, and knead at 180°C for 12 minutes to obtain a mixture D. Add 5 parts of antioxidant to the mixture D, mix for 8 minutes and then discharge the material, and leave the rubber material at room temperature for 24 hours to obtain a high-performance wear-resistant rain boots material. The obtained material is vulcanized and molded on a flat vulcanizer, the vulcanization temperature is 160°C, the vulcanization pressure is 15MPa, the vulcanization time is 60 minutes, and after demolding, secondary vulcanization is performed in an oven at 100°C for 3 hours to obtain a finished high-performance wear-resistant rain boots.

[0033] Comparative Example 1

[0034] Compared with Example 1, no anti-ultraviolet stabilizer was added, and other components and preparation processes were exactly the same, so as to prepare comparative rain boots 1.

[0035] Comparative Example 2

[0036] Compared with Example 2, no antibacterial agent was added, and other components and preparation process remained unchanged, so as to prepare comparative rain boots 2.

[0037] Comparative Example 3

[0038] Compared with Example 3, no fluorescent tracer was added, and other components and preparation process were kept consistent to prepare comparison rain boots 3.

[0039] The following performance tests were performed on the rain boots obtained from Examples 1-3 and Comparative Examples 1-3:

[0040] Wear resistance test: Use Taber abrasion tester according to ASTMD394-16 standard and CS-17 grinding wheel to apply 5N pressure to key parts of the sole and upper of the rain boots. After rotating 500 times at 72r / min, measure the mass loss of the sample.

[0041] Anti-ultraviolet performance test: According to GB / T16422.3 standard, after 100 hours of exposure to simulated sunlight, the tensile strength retention rate (%) of the rain boots material is tested.

[0042] Antibacterial performance test: Referring to the AATCC100-2012 standard, Staphylococcus aureus and Escherichia coli were used as test bacteria. A certain amount of Staphylococcus aureus and Escherichia coli were inoculated on the inner surface of the rain boots. After culturing at 37°C and 90% humidity for 24 hours, the number of surviving bacteria was determined by the live bacteria counting method, and the antibacterial rate was calculated.

[0043] Fluorescent tracing effect test: In a dark environment, measure the visible distance of the rain boots' fluorescence (unit: m).

[0044] The test data are shown in the following table:

[0045]

[0046] From the comparison of the above table data, we can see that:

[0047] In terms of wear resistance: the wear amount of Examples 1-3 gradually decreases, indicating that with the optimization of the proportion of rubber, reinforcing filling materials and other components, the wear resistance of the rain boots is gradually improved. For example, increasing the amount of nitrile rubber, chloroprene rubber, and natural rubber, as well as the reasonable addition of fumed silica, nano-calcium carbonate, and aramid fiber, effectively enhances the ability of the rain boots to resist friction loss.

[0048] In terms of anti-ultraviolet performance: Comparative Example 1 does not add anti-ultraviolet stabilizers, and its tensile strength retention rate is significantly lower than that of Example 1, indicating that anti-ultraviolet stabilizers play a key role in preventing the performance of rain boots from deteriorating under sunlight. In addition, with the optimization of the ratio and parameters of hindered amine light stabilizers and benzotriazole ultraviolet absorbers in the anti-ultraviolet stabilizers (from Example 1 to Example 3), the anti-ultraviolet performance of the rain boots is gradually enhanced.

[0049] In terms of antibacterial performance: Comparative Example 2 did not add antibacterial agent, and its inhibition rate against Escherichia coli and Staphylococcus aureus was much lower than that of Example 2, which fully proved that the antibacterial agent was effective in inhibiting the growth of bacteria inside the rain boots. In Example 2-3, the amount of antibacterial agent added was increased, and the antibacterial effect was further improved.

[0050] In terms of fluorescent tracing effect: Comparative Example 3 did not add fluorescent tracers, and its fluorescent visible distance was 0, while the fluorescent visible distances of Examples 1-3 gradually increased, indicating that the addition of fluorescent tracers effectively improved the visibility of rain boots in low light or night environments, and as the amount added increased, the visible distance was farther.

[0051] In summary, the present invention adopts a non-single rubber formula, adds multiple functional additives, and optimizes the production process to prepare wear-resistant rain boots that have excellent performance in wear resistance, UV resistance, antibacterial and fluorescent tracing. The various components and process parameters work together to improve the comprehensive performance of the rain boots, meet the needs of different usage scenarios, and have good application prospects.

[0052] The above description of the embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A wear-resistant rain boot, characterized in that: The invention comprises the following ingredients in parts by weight: 40-60 parts of nitrile rubber, 30-50 parts of chloroprene rubber, 20-40 parts of natural rubber, 20-35 parts of fumed silica, 15-25 parts of nano calcium carbonate, 8-15 parts of aramid fiber, 8-12 parts of environmentally friendly plasticizer, 2-4 parts of vulcanization accelerator, 3-6 parts of activator and 3-5 parts of antioxidant.

2. A wear-resistant rain boot according to claim 1, characterized in that: It also includes 3-6 parts of an anti-ultraviolet stabilizer, which is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in a mass ratio of 2:1-3:1, wherein the molecular weight of the hindered amine light stabilizer is 1000-3000, and the maximum absorption wavelength of the benzotriazole ultraviolet absorber is in the range of 300-380nm.

3. The wear-resistant rain boots according to claim 1, characterized in that: It also includes 2-5 parts of an antibacterial agent, the preparation method of the antibacterial agent is as follows: The nano silver particles and the quaternary ammonium salt antibacterial agent are mixed in a mass ratio of 1:3-1:5, and 5%-10% of the mass of the nano silver particles of the dispersant polyvinyl pyrrolidone are added, and the mixture is dispersed for 30-60 minutes under stirring at a speed of 1000-1500 rpm.

4. The wear-resistant rain boots according to claim 1, characterized in that: It also includes 3-8 parts of a fluorescent tracer, and the preparation method of the fluorescent tracer is as follows: Sodium fluorescein and polyurethane microspheres are mixed in an organic solvent at a mass ratio of 1:2-1:4, wherein the organic solvent is toluene or xylene, dispersed for 30-60 minutes under an ultrasonic environment with a frequency of 20-40 kHz, and then the organic solvent is removed by a rotary evaporator at 50-70° C. and a vacuum degree of 0.08-0.1 MPa to obtain the product.

5. The wear-resistant rain boots according to claim 1, characterized in that: It also includes 5-10 portions of graphene nanosheets, wherein the graphene nanosheets have 3-10 layers, a sheet diameter of 1-5 μm, and a surface that has been carboxylated and modified by using chloroacetic acid as a modifier with a modification degree of 5%-10%.

6. A production process for wear-resistant rain boots according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1: premixing nitrile rubber, chloroprene rubber and natural rubber in an internal mixer at 80-100° C. for 5-10 minutes to obtain a premix A; S2: Add fumed silica, nano calcium carbonate and aramid fiber to premix A, raise the temperature to 120-140° C., and knead for 15-20 minutes to obtain mixture B; S3: adding an anti-ultraviolet stabilizer, graphene nanosheets, an environmentally friendly plasticizer, a vulcanization accelerator, and an active agent to the mixture B, and continuing to knead at 150-170° C. for 10-15 minutes to obtain a mixture C; S4: adding an antimicrobial agent and a fluorescent tracer to the mixture C, and kneading at 160-180° C. for 8-12 minutes to obtain a mixture D; S5: adding an antioxidant to the mixture D, discharging the mixture after mixing for 5-8 minutes, and leaving the rubber material at room temperature for 12-24 hours to obtain a wear-resistant rain boot material.

7. The production process of wear-resistant rain boots according to claim 6, characterized in that: The production process of the wear-resistant rain boots comprises: The obtained wear-resistant rain boots material is vulcanized on a flat vulcanizer at a vulcanization temperature of 140-160° C., a vulcanization pressure of 10-15 MPa, and a vulcanization time of 30-60 minutes. After demolding, secondary vulcanization is performed in an oven at 80-100° C. for 1-3 hours to obtain finished wear-resistant rain boots.

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