Cold-resistant non-slip rubber sole material and preparation method thereof
The cold-resistant anti-slip rubber sole material prepared through specific formulas and processes solves the problems of increased hardness and decreased anti-slip performance of rubber sole in extreme cold environments, and achieves good anti-slip performance and comfort at low temperatures.
Patent Information
- Application Number
- CN202510393540.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-07-22
AI Technical Summary
The existing rubber sole material has increased its hardness in extremely cold environments, resulting in a decrease in brittleness and anti-slip performance, which cannot meet the cold resistance and anti-slip requirements at low temperatures.
A specific proportion of natural rubber, styrene butadiene rubber, silaneized liquid silane rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softened oil are used to prepare cold-resistant anti-slip rubber sole materials through kneading and vulcanization. Combining Si-69 as a coupling agent to reduce Mooney's viscosity, white carbon black as a filler to improve hardness, and softening oil to improve cold resistance.
Maintaining good elasticity, wear resistance and anti-slip properties in extremely low temperature environments improves the comfort and anti-slip properties of the sole, reduces the change in hardness, reduces the phenomenon of vulcanization and charring, and improves the processability and physical properties.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of rubber sole materials, and specifically relates to a cold-resistant and anti-slip rubber sole material and a preparation method thereof. Background Art
[0002] Due to the rise of activities such as outdoor sports and adventure sports in recent years, as well as regional condition differences, new requirements have been put forward for certain special functions of shoes to meet the needs of extremely harsh low-temperature environments. At present, most shoe products can only meet the requirements of general cold degrees, and under extremely cold conditions, higher requirements are placed on the cold resistance performance of the soles. However, for ordinary rubber soles in a low-temperature environment (-20 °C), the hardness will continuously increase within 1 hour and reach its peak in 2 - 2.5 hours (the hardness increases by 8 - 10 degrees). At this time, the rubber becomes brittle, its performance deteriorates, it is prone to cracking, and the anti-slip performance drops severely. The current rubber sole materials still cannot meet the cold-resistant and anti-slip requirements at low temperatures and need to be further improved. Summary of the Invention
[0003] The purpose of the present invention is to provide a cold-resistant and anti-slip rubber sole material that can still maintain the anti-slip performance of the rubber in a low-temperature environment.
[0004] The present invention also aims to provide a preparation method for the above-mentioned cold-resistant and anti-slip rubber sole material.
[0005] To achieve the above objectives, the solution of the present invention is as follows: A cold-resistant and anti-slip rubber sole material, comprising the following raw materials in parts by weight: 20 - 60 parts of natural rubber 0 - 50 parts of styrene-butadiene rubber 20 - 50 parts of cis-butadiene rubber 3 - 30 parts of silanized liquid cis-butadiene rubber 30 - 65 parts of white carbon black 2 - 2.8 parts of Si-69 2 - 3.5 parts of tackifying resin 2 - 2.5 parts of PEG-4000 5 - 20 parts of softening oil; The natural rubber has the brand of Sinopec NR-35L, the styrene-butadiene rubber has the brand of Sinopec SBR-1502, and the cis-butadiene rubber has the brand of BR-9000.
[0006] A cold-resistant and anti-slip rubber sole material, comprising the following raw materials in parts by weight: 30 parts of natural rubber 30 parts of styrene-butadiene rubber 40 parts of cis-butadiene rubber 30 parts of silanized liquid cis-butadiene rubber 65 parts of silica 2.4 parts of Si-69 3.0 parts of tackifying resin 2.0 parts of PEG-4000 15 parts of softening oil
[0007] The grade of the silanized liquid cis-butadiene rubber is Goodyear N-234
[0008] The cold-resistant anti-slip rubber sole material further comprises a vulcanizing agent, and the vulcanizing agent comprises the following raw materials in parts by weight: 1.0 - 1.4 parts of sulfur 0.7 - 0.9 parts of accelerator 0.2 - 0.35 parts of anti-yellowing agent 0.07 - 0.12 parts of TBzTD
[0009] A preparation method of a cold-resistant anti-slip rubber sole material comprises the following steps: Step 1, weighing materials: First, weigh natural rubber, styrene-butadiene rubber and cis-butadiene rubber according to the ratio to obtain the main rubber material, and then weigh silanized liquid cis-butadiene rubber, silica, Si-69, tackifying resin, PEG-4000 and softening oil according to the ratio; Step 2, internal mixing: Then mix the main rubber material, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the silica, put them into an internal mixer and mix for 2 - 3 min, then put Si-69, tackifying resin, PEG-4000 and the remaining one-third of the silica into the internal mixer and continue to mix for 8 - 12 min to obtain the base material; Step 3, open mixing: Then put the base material into a mixing mill for open mixing for 3 - 6 min, pass the sheet through cooling water after taking it out, and then pass it through an anti-sticking tank to obtain a sheet material; Step 4, vulcanization: After the sheet material is cooled and ripened, cut the sheet material into the corresponding thickness according to the specific thickness of the required shape, then cut it into the required shape, and vulcanize it on a rubber vulcanizer to obtain the finished product; Step 5, packaging and warehousing: Finally, after trimming and finishing the finished product after shrinkage stabilization, package it and store it in the warehouse and keep it away from light.
[0010] In step 2, the temperature of the mixing is 80 - 120 °C.
[0011] In step 3, the base material is discharged after being open-mixed to 60 - 80 °C.
[0012] In step 4, the vulcanization temperature is 155~175°C, and the vulcanization time is 330~400 s.
[0013] After adopting the above technical solution, a cold-resistant and anti-slip rubber sole material of the present invention has the following beneficial effects: 1. This application specifies the mixed use of natural rubber, styrene-butadiene rubber and cis-butadiene rubber of specific models, which can complement each other in performance, so that the prepared rubber sole material has cold resistance and anti-slip performance, and can maintain good elasticity, wear resistance and anti-slip performance in a cold environment of -20°C, meeting the sole comfort requirements in cold environments; 2. Select silanized liquid cis-butadiene rubber that can remain stable in a lower temperature environment (-100°C), which has better compatibility with other rubbers. Combine it with cis-butadiene rubber with excellent anti-slip and wear-resistant performance, and finally combine it with cold-resistant styrene-butadiene rubber, which can improve the anti-yellowing performance of the product and simultaneously improve the anti-slip performance; 3. Use Si-69 as a coupling agent, which can reduce the Mooney viscosity, further improve the anti-slip performance of the product, reduce the phenomenon of vulcanization scorching. Combine with the use of PEG-4000 to improve the vulcanization rate and facilitate demoulding; use white carbon black as a filler to increase the stability of the molecular structure, improve the hardness of the product, enhance the processability and improve the physical properties of the finished product; 4. Add softening oil to the formula. The basic composition of the softening oil is made of mineral oil or synthetic oil plus other auxiliary materials, and its freezing point is relatively low, which can improve the cold resistance of the rubber sole material. The softening oil can also improve the rebound performance of the product and still maintain it in a low temperature environment. The common feature of anti-slip materials is low hardness, so adding softening oil can reduce the hardness of the material, thereby improving the anti-slip performance. Specific Embodiments
[0014] In order to further explain the technical solution of the present invention, the present invention will be elaborated in detail through specific embodiments below.
[0015] Example 1 A preparation method of a cold-resistant and anti-slip rubber sole material includes the following steps: Step 1. Weighing materials: First, weigh natural rubber, styrene-butadiene rubber and cis-butadiene rubber according to the ratio in Table 1 to obtain the main rubber material, and then weigh silanized liquid cis-butadiene rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softening oil according to the ratio; Step 2. Internal mixing: Then mix the main rubber material, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the white carbon black, put them into an internal mixer, mix at 100°C for 3 min, and then put Si-69, tackifying resin, PEG-4000 and the remaining one-third of the white carbon black into the internal mixer, and continue to mix at 100°C for 10 min to obtain the base material; Step 3, Open Mill: Then put the base material into an open mill for mixing for 6 min to raise the material temperature to 80 °C. After taking out the sheet, pass it through cooling water and then through an anti-sticking tank to obtain sheet-shaped materials. Step 4, Vulcanization: After the sheet-shaped materials are cooled and ripened, cut the sheet-shaped materials into corresponding thicknesses according to the specific thickness of the required shape, then cut them into the required shapes, add the vulcanizing agent as shown in Table 1, and carry out vulcanization on a rubber vulcanizer. The vulcanization temperature is 160 °C and the vulcanization time is 360 s to obtain the finished product. Step 5, Packaging and Warehousing: Finally, after trimming and finishing the finished product with stable shrinkage, package it and store it in the warehouse and store it away from light.
[0016] Example 2 A preparation method of a cold-resistant anti-slip rubber sole material, comprising the following steps: Step 1, Weighing Materials: First, weigh natural rubber, styrene-butadiene rubber and cis-butadiene rubber according to the ratio in Table 1 to obtain the main rubber material, and then weigh silanized liquid cis-butadiene rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softening oil according to the ratio. Step 2, Internal Mixing: Then mix the main rubber material, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the white carbon black, put them into an internal mixer, mix for 2 min at 80 °C, and then put Si-69, tackifying resin, PEG-4000 and the remaining one-third of the white carbon black into the internal mixer and continue to mix for 8 min at 80 °C to obtain the base material. Step 3, Open Mill: Then put the base material into an open mill for mixing for 3 min to raise the material temperature to 60 °C. After taking out the sheet, pass it through cooling water and then through an anti-sticking tank to obtain sheet-shaped materials. Step 4, Vulcanization: After the sheet-shaped materials are cooled and ripened, cut the sheet-shaped materials into corresponding thicknesses according to the specific thickness of the required shape, then cut them into the required shapes, add the vulcanizing agent as shown in Table 1, and carry out vulcanization on a rubber vulcanizer. The vulcanization temperature is 155 °C and the vulcanization time is 330 s to obtain the finished product. Step 5, Packaging and Warehousing: Finally, after trimming and finishing the finished product with stable shrinkage, package it and store it in the warehouse and store it away from light.
[0017] Example 3 A preparation method of a cold-resistant anti-slip rubber sole material, comprising the following steps: Step 1, Weighing Materials: First, weigh natural rubber, styrene-butadiene rubber and cis-butadiene rubber according to the ratio in Table 1 to obtain the main rubber compound. Then, weigh silanized liquid cis-butadiene rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softening oil according to the ratio. Step 2, Banbury mixing: Then mix the main rubber compound, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the white carbon black, put them into a Banbury mixer, mix at 120 °C for 3 min, and then put Si-69, tackifying resin, PEG-4000 and the remaining one-third of the white carbon black into the Banbury mixer, and continue to mix at 120 °C for 12 min to obtain the base material. Step 3, Open mill mixing: Then put the base material into an open mill for mixing for 4 min to raise the material temperature to 70 °C. After taking out the sheet, pass it through cooling water and then through an anti-sticking tank to obtain a sheet-shaped material. Step 4, Vulcanization: After the sheet-shaped material is cooled and ripened, cut the sheet-shaped material into the corresponding thickness according to the specific thickness of the required shape, then cut it into the required shape, add the vulcanizing agent as shown in Table 1, and carry out vulcanization on a rubber vulcanizer. The vulcanization temperature is 175 °C and the vulcanization time is 400 s to obtain the finished product. Step 5, Packaging and warehousing: Finally, after trimming and finishing the finished product after shrinkage stabilization, package it and store it in the warehouse and store it in the dark.
[0018] Example 4 A preparation method of a cold-resistant anti-slip rubber sole material, comprising the following steps: Step 1, Weighing materials: First, weigh natural rubber, styrene-butadiene rubber and cis-butadiene rubber according to the ratio in Table 1 to obtain the main rubber compound. Then, weigh silanized liquid cis-butadiene rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softening oil according to the ratio. Step 2, Banbury mixing: Then mix the main rubber compound, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the white carbon black, put them into a Banbury mixer, mix at 100 °C for 3 min, and then put Si-69, tackifying resin, PEG-4000 and the remaining one-third of the white carbon black into the Banbury mixer, and continue to mix at 100 °C for 10 min to obtain the base material. Step 3, Open mill mixing: Then put the base material into an open mill for mixing for 6 min to raise the material temperature to 80 °C. After taking out the sheet, pass it through cooling water and then through an anti-sticking tank to obtain a sheet-shaped material. Step 4, Vulcanization: After the sheet material is cooled and ripened, the sheet material is sliced into a corresponding thickness according to the specific thickness of the required shape, then cut into the required shape, and a vulcanizing agent as shown in Table 1 is added, and vulcanization is carried out on a rubber vulcanizer. The vulcanization temperature is 165 °C and the vulcanization time is 360 s to obtain the finished product; Step 5, Packaging and warehousing: Finally, after trimming and finishing the finished product with stable shrinkage, it is packaged and warehoused and stored away from light.
[0019] Example 5 A preparation method of a cold-resistant anti-slip rubber sole material includes the following steps: Step 1, Weighing materials: First, natural rubber, styrene-butadiene rubber and cis-butadiene rubber are weighed according to the ratio in Table 1 to obtain the main rubber material, and then silanized liquid cis-butadiene rubber, white carbon black, Si-69, tackifying resin, PEG-4000 and softening oil are weighed according to the ratio; Step 2, Internal mixing: Then the main rubber material, silanized liquid cis-butadiene rubber, softening oil and two-thirds of the white carbon black are mixed and put into an internal mixer, and mixed at 80 °C for 3 min. Then Si-69, tackifying resin, PEG-4000 and the remaining one-third of the white carbon black are put into the internal mixer and continue to be mixed at 80 °C for 12 min to obtain the base material; Step 3, Open mixing: Then the base material is put into an open mixer for open mixing for 6 min to raise the material temperature to 80 °C. After slicing, it passes through cooling water and then through an anti-sticking tank to obtain a sheet material; Step 4, Vulcanization: After the sheet material is cooled and ripened, the sheet material is sliced into a corresponding thickness according to the specific thickness of the required shape, then cut into the required shape, and a vulcanizing agent as shown in Table 1 is added, and vulcanization is carried out on a rubber vulcanizer. The vulcanization temperature is 165 °C and the vulcanization time is 360 s to obtain the finished product; Step 5, Packaging and warehousing: Finally, after trimming and finishing the finished product with stable shrinkage, it is packaged and warehoused and stored away from light.
[0020] In the above examples, all raw materials are obtained by purchasing in the market, and the manufacturers and grades are shown in Table 2.
[0021] Table 1 Composition and dosage of raw materials in each example
[0022] Table 2 Manufacturers and grades of raw materials
[0023] The rubber sole materials prepared in Examples 1-5 were subjected to physical property tests according to national test standards, and the test data are shown in Table 3.
[0024] Table 3 Properties of the rubber sole materials in each example
[0025] It can be found from the data in Table 3 that in Examples 1-3, with the increase in the amount of silanized liquid cis-butadiene rubber, the change in low-temperature hardness of the rubber sole material can be reduced, and the anti-slip performance can be improved. With the increase in the amount of styrene-butadiene rubber, the change in low-temperature hardness of the finished product is also small, but the hardness is low. Therefore, the filler white carbon black is added to increase the overall hardness and ensure the basic physical properties. The increase in the amount of softening oil can also further improve the anti-slip performance of the material in a low-temperature environment.
[0026] When the amount of silanized liquid cis-butadiene rubber is 30 parts, the amount of natural rubber is 30 parts, the amount of styrene-butadiene rubber is 30 parts, and the amount of cis-butadiene rubber is 40 parts, the rubber sole material has the best cold resistance, anti-slip, wear resistance and yellowing resistance.
[0027] The above embodiments do not limit the product form and style of the present invention. Any appropriate changes or modifications made by those of ordinary skill in the relevant technical field shall be regarded as not departing from the patent scope of the present invention.
Claims
1. A cold-resistant and anti-slip rubber sole material, characterized in that: It comprises raw materials in the following parts by weight: 20 - 60 parts of natural rubber 0 - 50 parts of styrene - butadiene rubber 20 - 50 parts of cis - 1,4 - polybutadiene rubber 3 - 30 parts of silanized liquid cis - 1,4 - polybutadiene rubber 30 - 65 parts of white carbon black 2 - 2.8 parts of Si - 69 2 - 3.5 parts of tackifying resin 2 - 2.5 parts of PEG - 4000 5 - 20 parts of softening oil; The grade of the natural rubber is Sinopec NR - 35L, the grade of the styrene - butadiene rubber is Sinopec SBR - 1502, and the grade of the cis - 1,4 - polybutadiene rubber is BR - 9000.
2. The cold-resistant and anti-slip rubber sole material according to claim 1, characterized in that: It comprises raw materials in the following parts by weight: 30 parts of natural rubber 30 parts of styrene - butadiene rubber 40 parts of cis - 1,4 - polybutadiene rubber 30 parts of silanized liquid cis - 1,4 - polybutadiene rubber 65 parts of white carbon black 2.4 parts of Si - 69 3.0 parts of tackifying resin 2.0 parts of PEG - 4000 15 parts of softening oil.
3. The cold-resistant and anti-slip rubber sole material according to claim 1, characterized in that: The grade of the silanized liquid cis - 1,4 - polybutadiene rubber is Goodyear N - 234.
4. The cold-resistant and anti-slip rubber sole material according to claim 1, characterized in that: It further comprises a vulcanizing agent, and the vulcanizing agent comprises raw materials in the following parts by weight: 1.0 - 1.4 parts of sulfur 0.7 - 0.9 parts of accelerator 0.2 - 0.35 parts of anti - yellowing agent 0.07 - 0.12 parts of TBzTD.
5. A preparation method of a cold-resistant and anti-slip rubber sole material as claimed in claim 1, characterized in that: It includes the following steps: Step 1, weighing materials: First, weigh natural rubber, styrene - butadiene rubber and cis - 1,4 - polybutadiene rubber according to the proportion to obtain the main rubber material, and then weigh silanized liquid cis - 1,4 - polybutadiene rubber, white carbon black, Si - 69, tackifying resin, PEG - 4000 and softening oil according to the proportion; Step 2, internal mixing: Then mix the main rubber material, silanized liquid cis - 1,4 - polybutadiene rubber, softening oil and two - thirds of the white carbon black, put them into an internal mixer and mix for 2 - 3 min, then put Si - 69, tackifying resin, PEG - 4000 and the remaining one - third of the white carbon black into the internal mixer and continue to mix for 8 - 12 min to obtain the base material; Step 3, open mixing: Then put the base material into an open mill for open mixing, mix for 3 - 6 min, pass the sheet through cooling water after taking it out, and then through an anti - sticking tank to obtain a sheet - shaped material; Step 4, vulcanization: After the sheet - shaped material is cooled and ripened, cut the sheet - shaped material into the corresponding thickness according to the specific thickness of the required shape, then cut it into the required shape, and vulcanize it on a rubber vulcanizer to obtain the finished product; Step 5, packaging and warehousing: Finally, after trimming and finishing the finished product with stable shrinkage, package it and store it in the warehouse and keep it away from light.
6. The preparation method of a cold-resistant and anti-slip rubber sole material according to claim 5, characterized in that: In step 2, the temperature of the mixing is 80 - 120 °C.
7. The preparation method of a cold-resistant and anti-slip rubber sole material according to claim 5, characterized in that: In step 3, the base material is discharged after being open - mixed to 60 - 80 °C.
8. The preparation method of a cold-resistant and anti-slip rubber sole material according to claim 5, characterized in that: In step 4, the temperature of the vulcanization is 155 - 175 °C, and the time of the vulcanization is 330 - 400 s.