Wear-resistant non-slip rubber for shoe soles and method for manufacturing the same

Abstract

The application discloses a wear-resistant and skid-resistant rubber for shoe sole, which is prepared from raw material components A and B. The component A is prepared from rare earth butadiene rubber 49-60%, isoprene rubber 6-10%, ethylene-propylene-diene rubber 3-6%, bio-based white carbon black 15.1-20%, stearic acid 0.3-0.5%, zinc oxide 3-5%, antioxidant HP-264 2-3.5%, antioxidant SP-B 0.6-1%, microcrystalline wax 0.3-0.5%, white smoke activator 1.8-2.5%, silane coupling agent 2.5-3.5% and rosin resin 0.3-0.6% according to mass percentage. The component B is prepared from insoluble sulfur, a first accelerator and a second accelerator. The application further discloses a manufacturing method of the wear-resistant and skid-resistant rubber for shoe sole. The rare earth butadiene rubber has outstanding wear resistance and stable physical and chemical properties, the bio-based white carbon black is used as a filling agent, the reinforcing effect is better, and the bio-based white carbon black is low-carbon and environment-friendly, so that the green emission reduction is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of shoe sole material, in particular to a wear-resistant and slip-resistant rubber for shoe sole and a manufacturing method thereof. BACKGROUND

[0002] The slip resistance of shoe sole refers to the grip of the outsole on the ground or the slip resistance when sliding during walking. Qualified sports shoes should have certain slip resistance, which is an important indicator for judging the quality of shoes. The slip resistance of shoe sole directly affects the comfort and safety of wearing shoes. People are prone to slipping and falling and other safety accidents when wearing shoes with poor slip resistance. In order to obtain good slip resistance, researchers not only choose good slip-resistant materials, but also design good anti-slip patterns. The slip resistance of some shoe soles with patterns is good at first, but the slip resistance decreases quickly with the wear of the shoe sole.

[0003] The slip resistance of shoe sole varies with different shoe sole materials, different humidity environments, and different road surfaces. Therefore, when manufacturing shoe sole materials, the influence of various factors on the slip resistance of shoe sole should be considered comprehensively.

[0004] Rubber is one of the commonly used shoe sole materials. Although it has been challenged by some emerging thermoplastic materials in recent years, and a part of the market of rubber shoe sole materials has been replaced by other new materials, the excellent folding resistance, wear resistance, cold resistance, warmth retention, and waterproof performance of rubber shoe sole are far superior to those of other materials. Therefore, at present, it is still the most widely used shoe sole material. However, the wear resistance and slip resistance of rubber shoe sole materials are difficult to meet the use requirements at the same time.

[0005] A Chinese invention patent with the authorized announcement number CN102964645B discloses an ice surface slip-resistant rubber sports shoe sole and a manufacturing method thereof, which relates to a shoe sole. The ice surface slip-resistant rubber sports shoe sole and the manufacturing method thereof have good slip resistance on the road surface interface of thin ice, snow, and frozen soil layer, and have a longer service life. The raw material composition of the ice surface slip-resistant rubber sports shoe sole includes component A and component B. The component A includes cis-butadiene rubber, nitrile rubber, natural rubber, brominated butyl rubber, white carbon black, stearic acid, zinc oxide, anti-aging agent, microcrystalline wax, white smoke activator, silane coupling agent, rosin resin, aluminum oxide, and glass fiber. The component B includes insoluble sulfur, the first accelerator, the second accelerator, and pound material. The manufacturing method includes mixing, opening, adding medicine, measuring the sulfurization curve, and oil pressure forming. However, there are few reports on the wear-resistant and slip-resistant rubber shoe sole for ordinary outdoor sports. SUMMARY

[0006] The present application aims to provide a wear-resistant and slip-resistant rubber for shoe sole, which has good slip resistance and wear resistance, excellent ozone resistance and tear resistance, and meets the comprehensive performance requirements of shoe sole for outdoor sports.

[0007] In order to achieve the above-mentioned purpose, the solution of the present application is:

[0008] A wear-resistant and slip-resistant rubber for shoe sole, which comprises components A and B, wherein the component A is formulated according to the following mass percentage: 49-60% of rare earth butadiene rubber, 6-10% of isoprene rubber, 3-6% of ethylene-propylene-diene rubber, 15.1-20% of bio-based white carbon black, 0.3-0.5% of stearic acid, 3-5% of zinc oxide, 2-3.5% of antioxidant HP-264, 0.6-1% of antioxidant SP-B, 0.3-0.5% of microcrystalline wax, 1.8-2.5% of white smoke activator, 2.5-3.5% of silane coupling agent and 0.3-0.6% of rosin resin; and the component B is formulated as follows: insoluble sulfur, a first accelerator and a second accelerator, wherein the insoluble sulfur is added in an amount of 0.9-1.1% of the total mass of the component A, the first accelerator is added in an amount of 1-1.4% of the total mass of the component A, and the second accelerator is added in an amount of 0.2-0.3% of the total mass of the component A.

[0009] The insoluble sulfur is insoluble sulfur IS-75 / G.

[0010] A manufacturing method of the wear-resistant and slip-resistant rubber for shoe sole, which comprises the following steps:

[0011] Step 1, weighing:

[0012] ①Rare earth butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber and rosin resin are weighed according to the formula proportion to obtain a rubber main material mixture;

[0013] ②Bio-based white carbon black is weighed according to the formula proportion to obtain a filler;

[0014] ③Stearic acid, zinc oxide, antioxidant HP-264, antioxidant SP-B, microcrystalline wax, white smoke activator and silane coupling agent are weighed according to the formula proportion and mixed to obtain an additive mixture;

[0015] Step 2, closed mixing:

[0016] Mix the rubber main material mixture, put it into the internal mixer, turn on the internal mixer and mix evenly, 1-2 minutes later, add 25%-35% of the total weight of the bio-based white carbon black, continue to mix, mix the rubber main material mixture and the white carbon black, re-knead, mix for 3-4 minutes, then add the remaining 65%-75% of the total weight of the bio-based white carbon black and the additive mixture when the temperature reaches 100-110℃, mix for 2-3 minutes, then discharge when the temperature continues to rise to 140-150℃, and the base material is obtained;

[0017] Step 3, open mixing:

[0018] After the internal mixing is completed, the base material is subjected to open mixing on the open mill. The initial roller gap is 3-4 mm, and then it is thinned to a roller gap of 1-1.5 mm. The thinning frequency is 2 times. Then the roller gap is adjusted to 5 mm to discharge the sheet. After passing through the cooling water and the anti-sticking tank, the sheet is cut and left to stand at room temperature for more than 24 hours. The main purpose of open mixing is to mix the rubber and the additives more uniformly. Another purpose is to discharge the rubber in the form of a sheet, which is convenient for further processing.

[0019] Step 4, adding chemicals:

[0020] After the base material is left to stand for 24 hours, the insoluble sulfur, the first accelerator and the second accelerator are added to the open mill. The sheet material is punched three times on the open mill to form triangular packages. The roller gap is adjusted to 1-1.5 mm for the first and second triangular packages, and to 3-4 mm or the standard thickness set according to the shoe type for the third triangular package. After mixing uniformly, the rubber is discharged in the form of a sheet.

[0021] Step 5, measuring the curing curve and oil pressure forming:

[0022] A small piece of the material with chemicals is cut and subjected to sulfur variation measurement to record the scorch time and the positive curing time. The oil press is adjusted according to the recorded scorch time and positive curing time. The material with chemicals is cut into the shape of a shoe sole and hot-pressed into a rubber shoe mold. Before vulcanization, the temperature of the oil press is checked to be 160±5℃, the pressure is checked to be 150±5 MPa, and the vulcanization time is set correctly. The material is vulcanized for the set time. After vulcanization, the shoe sole is obtained.

[0023] The main physical properties include: hardness: 58±2A; specific gravity: ≤1.15 g / cm 3 ; DIN wear resistance: ≤60 mm 3 ; slip resistance: dry type: dry type slip resistance: ≥0.8, wet type slip resistance: ≥0.5; ozone resistance: ≥4 levels; tear resistance: ≥35 N / cm.

[0024] By adopting the technical scheme, the wear-resistant and slip-resistant rubber for shoe soles has outstanding wear-resistant performance of the rare earth butadiene rubber, stable physical and chemical performance, better reinforcing effect of the bio-based white carbon black, low-carbon and environmental protection, and achieves the purpose of green emission reduction.

[0025] The wear-resistant and slip-resistant rubber for shoe soles can achieve the slip-resistant performance of shoe soles on different outdoor interfaces, has a large friction coefficient when being in contact with different interfaces, especially has outstanding dry slip-resistant performance, and enhances the slip resistance and other comprehensive physical performance of the shoe soles. In order to meet the demand of outdoor ozone resistance of shoe soles, the rubber has high ozone resistance. DETAILED DESCRIPTION

[0026] In order to further explain the technical scheme of the present application, the present application will be described in detail through specific examples.

[0027] The product prepared by the formula and process of the present application can be tested for physical properties: after the prepared rubber shoe sole finished product is placed in a laboratory (23 DEG C) for 24 hours, the DIN wear resistance, hardness, slip resistance, ozone resistance and other physical properties are tested, and the wear resistance, hardness, slip resistance and ozone resistance test values are recorded. Among them:

[0028] Slip resistance experiment: the rubber slip resistance tester uses a SATRA STM 603 standard test machine, the tester is placed in a constant temperature environment of 23 DEG C ± 2 DEG C before testing, the test sample is cut into a standard specification, and is placed on a dry and wet ceramic tile interface for sliding test, and the maximum static friction force and sliding area ratio read by the computer is the sliding friction coefficient of the test sample.

[0029] The ozone resistance tester uses a high-iron OZ-0500AC, and the test conditions are: ozone concentration 50 DEG C ± 2 DEG C, temperature 40 DEG C ± 2 DEG C, humidity 65 DEG C ± 2 DEG C, and time 12 hours.

[0030] The formula range of the wear-resistant and slip-resistant rubber for shoe soles of the present application is shown in Table 1, and the values in each example of the wear-resistant and slip-resistant rubber for shoe soles are mass percentages (%) shown in Table 2.

[0031] Table 1 Formula range of wear-resistant and slip-resistant rubber for shoe soles

[0032]

[0033]

[0034] Table 2 Formula of each example of wear-resistant and slip-resistant rubber for shoe soles (%)

[0035]

[0036]

[0037] In the manufacturing method of the wear-resistant and slip-resistant rubber for the shoe sole in Embodiments 1-3, the following steps are included:

[0038] Step 1, weighing:

[0039] ① Rare earth butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber, and rosin resin are weighed according to the formula proportion to obtain a rubber main material mixture;

[0040] ② Bio-based white carbon black is weighed according to the formula proportion to obtain a filler;

[0041] ③ Stearic acid, zinc oxide, antioxidant HP-264, antioxidant SP-B, microcrystalline wax, white smoke activator, and silane coupling agent are mixed to obtain an additive mixture;

[0042] Step 2, internal mixing:

[0043] The rubber main material mixture is mixed and placed in an internal mixer. After mixing evenly, 25% of the total weight of bio-based white carbon black is added, and the rubber main material mixture and white carbon black are mixed and re-caked. After 3 minutes of mixing, when the temperature reaches 100°C, the remaining 75% of the total weight of bio-based white carbon black and the additive mixture are added. After 2 minutes of mixing, when the temperature continues to rise to 140°C, the material is discharged, and the base material is obtained;

[0044] Step 3, open mixing:

[0045] The base material after internal mixing is subjected to open mixing on an open mill. The initial roller gap is 3mm, and then it is thinned to a roller gap of 1mm, with 2 times of thinning. Then the roller gap is adjusted to 5mm to discharge the sheet, which is then cooled in water, passed through an anti-sticking tank, and then cut and left to stand at room temperature for more than 24 hours. The main purpose of open mixing is to mix the rubber and additives more uniformly, and another purpose is to discharge the material in sheet form for further processing;

[0046] Step 4, adding agents:

[0047] The base material after standing for 24 hours is added with insoluble sulfur, the first accelerator, and the second accelerator on the open mill. The sheet material is first packed into three triangular packages on the open mill, with a pile of rubber on top of the rollers. Then, the insoluble sulfur, the first accelerator, and the second accelerator are added to the pile of rubber, and the rubber is mixed and kneaded. The mixing method is changed to packing into three triangular packages and rolling. The roller gap for the first and second triangular packages is 1mm, and the roller gap for the third triangular package is 3mm. After mixing evenly, the material is discharged in sheet form;

[0048] Step 5, measuring the curing curve and oil pressure forming:

[0049] Cut a small piece of the material with the added medicine, and use a sulfur analyzer to measure the curing curve, record the scorch time and the positive curing time, adjust the oil press curing time according to the recorded scorch time and the positive curing time, cut the material with the added medicine into the shape of a shoe sole and put it into a rubber shoe mold for hot pressing, check the temperature of the oil press 160±5℃ and the pressure 150±5MPa before vulcanization, and check whether the setting of the curing time is correct, vulcanize according to the setting time, open the mold after vulcanization, take out the shoe sole, and the shoe sole made of wear-resistant and slip-resistant rubber is obtained.

[0050] In examples 4-6, the manufacturing method of the shoe sole made of wear-resistant and slip-resistant rubber includes the following steps:

[0051] Step 1, weighing:

[0052] ①According to the formula proportion, weigh the rare earth butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber and rosin resin to obtain the rubber main material mixture;

[0053] ②According to the formula proportion, weigh the bio-based white carbon black to obtain the filler;

[0054] ③According to the formula proportion, weigh the stearic acid, zinc oxide, antioxidant HP-264, antioxidant SP-B, microcrystalline wax, white smoke activator and silane coupling agent, and mix to obtain the additive mixture;

[0055] Step 2, mixing in an internal mixer:

[0056] Mix the rubber main material mixture, put it into the internal mixer, mix evenly, add 35% of the total weight of bio-based white carbon black after 2 minutes, continue mixing, mix the rubber main material mixture and white carbon black, re-knead, mix for 4 minutes, then add the remaining 65% of the total weight of bio-based white carbon black and the additive mixture when the temperature reaches 110℃, mix for 3 minutes, then discharge when the temperature continues to rise to 150℃, and the base material is obtained;

[0057] Step 3, mixing in an open mill:

[0058] The base material after mixing in the internal mixer is mixed in an open mill, the initial roller spacing is 4mm, then thinned to 1.5mm, the thinning frequency is 2 times, then the roller spacing is adjusted to 5mm to discharge the sheet, pass through cooling water, then pass through an anti-sticking tank, cut the sheet and place it at room temperature for more than 24h, the main purpose of mixing in an open mill is to mix the rubber and the additives more evenly, and the other purpose is to discharge the rubber in the form of a sheet for further processing;

[0059] Step 4, adding medicine:

[0060] The base material after standing for 24 h is added with insoluble sulfur, the first accelerator and the second accelerator on an open mill. The sheet material is first beaten into three triangular packs on the open mill, leaving a pile of rubber on the rollers, and the insoluble sulfur, the first accelerator and the second accelerator are added to the pile of rubber. Then the rubber is beaten and mixed, and the beating method is changed to beating into triangular packs and beating into rolls. The roller distance for the first and second triangular packs is 1.5 mm, and the roller distance for the third triangular pack is 4 mm or the standard thickness set according to the shoe type. After uniform mixing, the sheet material is discharged in a sheet shape;

[0061] Step 5, measuring the curing curve and oil pressure forming:

[0062] A small piece of the material added with the medicine is cut off, and the curing curve is measured by a sulfur change instrument to record the scorch time and the positive curing time. The oil press curing time is adjusted according to the recorded scorch time and the positive curing time. The material added with the medicine is cut into a shoe sole shape and placed in a rubber shoe mold for hot pressing. Before vulcanization, the temperature of the oil press is checked to be 160±5℃, the pressure is checked to be 150±5MPa, and the setting of the vulcanization time is checked to be correct. The vulcanization is performed according to the setting time. After the vulcanization is completed, the shoe sole is obtained by opening the mold and taking out the shoe sole.

[0063] In order to better illustrate the research results, the types of raw materials or the proportions of raw materials are changed so as not to reach or exceed the optimized proportion range (see Table 3). In Comparative Example 1, the rare earth butadiene rubber in Example 1 is replaced with ordinary butadiene rubber. In Comparative Example 2, the bio-based white carbon black in Example 1 is replaced with ordinary white carbon black. In Comparative Example 3, the rare earth butadiene rubber and the ethylene-propylene-diene rubber are not within the optimized proportion range. In Comparative Example 4, some additives are not within the optimized proportion range.

[0064] Table 3 Formulation of the shoe sole wear-resistant and slip-resistant shoe sole of each comparative example (%)

[0065]

[0066]

[0067] In the present application, the rare earth butadiene rubber is produced by Beijing Yanshan Petrochemical Co., Ltd., the isoprene rubber is IR2200 produced by Japan Zeon, the ethylene propylene diene rubber is EPDM9950 produced by Germany Arlanxeo, the bio-based white carbon black is 175 produced by Anhui Jinhua Silicon Nanometer Material Technology Co., Ltd., the stearic acid and zinc oxide are general products in the market, the antioxidant HP-264 and antioxidant SP-B are produced by Guangdong Hongbai Co., Ltd., the microcrystalline wax is produced by Fujian Guankao Co., Ltd., the white smoke activator is provided by Huaze Co., Ltd., the silane coupling agent is HP-1898B provided by Dongguan Hongbai Shoe Material Manufacturing Co., Ltd., the insoluble sulfur is IS-75 / G provided by Fujian Guankao Co., Ltd., the rosin resin is provided by Fujian Guankao Co., Ltd., the first accelerator is vulcanizing agent 106 provided by Fujian Guankao Co., Ltd., and the second accelerator is vulcanizing agent NS-80 provided by Taiwan Taixiang Co., Ltd.

[0068] Table 4 shows the test results of the properties of each example and comparative example

[0069]

[0070]

[0071] As can be seen from the data in Table 4, the tear resistance, wear resistance and slip resistance of each example all meet the standards, and compared with Comparative Example 1, the wear resistance of the sole using the rare earth butadiene rubber is more than 40% higher than that of the ordinary butadiene rubber, compared with Comparative Example 2, the comprehensive performance of the sole using the bio-based white carbon black is better than that of the ordinary white carbon black, and when the amount of raw materials of other comparative examples exceeds the set range, the wear resistance and slip resistance of the sole are also significantly reduced.

[0072] Therefore, the wear-resistant and slip-resistant rubber for soles prepared by the present application not only has good slip resistance and wear resistance, but also has excellent ozone resistance and tear resistance, and is a rubber material that meets the comprehensive performance requirements of soles for outdoor sports.

[0073] The above examples are not limited to the product form and style of the present application, and any appropriate changes or modifications made by those skilled in the art shall be considered as not departing from the scope of the present application.

Claims

1. A wear-resistant and slip-resistant rubber for shoe soles, which is composed of a raw material including a component A and a component B, characterized in that: The component A is formulated according to the mass percentage of: rare earth butadiene rubber 49%~60%, isoprene rubber 6%~10%, ethylene-propylene-diene rubber 3%~6%, bio-based white carbon black 15.1%~20%, stearic acid 0.3%~0.5%, zinc oxide 3%~5%, antioxidant HP-264 2%~3.5%, antioxidant SP-B 0.6%~1%, microcrystalline wax 0.3%~0.5%, white smoke active agent 1.8%~2.5%, silane coupling agent 2.5%~3.5%, and rosin resin 0.3%~0.6%; the component B is formulated as: insoluble sulfur, first accelerator and second accelerator, the insoluble sulfur is added in an amount of 0.9%~1.1% of the total mass of the component A, the first accelerator is added in an amount of 1%~1.4% of the total mass of the component A, and the second accelerator is added in an amount of 0.2%~0.3% of the total mass of the component A.

2. The wear-resistant slip-resistant rubber for shoe soles according to claim 1, characterized by: The insoluble sulfur is insoluble sulfur IS-75 / G.

3. A process for the preparation of a wear resistant slip resistant rubber for shoe soles as claimed in claim 1, characterized in that: The method comprises the following steps: Step 1, weighing: ①Rare earth butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber and rosin resin are weighed according to the formula proportion to obtain rubber main material mixture; ②Bio-based white carbon black is weighed according to the formula proportion to obtain filling material; ③Stearic acid, zinc oxide, antioxidant HP-264, antioxidant SP-B, microcrystalline wax, white smoke active agent and silane coupling agent are weighed according to the formula proportion and mixed to obtain auxiliary agent mixture; Step 2, mixing in an internal mixer: The rubber main material mixture is mixed and put into an internal mixer, and is mixed evenly after being started. After 1~2 minutes, 25%~35% of the total weight of bio-based white carbon black is added, and the mixing is continued. The rubber main material mixture and the white carbon black are mixed and re-bulked. After 3~4 minutes of mixing, when the temperature reaches 100~110℃, the remaining 65%~75% of the total weight of bio-based white carbon black and the auxiliary agent mixture are added. After 2~3 minutes of mixing, when the temperature continues to rise to 140~150℃, the material is discharged, and the base material is obtained; Step 3, mixing in an open mill: The base material after the completion of the internal mixing is mixed in an open mill. The initial roller distance is 3~4 mm, and then the roller distance is thinned to 1~1.5 mm for 2 times. Then the roller distance is adjusted to 5 mm to discharge the sheet, and the sheet is cooled in water, then passes through an anti-sticking tank, and is cut and placed at room temperature for more than 24 hours. The main purpose of the open mixing is to mix the rubber and the compounding agent more uniformly. Another purpose is to discharge the material in the form of sheet, which is convenient for further processing; Step 4, adding medicine: The base material after being placed for 24 hours is added with insoluble sulfur, first accelerator and second accelerator in an open mill. The sheet material is first packed into three triangular bags in the open mill, and the roller distance is adjusted to 1~1.5 mm. The insoluble sulfur, first accelerator and second accelerator are added on the accumulated rubber, and then the rubber is smashed and mixed. The mixing method is changed to packing into three triangular bags and rolling. The roller distance for the first and second packing into triangular bags is 1~1.5 mm, and the roller distance for the third packing into triangular bags is 3~4 mm or the standard thickness set according to the shoe type. After being mixed uniformly, the material is discharged in the form of sheet; Step 5, measuring the curing curve and oil pressure forming: Cut a small piece of the material with the added chemicals, and use a sulfur conversion instrument to measure the curing curve, record the scorch time and the optimum cure time, adjust the curing time of the oil press according to the recorded scorch time and optimum cure time, cut the material with the added chemicals into the shape of a shoe sole, and place it in a rubber shoe mold for hot pressing. Before vulcanization, check whether the temperature of the oil press (160±5℃) and the pressure (150±5MPa) meet the standards, and whether the curing time is set correctly. Vulcanize for the set time, open the mold, and take out the shoe sole, which is the sample of the wear-resistant and slip-resistant rubber shoe sole.

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