Efficient anti-yellowing anti-cracking rubber sole and preparation method thereof

Abstract

The invention relates to a high-efficiency anti-yellowing anti-cracking rubber sole and a preparation method thereof. The high-efficiency anti-yellowing anti-cracking rubber sole is prepared from the following raw materials in parts by weight: 8-10 parts of isoprene rubber; 8-10 parts of solution polymerized styrene-butadiene rubber; 25-30 parts of butadiene rubber; 0.5 to 1 part of liquid polyisobutylene rubber; 8-10 parts of naphthenic oil; 2.5 to 3.5 parts of polyethylene glycol; 24 to 28 parts of white carbon black; 0.4 to 0.5 part of wax; 1.7 to 1.9 parts of zinc oxide; 0.6 to 0.8 part of stearic acid; 0.4 to 0.6 part of a silane coupling agent; 0.4 to 0.7 part of an anti-aging agent 1076: 0.4 to 0.7 part of an anti-aging agent 2246; 12 to 14 parts of titanium dioxide R103; 0.6 to 1.0 part of insoluble sulfur IS-60; 0.7 to 1.0 part of an anti-yellowing accelerant No. 6; 0.15 to 0.3 part of an accelerant TBZTD; and 0.1 to 0.3 part of an accelerant NS. The preparation method comprises the following steps: weighing the raw materials according to the proportion, respectively putting the raw materials into an internal mixer for internal mixing, rubber discharging, open mixing and sheet discharging, and standing at room temperature for more than 24 hours; mixing on an open mill, discharging sheets, cooling, and finally vulcanizing and forming to obtain the high-efficiency yellowing-resistant anti-cracking rubber sole. According to the invention, the yellowing resistance and bending ozone cracking resistance of the rubber sole are obviously improved, and good wet skid resistance and processability are maintained.

Description

Technical Field

[0001] The invention relates to the field of sole preparation, and in particular to a high-efficiency yellowing-resistant and crack-resistant rubber sole and a preparation method thereof. Background Art

[0002] Rubber soles are made of natural rubber and synthetic rubber. Although they can achieve the basic wear-resistant and anti-slip effects of rubber outsoles, they are difficult to meet the needs of shoes with special functional requirements. For example, high-efficiency yellowing-resistant and crack-resistant rubber soles require the shoe material itself to have yellowing resistance, strong anti-oxidation, aging and weather resistance, so that it can meet the requirements of long-term sunlight exposure and an environment with relatively high humidity and ozone concentration in the air. The soles can resist the erosion of sunlight, yellowing and ozone, thereby achieving high-efficiency yellowing resistance and anti-cracking effects.

[0003] In order to solve the yellowing and cracking problems of rubber soles, different testing methods are set in the shoe material industry. The following solutions are mainly adopted: the main rubber material for yellowing resistance of the soles is a light-colored synthetic rubber, and then a yellowing resistance accelerator and high-quality titanium dioxide are used to improve the yellowing resistance effect. For example, the anti-cracking technology of tire rubber is used to add anti-cracking wax, anti-aging agent A, anti-aging agent D and other ketoamine antioxidants, or anti-aging agent 4010NA, anti-aging agent 4010 and other p-phenylenediamine antioxidants to the rubber soles; however, the former will not be able to protect against the cracking problem caused by ozone and external stress, while the latter has a good protective effect, but it is highly polluting and cannot achieve the yellowing resistance effect. If a certain proportion of EPDM rubber is added to the main rubber material, and then anti-cracking wax, anti-yellowing accelerator, non-polluting antioxidant, etc. are used, the yellowing resistance and bending ozone cracking of the sole are improved. However, after using a certain amount of EPDM rubber, the tension, tearing and wear resistance of the sole are deteriorated. After the upper and the outsole are combined, the peeling strength is poor and there is a great risk. The formula of rubber soles needs to be further improved. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a high-efficiency yellowing-resistant and cracking-resistant rubber sole having good yellowing-resistant, cracking-resistant and wet-slip resistance properties and a preparation method thereof.

[0005] The purpose of the present invention is achieved through the following technical scheme: a highly efficient yellowing-resistant and crack-resistant rubber sole, which is composed of the following raw materials in parts by weight: 8-10 parts of isoprene rubber; 8-10 parts of solution polymerized styrene-butadiene rubber; 25-30 parts of butadiene rubber; Liquid polyisobutylene rubber 0.5-1 part; 8-10 parts of naphthenic oil; 2.5-3.5 parts of polyethylene glycol; 24-28 parts of white carbon black; 0.4-0.5 parts of wax; Zinc oxide 1.7-1.9 parts; Stearic acid 0.6-0.8 parts; Silane coupling agent 0.4-0.6 parts; Antiaging agent 1076: 0.4-0.7 parts: Antiaging agent 2246: 0.4-0.7 parts; Titanium dioxide R103: 12-14 parts; Insoluble sulfur IS-60: 0.6-1.0 parts; Anti-yellowing accelerator No. 6: 0.7-1.0 part; Accelerator TBZTD: 0.15-0.3 parts; Accelerator NS: 0.1-0.3 parts.

[0006] Furthermore, the double bonds at the end of the side chains of the isoprene rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber are all cross-linked, and the double bonds on the main chain are not affected.

[0007] Furthermore, the mass ratio of cis-polybutadiene in the butadiene rubber is not less than 90%.

[0008] The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole comprises the following steps: Step 1, weighing butadiene rubber, solution polystyrene butadiene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, and titanium dioxide R103 according to the proportion of the raw materials, putting them into an internal mixer for internal mixing, discharging the rubber at 115-118°C, refining, discharging the sheets, and leaving them at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on an open mill, and adding insoluble sulfur IS-60, anti-yellowing accelerator No. 6, accelerator TBZTD, and accelerator NS weighed in proportion to the raw materials, mixing evenly, cooling the sheets, and finally cutting the sheets into the shape of soles and putting them into a rubber shoe mold for vulcanization to obtain the high-efficiency, anti-yellowing and anti-cracking rubber soles.

[0009] Furthermore, in step 2, the temperature of the vulcanization molding is 155-160°C.

[0010] Compared with the prior art, the beneficial effects of the present invention are as follows: the present application adopts conventional light-colored synthetic rubber: cis-1,4-butadiene rubber, solution-polymerized styrene-butadiene rubber and isoprene rubber, and specifically defines the weight proportion of the three, and compares the yellowing resistance and bending ozone cracking test by using anti-yellowing promoter No. 6 and adding titanium dioxide R103 to determine the yellowing resistance and anti-cracking performance of the white rubber sole, solving the problem of yellowing resistance and anti-cracking of the rubber sole toe; solution-polymerized styrene-butadiene rubber improves the material's yellowing resistance and anti-wet-slip performance and processing performance. The present invention significantly improves the yellowing resistance and anti-bending ozone cracking performance of the rubber sole through the appropriate amount of titanium dioxide R103, solves the problem of yellowing resistance and anti-cracking of the rubber sole toe, and maintains good anti-wet-slip performance and processing performance through formula adjustment. DETAILED DESCRIPTION

[0011] The present invention is further described in detail below through specific implementation modes.

[0012] Experimental Example 1: A highly efficient, yellowing-resistant and crack-resistant rubber sole is composed of the following raw materials in parts by weight (see Table 1).

[0013]

[0014] The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole comprises the following steps: Step 1: Weigh butadiene rubber, solution-polymerized styrene-butadiene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, titanium dioxide R103, etc. according to the proportion of raw materials and put them into an internal mixer for internal mixing, and place them at 115-118°C for rubber removal, refining, and sheeting at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on a double-roll mill, and adding accurately weighed insoluble sulfur IS-60, yellowing resistance accelerator No. 6, accelerator TBZTD, and accelerator NS (the latter three are collectively referred to as vulcanization accelerators), mixing evenly, cooling the sheet, and finally cutting the sheet rubber into the shape of a sole and putting it into a rubber shoe mold for vulcanization molding to obtain the high-efficiency yellowing and cracking-resistant rubber sole.

[0015] Furthermore, in step 2, the temperature of the vulcanization molding is 155-160°C.

[0016] It can be seen from the above description of the present invention that, compared with the prior art, the present invention has the following beneficial effects: First, this application uses conventional light-colored synthetic rubber: cis-1,4-butadiene rubber, solution-polymerized styrene-butadiene rubber and isoprene rubber, and specifically limits the proportion of the three. By matching the yellowing resistance promoter No. 6 and adding different amounts of titanium dioxide R103 to compare the yellowing resistance and bending ozone cracking test, the yellowing resistance and cracking resistance of the white rubber sole are determined, solving the problem of yellowing resistance and cracking resistance of the rubber sole toe; solution-polymerized styrene-butadiene rubber improves the material's yellowing resistance, anti-slip performance and processing performance. The present invention significantly improves the yellowing resistance and bending ozone cracking performance of the rubber sole by increasing the amount of titanium dioxide R103, solving the problem of yellowing resistance and cracking resistance of the rubber sole toe, and maintaining good anti-slip performance and processing performance through formula adjustment; Second, through experimental comparison, when the amount of titanium dioxide R103 is 8 parts and 10 parts, the yellowing resistance can reach the 4th level standard, but there is cracking in the bending ozone test. If the amount of titanium dioxide R103 is 12 parts and 14 parts, better yellowing resistance and anti-cracking effects can be obtained. The rubber sole prepared by this application achieves high-efficiency yellowing resistance and anti-cracking effects.

[0017] Experimental Example 2: A highly efficient, yellowing-resistant and crack-resistant rubber sole is composed of the following raw materials in parts by weight (see Table 2).

[0018]

[0019] The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole comprises the following steps: Step 1: Weigh butadiene rubber, solution-polymerized styrene-butadiene rubber, ethylene-propylene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, titanium dioxide R103, etc. according to the proportion of raw materials and put them into an internal mixer for internal mixing, discharge the rubber at 115-118°C, start mixing, and produce sheets, and place them at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on a double-roll mill, and adding accurately weighed insoluble sulfur IS-60, anti-yellowing accelerator No. 6, accelerator TBZTD, and accelerator NS (the latter three are collectively referred to as vulcanization accelerators), mixing evenly, cooling the sheet, and finally cutting the sheet rubber into the shape of a sole and putting it into a rubber shoe mold for vulcanization molding to obtain the high-efficiency anti-yellowing and anti-cracking rubber sole.

[0020] Furthermore, in step 2, the temperature of the vulcanization molding is 155-160°C.

[0021] It can be seen from the above description of the present invention that, compared with the prior art, the present invention has the following beneficial effects: First, the present application adopts conventional light-colored synthetic rubber: butadiene rubber, ethylene-propylene rubber, solution-polymerized styrene-butadiene rubber and isoprene rubber, and specifically defines the weight proportion of the four. Two comparative tests E and F formulas are conducted. By using the same anti-yellowing promoter No. 6 and adding 8 parts of titanium dioxide R103 in the same proportion to compare the bending ozone cracking and yellowing resistance test results, the yellowing resistance and cracking resistance of the white rubber sole is determined, and the problem of high-efficiency yellowing resistance and cracking resistance of the rubber sole toe is solved; the present application uses an equal amount of titanium dioxide R103 in a different amount from the main rubber material, and finds that the E formula without the use of ethylene-propylene rubber has bending ozone cracking, and the use of ethylene-propylene rubber can significantly improve the yellowing resistance and anti-bending ozone cracking dynamic aging performance of the rubber sole, which can solve the yellowing resistance and cracking resistance problems of the rubber sole toe, but the addition of ethylene-propylene rubber formula has a certain loss in tension, tearing and wear resistance, and the bonding performance of the upper and the outsole is affected, and the rubber shoe mold is prone to blackening and pollution. Second, the soles made by the E formula test scheme of the present application failed to crack under bending ozone. The F formula test scheme and the use of 5 parts of EPDM can improve the effect of rubber anti-cracking, but it affects the adhesion performance of the upper and the mold contamination problem, and further comparative tests are needed.

[0022] Experimental Example 3: A highly efficient, yellowing-resistant and crack-resistant rubber sole is composed of the following raw materials in parts by weight (see Table 3).

[0023]

[0024] The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole comprises the following steps: Step 1, weighing butadiene rubber, solution polystyrene butadiene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, titanium dioxide R103 and the like according to the proportion of raw materials into an internal mixer for internal mixing, discharging the rubber at 115-118°C, refining and discharging the sheets, and leaving them at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on a double-roll mill, and adding accurately weighed insoluble sulfur IS-60, yellowing resistance accelerator No. 6, accelerator TBZTD, and accelerator NS (the latter three are collectively referred to as vulcanization accelerators), mixing evenly, cooling the sheet, and finally cutting the sheet rubber into the shape of a sole and putting it into a rubber shoe mold for vulcanization molding to obtain the high-efficiency yellowing and cracking-resistant rubber sole.

[0025] Furthermore, in step 2, the temperature of the vulcanization molding is 155-160°C.

[0026] It can be seen from the above description of the present invention that, compared with the prior art, the present invention has the following beneficial effects: First, the present application adopts conventional light-colored synthetic rubber: butadiene rubber, solution-polymerized styrene butadiene rubber and isoprene rubber, and specifically defines the weight ratio of the three, three comparative test formulas with different dosages of insoluble sulfur IS-60, using the same anti-yellowing accelerator No. 6 and adding the same 12 parts of titanium dioxide R103 for comparison, bending ozone cracking and yellowing resistance test results, to determine the high-efficiency yellowing resistance and cracking resistance of the white rubber sole, solving the problem of high-efficiency yellowing resistance and cracking resistance of the rubber sole toe; Second, through the test comparison of insoluble sulfur IS-60 in different proportions, the present application found that 0.7 parts of insoluble sulfur IS-60 can improve the cross-linking density of rubber and have better yellowing resistance. The rubber has a longer anti-scorch time, the vulcanized rubber has a longer storage time, and has good yellowing resistance and anti-bending ozone cracking performance, which can solve the yellowing and cracking resistance problems of rubber soles and toes.

[0027] Experimental Example 4: A highly efficient, yellowing-resistant and crack-resistant rubber sole is composed of the following raw materials in parts by weight (see Table 4).

[0028]

[0029] The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole comprises the following steps: Step 1, weighing butadiene rubber, solution polystyrene butadiene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, titanium dioxide R103 and the like according to the proportion of raw materials into an internal mixer for internal mixing, discharging the rubber at 115-118°C, refining and discharging the sheets, and leaving them at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on a double-roll mill, and adding accurately weighed insoluble sulfur IS-60, yellowing resistance accelerator No. 6, accelerator TBZTD, and accelerator NS (the latter three are collectively referred to as vulcanization accelerators), mixing evenly, cooling the sheet, and finally cutting the sheet rubber into the shape of a sole and putting it into a rubber shoe mold for vulcanization molding to obtain the high-efficiency yellowing and cracking-resistant rubber sole.

[0030] Furthermore, in step 2, the temperature of the vulcanization molding is 155-160°C.

[0031] It can be seen from the above description of the present invention that, compared with the prior art, the present invention has the following beneficial effects: This application adopts conventional light-colored synthetic rubber: butadiene rubber, solution-polymerized styrene-butadiene rubber and isoprene rubber, and specifically defines the weight proportion of the three. Two comparative test formulas are used. Two different common accelerators are matched, the same anti-yellowing accelerator No. 6, insoluble sulfur IS-60, and the same 12 parts of titanium dioxide R103 are added to compare the bending ozone cracking and yellowing resistance test results. Both yellowing resistance test results are excellent. It is found that the vulcanized rubber obtained by adding accelerator NS has better anti-scorch performance and anti-bending ozone cracking performance, which can solve the yellowing resistance and cracking resistance problems of rubber soles and toes.

[0032] In the formula of Experimental Example 1, the main rubber material remains unchanged, and the amount of titanium dioxide R103 is changed. It is determined that when the amount of titanium dioxide R103 exceeds 12 parts, the shoe material formula has better yellowing resistance and anti-bending ozone cracking effects.

[0033] In the formula of Experimental Example 2, the amount of titanium dioxide R103 is fixed at 8 parts, and 5 parts of EPDM rubber are used as the main rubber material. The shoe material formula has better yellowing resistance and better resistance to bending and ozone cracking, but the tensile strength, tearing and wear resistance are damaged, the mold is contaminated and the bonding performance is deteriorated. It can be determined that the use of EPDM rubber together fails to achieve the desired effect.

[0034] In the formula of Experimental Example 3, the dosage of the main rubber material and titanium dioxide R103 is fixed, and the dosage of insoluble sulfur IS-60 is changed. When the dosage of insoluble sulfur IS-60 is increased to 0.7 parts, the yellowing resistance, cracking resistance and scorch resistance of the rubber material are better.

[0035] In the formula of Experimental Example 4, the main rubber material, titanium dioxide R103 and insoluble sulfur IS-60 are fixed, different common accelerators are matched with an equal amount of yellowing resistance accelerator No. 6, and the vulcanized rubber material obtained by adding accelerator NS has better anti-scorch safety performance.

[0036] By comparing Experimental Examples 1-4, it can be determined that the solution of Experimental Example 1 does not use EPDM rubber, but uses ordinary rubber materials to increase the amount of titanium dioxide R103, thereby achieving high-efficiency yellowing resistance and anti-bending ozone cracking effects, which is a breakthrough in shoe material formula.

[0037] In the above experimental examples 1-4, the hardness was tested by GS-706G hardness tester; DIN wear resistance was tested according to GB / T 9867-2008; yellowing resistance was tested according to HG / T 3689, sunlight, 50°C, 20 hours; ozone resistance was tested by ozone tester, temperature 50°C, humidity 65%, ozone concentration 100pphm, time 6 hours, the sample was tested by bending the test piece into a cylinder with a circumference of 40mm for ozone test, simulating the ozone test of toe stress and stretching. Xenon lamp aging test was tested according to GB / T 12831, 102 minutes of light, temperature 65°C, irradiance (340nm) of 0.51W / (m 2·nm), then spray for 18 minutes, cycle test for 168 hours; hydrolysis resistance test according to GB / T 3903.7-2005, temperature 70℃, humidity 95%, time 96 hours; peel strength test according to GB / T 532-2008, the bonding strength between the outsole and the standard EVA test piece. Specific test data results are shown in Table 5.

[0038]

[0039] As shown in Table 5, the present invention adopts common light-colored synthetic rubber: cis-1,4-butadiene rubber, solution-polymerized styrene-butadiene rubber, and isoprene rubber, and specifically limits the weight proportion of the three. By increasing the amount of titanium dioxide R103, the yellowing resistance and cracking resistance of the rubber sole are improved, and the problem of cracking of the rubber sole toe is solved; the double bond at the end of the branch chain of solution-polymerized styrene-butadiene rubber can improve the material's anti-slip performance and processing performance, and a variety of non-polluting antioxidants are used to resist rubber aging. The present invention application will increase the amount of titanium dioxide R103 to improve the high-efficiency yellowing resistance and ozone aging resistance of the rubber sole, solving the problem of cracking of the rubber sole toe. At the same time, through formula adjustment, the vulcanized rubber obtained by adding accelerator NS has better anti-scorch properties and maintains good anti-slip performance and processing performance.

[0040] The above description is only a preferred experimental example of the present invention, and therefore cannot be used to limit the scope of implementation of the present invention. That is, equivalent changes and modifications made according to the scope of the patent application of the present invention and the contents of the specification should still fall within the scope covered by the patent of the present invention.

Claims

1. High-efficiency yellowing-resistant and crack-resistant rubber sole, characterized by: It is composed of the following raw materials in parts by weight: 8-10 parts of isoprene rubber; 8-10 parts of solution polymerized styrene-butadiene rubber; 25-30 parts of butadiene rubber; Liquid polyisobutylene rubber 0.5-1 part; 8-10 parts of naphthenic oil; 2.5-3.5 parts of polyethylene glycol; 24-28 parts of white carbon black; 0.4-0.5 parts of wax; Zinc oxide 1.7-1.9 parts; Stearic acid 0.6-0.8 parts; Silane coupling agent 0.4-0.6 parts; Antiaging agent 1076: 0.4-0.7 parts: Antiaging agent 2246: 0.4-0.7 parts; Titanium dioxide R103: 12-14 parts; Insoluble sulfur IS-60: 0.6-1.0 parts; Anti-yellowing accelerator No. 6: 0.7-1.0 part; Accelerator TBZTD: 0.15-0.3 parts; Accelerator NS: 0.1-0.3 parts.

2. The high-efficiency yellowing-resistant and crack-resistant rubber sole according to claim 1, characterized in that: The double bonds at the end of the side chains of the isoprene rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber are all cross-linked, and the double bonds on the main chain are not affected.

3. The high-efficiency, yellowing-resistant and crack-resistant rubber sole according to claim 1 or 2, characterized in that: The mass ratio of cis-polybutadiene in the butadiene rubber is not less than 90%.

4. The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole according to claim 1, characterized in that: The following steps are involved: Step 1, weighing butadiene rubber, solution polystyrene butadiene rubber, isoprene rubber, liquid polyisobutylene rubber, naphthenic oil, white carbon black, polyethylene glycol, wax, zinc oxide, stearic acid, silane coupling agent, antioxidant 1076, antioxidant 2246, and titanium dioxide R103 according to the proportion of the raw materials, putting them into an internal mixer for internal mixing, discharging the rubber at 115-118°C, refining, discharging the sheets, and leaving them at room temperature for more than 24 hours; Step 2, mixing the mixture prepared in step 1 on an open mill, and adding insoluble sulfur IS-60, anti-yellowing accelerator No. 6, accelerator TBZTD, and accelerator NS weighed in proportion to the raw materials, mixing evenly, cooling the sheets, and finally cutting the sheets into the shape of soles and putting them into a rubber shoe mold for vulcanization to obtain the high-efficiency, anti-yellowing and anti-cracking rubber soles.

5. The method for preparing the high-efficiency yellowing-resistant and crack-resistant rubber sole according to claim 4, characterized in that: In step 2, the vulcanization molding temperature is 155-160°C.

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