A rubber shoe material with normal temperature and low temperature anti-wet skid resistance and a preparation method thereof

Abstract

The application discloses a kind of normal temperature and low temperature anti-wet skid rubber shoe material and preparation method thereof, wherein shoe material is by following material according to weight fraction Composition:100 parts rubber, 40-60 parts reinforcing filler, 10-30 parts functional filler, 4-8 parts modified resin, 2-6 parts coupling agent, 3-6 parts zinc oxide, 1-2 parts stearic acid, 3-8 parts active agent, 1-3 anti-aging agent, 1-5 parts plasticizer, 1-3 parts sulfur, 1-5 parts accelerator;The functional filler is any one or several combinations of calcium sulfate whisker, basic magnesium sulfate whisker, potassium titanate whisker, borate whisker and phosphate whisker.The product of the application has excellent anti-wet skid effect while maintaining good physical properties, and can be applied to safety shoes, outdoor shoes, sports shoes and other high-demand application scenarios, especially in cold regions.

Description

Technical Field

[0001] This invention belongs to the field of footwear technology, specifically a rubber footwear material that is both room temperature and low temperature resistant to wet and slippery conditions, and its preparation method. Background Technology

[0002] The anti-slip performance of shoe soles directly affects walking safety, making the anti-slip effect of shoe soles a key focus. Relatively speaking, traditional rubber soles are far less effective at preventing slipping on wet or puddled surfaces than on dry surfaces, especially in cold regions like northern areas where low temperatures further reduce their wet-wet slip resistance. Therefore, improving the wet-wet performance of rubber soles, particularly in low-temperature environments, has become a continuous goal for shoe sole developers.

[0003] Improving wet slip performance by introducing new materials or technologies based on existing rubber materials and processes has always been a research hotspot. For example, Chinese patent application (application publication number CN119699723A) discloses a method that improves the drainage effect of shoe soles in wet and slippery grass or waterlogged environments by designing a special bottom pattern based on existing materials, ultimately improving the anti-slip performance of shoe sole products. Chinese patent (CN121271131A) discloses a technical solution for improving the anti-slip effect of shoe soles using bio-based crystalline fibers (50-500nm in length and 2-50nm in diameter). Its nanoscale size also helps to reinforce rubber materials and improve physical properties. In addition, according to public reports, adding glass fibers to rubber materials can increase the anti-slip ability of shoe soles on wet or icy surfaces because they can penetrate water films and form strong physical anchor points with the ground. This technical solution is relatively mature and widely used in the production of related shoe sole products.

[0004] The design of the outsole pattern has a significant impact on the product's anti-slip performance, but it needs to work in conjunction with the excellent anti-slip properties of the outsole material itself to achieve the best results. Furthermore, while glass fiber has the advantage of improving wet or ice slip resistance, its production requires additional processing techniques to ensure the directional arrangement of the glass fibers within the rubber. Also, due to the high hardness of glass fiber (Mohs hardness 6.5), it remains difficult to effectively address the issue of it damaging floors when worn indoors. Moreover, during wear, as the fiber material wears down, the anti-slip effect of the outsole also decreases significantly. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a rubber shoe material that is both suitable for room temperature and low temperature slip resistance.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] A rubber shoe material that provides both room temperature and low temperature slip resistance is composed of the following materials in parts by weight: 100-130 parts rubber, 40-60 parts reinforcing filler, 10-30 parts functional filler, 4-8 parts modified resin, 2-6 parts coupling agent, 3-6 parts zinc oxide, 1-2 parts stearic acid, 3-8 parts activator, 1-3 parts anti-aging agent, 1-5 parts plasticizer, 1-3 parts sulfur, and 1-5 parts accelerator; wherein the functional filler is any one or a combination of several of calcium sulfate whiskers, basic magnesium sulfate whiskers, potassium titanate whiskers, borate whiskers, and phosphate whiskers.

[0008] The potassium titanate whiskers include potassium hexatitanate whiskers and potassium octatitanate whiskers.

[0009] The modified resin is selected from any one or a combination of several of petroleum resins and their derivatives, rosin resins and their derivatives, and terpene resins and their derivatives.

[0010] The rubber is selected from any one or a combination of several of the following: natural rubber, isoprene rubber, cis-butadiene rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, and halogenated butyl rubber.

[0011] The cis-butadiene rubber includes high cis-polybutadiene rubber, high vinyl polybutadiene rubber, liquid polybutadiene rubber, and silane-modified liquid polybutadiene rubber.

[0012] The reinforcing filler is selected from any one or a combination of several of precipitated silica, fumed silica, talc, and clay.

[0013] The silane coupling agent is a silane coupling agent containing thiol, polysulfide, amino, vinyl or epoxy groups, and / or a titanate coupling agent.

[0014] The anti-aging agent is selected from any one or a combination of several of hindered phenols, p-phenylenediamine and its derivatives, hindered amines, or protective waxes.

[0015] Furthermore, the anti-aging agent is a combination of anti-aging agent BHT and protective wax RW159, and the mass ratio of anti-aging agent BHT to protective wax RW159 is (1-2):(0.5-1).

[0016] The accelerator is selected from any one or a combination of several of the following: thiazoles, sulfenamides, thiurams, thiophosphates, xanthates, and thioureas.

[0017] Furthermore, the accelerator is a combination of accelerator DM-75 and accelerator TS-80, and the mass ratio of accelerator DM-75 to accelerator TS-80 is (1.6-2):(0.1-0.5).

[0018] A method for preparing a rubber shoe material that is both suitable for room temperature and low temperature slip resistance includes the following steps:

[0019] S1, control the initial temperature of the internal mixer to 80-85℃, add rubber and modified resin, mix for 1-2 minutes, and control the material temperature in the mixing chamber to 95-105℃;

[0020] S2, add zinc oxide, stearic acid, reinforcing filler and coupling agent, mix for 2-3 minutes, and control the material temperature in the mixing chamber to 105-115℃;

[0021] S3, add functional fillers, plasticizers, activators and anti-aging agents, mix for 2-3 minutes, and control the material temperature in the mixing chamber to 110-120℃;

[0022] S4, continue mixing for 1-2 minutes and then stop the internal mixing to obtain a mixture. Keep the temperature of the mixture at 120-130℃.

[0023] S5, take the mixture from the internal mixer and add it. The temperature of the front roll in the two-roll mill should not exceed 80℃. Mix the rubber for 3-4 minutes to obtain the compound. Then add sulfur and accelerator to mix with the compound. Mix in the two-roll mill for 3-5 minutes. Control the roll gap to >5mm and the material temperature to 80-100℃ throughout the entire operation.

[0024] S6, the roll gap is set according to the production requirements to produce sheet material, the sheet material is cooled down, then the surface moisture is removed and the rubber material is taken out;

[0025] S7. The rubber compound is left to stand in an environment of 20-30℃ for 3-4 hours, and then tested, including at least sulfur change test and scorch test. If the rubber compound is qualified, it is released to proceed to the next preparation step; otherwise, it is isolated and sealed.

[0026] S8, set the mold temperature to 150-160℃ and the pressure to 150-200 kgf / cm. 2 The qualified rubber material is placed into the mold and vulcanized. The molding time is controlled to be 3-6 minutes according to the vulcanization process requirements to complete the preparation of the shoe material.

[0027] The present invention has the following beneficial technical effects:

[0028] 1. This invention provides a rubber shoe material product that combines room temperature and low temperature anti-slip properties. By optimizing the selection and combination of raw materials in the system and controlling the amount added, the product's anti-slip performance is significantly improved in both room temperature and low temperature environments while ensuring physical properties, thus better guaranteeing the wearer's safety.

[0029] 2. This invention introduces inorganic salt whiskers and modified resin into the formulation system simultaneously, particularly potassium titanate whiskers and rosin resin in a mass ratio of (2-5):(1-2). The potassium titanate whiskers, with their micron-sized dimensions, ensure good dispersion in the rubber and have a lower hardness than glass fiber (glass fiber has a Mohs hardness of approximately 6.5), thus achieving both water film penetration and floor protection. The modified resin, containing polar groups, exhibits good hydrophilicity and synergistically works with the potassium titanate whiskers in penetrating the water film. Furthermore, the alkaline nature of the potassium titanate whiskers effectively neutralizes the slowing effect of the acidic modified resin on the vulcanization rate. In addition, the introduction of liquid rubber into the formulation significantly reduces the glass transition temperature of the rubber compound while maintaining physical properties, improving the flexibility and dynamic hysteresis of the sole in low-temperature environments and ensuring its anti-slip performance. The combined use of both also further optimizes the vulcanization rate of the rubber compound, facilitating processing and improving appearance while making the material more suitable for the application requirements of footwear products.

[0030] 3. This invention introduces silane-modified polybutene rubber, which significantly reduces the glass transition temperature of the material while ensuring the physical properties of the rubber compound, improves the flexibility and dynamic hysteresis performance of the sole in low-temperature environments, and enhances its anti-slip effect in low-temperature environments.

[0031] 4. This invention optimizes the rubber composition, reinforcing filler, silane coupling agent and activator to improve the reinforcement and vulcanization efficiency, and optimizes the combination of additives and vulcanization system to provide products with a hardness of 50-55 (Shor A), tensile strength ≥11MPa, elongation at break ≥500%, trouser tear ≥12.0MPa, wet slip at room temperature ≥0.87, and wet slip at low temperature ≥0.51.

[0032] 5. The product provided by this invention maintains good physical properties while having excellent anti-slip properties, and is suitable for high-requirement application scenarios such as work shoes, outdoor shoes, and sports shoes, especially footwear products used in cold regions. Detailed Implementation

[0033] The technical content of the present invention will be described in detail below with reference to specific embodiments.

[0034] A rubber shoe material that provides both room temperature and low temperature slip resistance is composed of the following materials in parts by weight: 100-130 parts rubber, 40-60 parts reinforcing filler, 10-30 parts functional filler, 4-8 parts modified resin, 2-6 parts coupling agent, 3-6 parts zinc oxide, 1-2 parts stearic acid, 3-8 parts activator, 1-3 parts anti-aging agent, 1-5 parts plasticizer, 1-3 parts sulfur, and 1-5 parts accelerator; wherein the functional filler is any one or a combination of several of calcium sulfate whiskers, basic magnesium sulfate whiskers, potassium titanate whiskers, borate whiskers, and phosphate whiskers.

[0035] The potassium titanate whiskers include potassium hexatitanate whiskers and potassium octatitanate whiskers. The potassium octatitanate whiskers have a length of 10-100 micrometers, a diameter of 0.1-1.5 micrometers, and a Mohs hardness of 5-5.5.

[0036] The modified resin is selected from any one or a combination of several of petroleum resins and their derivatives, rosin resins and their derivatives, and terpene resins and their derivatives. The rosin resin and its derivatives are rosin, with an acid value of 160-170 mg KOH / g and a softening point of 80-90℃.

[0037] The rubber is selected from any one or a combination of several of the following: natural rubber, isoprene rubber, cis-butadiene rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, and halogenated butyl rubber. The cis-butadiene rubber includes high-cis polybutadiene rubber, high-vinyl polybutadiene rubber, liquid polybutadiene rubber, and silane-modified liquid polybutadiene rubber. The average molecular weight of the silane-modified liquid polybutadiene rubber is 6000-10000 g / mol.

[0038] The reinforcing filler is selected from any one or a combination of several of precipitated silica, fumed silica, talc, and clay.

[0039] The silane coupling agent is a silane coupling agent containing thiol, polysulfide, amino, vinyl or epoxy groups, and / or a titanate coupling agent.

[0040] The anti-aging agent is selected from any one or a combination of hindered phenols, p-phenylenediamine and its derivatives, hindered amines, or protective waxes. The anti-aging agent is a combination of anti-aging agent BHT and protective wax RW159, and the mass ratio of anti-aging agent BHT to protective wax RW159 is (1-2):(0.5-1).

[0041] The accelerator is selected from any one or a combination of several of the following: thiazoles, sulfenamides, thiurams, thiophosphates, xanthates, and thioureas. The accelerator is a combination of accelerator DM-75 and accelerator TS-80, and the mass ratio of accelerator DM-75 to accelerator TS-80 is (1.6-2):(0.1-0.5).

[0042] The plasticizer can be a white naphthenic oil.

[0043] For various materials, select the appropriate model as shown in Table 1 below.

[0044] Table 1

[0045] There are no special restrictions on other materials.

[0046] The following five examples illustrate the different proportions of each material, as shown in Table 2.

[0047] Table 2

[0048] The shoe materials in the above five embodiments were all prepared according to the following methods.

[0049] A method for preparing rubber shoe materials that are suitable for both room temperature and low-temperature slippery conditions includes the following steps:

[0050] In S1, in a mixer equipped with a cooling water system, the initial temperature is controlled at 80-85℃. Isoprene rubber, high cis polybutadiene rubber, styrene-butadiene rubber, brominated butyl rubber, and modified resin are added. The mixture is hammer-mixed for 1-2 minutes, and the material temperature in the mixing chamber is controlled at 95-105℃.

[0051] S2, after lifting the hammer, add zinc oxide, stearic acid, silica and silane coupling agent, silane-modified liquid polybutadiene rubber, and hammer mix for 2-3 minutes, controlling the material temperature in the mixing chamber to be 105-115℃.

[0052] S3, after cleaning with the hammer, add potassium octatitanate whiskers, naphthenic oil, activator and antioxidant, and hammer mix for 2-3 minutes, controlling the material temperature in the mixing chamber to 110-120℃, and lift the hammer once in the middle.

[0053] S4, after sweeping with the hammer, continue mixing for 1-2 minutes before stopping the internal mixing, confirming that the material temperature is 120-130℃ at this time.

[0054] The S5 is a two-roll mill equipped with a cooling water system and a material turning system. Before feeding, the roll temperature does not exceed 80°C. The compound rubber is mixed with sulfur and accelerator through the two-roll mill. The material turning system is started to assist in mixing for 3-5 minutes. The roll gap is controlled to be >5mm and the material temperature is 80-100°C throughout the operation.

[0055] S6, the roll gap is set according to production requirements for sheet output. The sheet material passes through the cooling water tank and the anti-sticking liquid tank in succession. Then, the surface moisture is removed by hanging or air blowing. After drying, it is stacked and stored.

[0056] S7, after being left to stand in an environment of 20-30℃ for 3-4 hours, the rubber compound is tested, including at least a sulfur change test and a scorch test. If the rubber compound is deemed qualified, it is released to proceed to the next preparation step; otherwise, it is isolated and sealed.

[0057] S8, set the mold temperature to 150-160℃ and the pressure to 150-200 kgf / cm. 2 The material is then placed in the mold and vulcanized. The molding time is controlled to be 3-6 minutes according to the vulcanization process requirements.

[0058] Performance testing

[0059] 1. The following performance tests were performed on the products prepared in the five embodiments. The test reference standards are as follows, and the test results are shown in Table 3.

[0060] (1) Test the hardness of the vulcanized rubber sample according to GB / T531.1-2008.

[0061] (2) The tensile strain properties of the vulcanized rubber samples were tested in accordance with GB / T528-2009, including dumbbell-shaped specimen type I, 300% constant elongation stress, tensile strength, and elongation at break.

[0062] (3) Test the tear strength of the vulcanized rubber sample according to GB / T529-2008 (right-angle tear strength without cut, trouser tear strength).

[0063] (4) The wet slip performance of the vulcanized rubber samples was tested according to GB / T 28287-2012. The low temperature group samples were treated as follows: the samples were placed in an environment of -20℃ for 3 hours before the test, and the test was carried out immediately after they were taken out.

[0064] Table 3

[0065] 2. The vulcanization characteristics (155℃) of the rubber compounds in each example were tested according to GB / T-16584-1996, and the results are shown in Table 4.

[0066] Table 4

[0067]

[0068] Analysis of Tables 3 and 4 shows that the rubber shoe sole product provided in Example 5 of the present invention, which is suitable for both room temperature and low temperature wet slip, has a significant improvement in anti-slip performance compared with the products provided in Examples 1-4. That is, the materials and their dosage ratios corresponding to Example 5 are optimal.

[0069] It should be noted that the above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. However, any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A rubber shoe material that combines room temperature and low-temperature slip resistance, characterized in that, It is composed of the following materials in parts by weight: 100 parts rubber, 40-60 parts reinforcing filler, 10-30 parts functional filler, 4-8 parts modified resin, 2-6 parts coupling agent, 3-6 parts zinc oxide, 1-2 parts stearic acid, 3-8 parts activator, 1-3 parts anti-aging agent, 1-5 parts plasticizer, 1-3 parts sulfur, and 1-5 parts accelerator; the functional filler is any one or a combination of several of calcium sulfate whiskers, basic magnesium sulfate whiskers, potassium titanate whiskers, borate whiskers, and phosphate whiskers.

2. The rubber shoe material that combines room temperature and low temperature slip resistance according to claim 1, characterized in that, The potassium titanate whiskers include potassium hexatitanate whiskers and potassium octatitanate whiskers.

3. The rubber shoe material according to claim 1, which combines room temperature and low temperature slip resistance, is characterized in that... The modified resin is selected from any one or a combination of several of petroleum resins and their derivatives, rosin resins and their derivatives, and terpene resins and their derivatives.

4. The rubber shoe material that combines room temperature and low temperature slip resistance according to claim 1, characterized in that, The rubber is selected from any one or a combination of several of the following: natural rubber, isoprene rubber, cis-butadiene rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, and halogenated butyl rubber.

5. The rubber shoe material according to claim 4, which combines room temperature and low temperature slip resistance, is characterized in that... The cis-butadiene rubber includes high cis-polybutadiene rubber, high vinyl polybutadiene rubber, liquid polybutadiene rubber, and silane-modified liquid polybutadiene rubber.

6. The rubber shoe material according to claim 1, which combines room temperature and low temperature slip resistance, is characterized in that... The reinforcing filler is selected from any one or a combination of several of precipitated silica, fumed silica, talc, and clay.

7. The rubber shoe material according to claim 1, which combines room temperature and low temperature slip resistance, is characterized in that... The silane coupling agent is a silane coupling agent containing thiol, polysulfide, amino, vinyl or epoxy groups, and / or a titanate coupling agent.

8. The rubber shoe material according to claim 1, which combines room temperature and low temperature slip resistance, is characterized in that... The anti-aging agent is selected from any one or a combination of several of hindered phenols, p-phenylenediamine and its derivatives, hindered amines, or protective waxes.

9. The rubber shoe material according to claim 1, which combines room temperature and low temperature slip resistance, is characterized in that... The accelerator is selected from any one or a combination of several of the following: thiazoles, sulfenamides, thiurams, thiophosphates, xanthates, and thioureas.

10. A method for preparing a rubber shoe material that combines room temperature and low temperature slip resistance according to any one of claims 1-9, characterized in that, Includes the following steps: S1, control the initial temperature of the internal mixer to 80-85℃, add rubber and modified resin, mix for 1-2 minutes, and control the material temperature in the mixing chamber to 95-105℃; S2, add zinc oxide, stearic acid, reinforcing filler and coupling agent, mix for 2-3 minutes, and control the material temperature in the mixing chamber to 105-115℃; S3, add functional fillers, plasticizers, activators and anti-aging agents, mix for 2-3 minutes, and control the material temperature in the mixing chamber to 110-120℃; S4, continue mixing for 1-2 minutes and then stop the internal mixing to obtain a mixture. Keep the temperature of the mixture at 120-130℃. S5, take the mixture from the internal mixer and add it. The temperature of the front roll in the two-roll mill should not exceed 80℃. Mix the rubber for 3-4 minutes to obtain the compound. Then add sulfur and accelerator to mix with the compound. Mix in the two-roll mill for 3-5 minutes. Control the roll gap to >5mm and the material temperature to 80-100℃ throughout the entire operation. S6, the roll gap is set according to the production requirements to produce sheet material, the sheet material is cooled down, then the surface moisture is removed and the rubber material is taken out; S7. The rubber compound is left to stand in an environment of 20-30℃ for 3-4 hours, and then tested, including at least sulfur change test and scorch test. If the rubber compound is qualified, it is released to proceed to the next preparation step; otherwise, it is isolated and sealed. S8, set the mold temperature to 150-160℃ and the pressure to 150-200 kgf / cm. 2 The qualified rubber material is placed into the mold and vulcanized. The molding time is controlled to be 3-6 minutes according to the vulcanization process requirements to complete the preparation of the shoe material.

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