CN113583308B - Tear-resistant sole material and sole with same - Google Patents
Tear-resistant sole material and sole with same Download PDFInfo
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- CN113583308B CN113583308B CN202110992514.XA CN202110992514A CN113583308B CN 113583308 B CN113583308 B CN 113583308B CN 202110992514 A CN202110992514 A CN 202110992514A CN 113583308 B CN113583308 B CN 113583308B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The application relates to the field of clothes, and particularly discloses a tear-resistant sole material and a sole with the tear-resistant sole material. A tear-resistant sole material comprises the following substances in parts by weight: 80-100 parts of rubber, 5-10 parts of a tear resistance agent, 3-5 parts of zinc oxide, 0.1-1 part of stearic acid, 1-2 parts of dicumyl peroxide and 1-2 parts of an accelerator, wherein the tear resistance agent is a mixed fiber material with an entangled structure, the mixed fiber material comprises carbon fiber and aramid pulp, and the rubber comprises natural rubber; the tear-resistant sole is prepared by adopting the following scheme: s1, crushing; s2, discharging the sheet for the first time; s3, mixing and extruding; s4, packaging; s5, preparing the sole. The utility model provides a sole of tearing can be used to sports shoes, running shoes, playshoes etc. and it has wear-resisting and advantage of tearing the effect preferred.
Description
Technical Field
The application relates to the field of clothes, in particular to a tear-resistant sole material and a sole with the tear-resistant sole material.
Background
The sole may include an outsole, a midsole, a heel, and the like, all of which comprise the material of the bottom of the shoe, and is commonly referred to as the outsole of the shoe. The materials for preparing the soles need to have the characteristics of wear resistance, water resistance, oil resistance, heat resistance, impact resistance and the like, the feet are protected, common sole materials can be divided into natural types and synthetic types, and the natural types comprise natural sole leather, bamboo, wood and the like; the synthetic class includes rubber, plastics, rubber-plastic synthetic materials, and the like. At present, the rubber sole material is widely applied in the market.
In order to reduce the possibility of cracks in the sole, a tearing-resistant agent is usually added into a sole material to increase the tearing-resistant effect of the sole material and prolong the service life of the sole.
In view of the above related technologies, the inventor thinks that simply adding a tear-resistant agent to a sole material results in poor dispersion effect of the tear-resistant agent in the sole material due to the high modulus of the sole material, resulting in uneven and unstable tear-resistant effect of the sole material, and further the sole has the defects of poor tear-resistant effect and short service life.
Disclosure of Invention
In order to improve the not good, the short defect of life of the anti tear effect of sole, this application provides a tear-resistant sole material and sole that has it, adopts following technical scheme:
in a first aspect, the application provides a tear-resistant sole material, which adopts the following technical scheme:
the tear-resistant sole material comprises the following substances in parts by weight: 80-100 parts of rubber, 5-10 parts of a tear resistance agent, 3-5 parts of zinc oxide, 0.1-1 part of stearic acid, 1-2 parts of dicumyl peroxide and 1-2 parts of an accelerant, wherein the tear resistance agent is a mixed fiber material with an entangled structure, the mixed fiber material comprises carbon fiber and aramid pulp, and the rubber comprises natural rubber.
By adopting the technical scheme, the anti-tearing agent prepared by compounding the carbon fiber and the aramid pulp has a good fiber linear structure, and can be used for connecting the base materials in the sole material after being added into the sole material, so that the possibility of sole cracking is reduced, the anti-tearing effect of the sole is improved, and the service life of the sole is prolonged.
And secondly, the modulus of the aramid fiber pulp is similar to that of rubber, so that the dispersion effect of the aramid fiber pulp in the sole material is better, the anti-tearing agent base materials can be tangled through the entanglement effect of fibers, the dispersion effect of the anti-tearing agent in the sole material is improved, the sole obtains a relatively uniform anti-tearing effect, and the service life of the sole is prolonged.
Finally, the aramid pulp has more active groups on the surface, so that after the aramid pulp is entangled with the carbon fibers, the specific surface area of the anti-tearing agent is increased, the combination effect between the anti-tearing agent and a sole material base material is further improved, the anti-tearing effect of the sole is enhanced, and the prepared sole obtains a uniform and stable anti-tearing effect.
Preferably, the rubber further comprises one or two of styrene-butadiene rubber and polyurethane rubber, and the mass ratio of the natural rubber to the styrene-butadiene rubber to the polyurethane rubber is 2: 0-1: 0-2.
By adopting the technical scheme, the synthetic rubber is compounded in the natural rubber, so that the modulus of the natural rubber can be effectively improved, the dispersion effect of the anti-tearing agent in the sole material is improved, and the sole can obtain a relatively uniform anti-tearing effect.
The styrene butadiene rubber has better wear resistance and hardness, so the wear resistance and hardness of the rubber can be effectively improved by compounding the styrene butadiene rubber and the natural rubber, and the service life of the sole material can be further prolonged. Because the polyurethane rubber has better elasticity and toughness, the elasticity of the sole is ensured by compounding the polyurethane and the natural rubber, the possibility of poor elasticity of the sole caused by the addition of the anti-tearing agent is reduced, and the anti-tearing effect of the sole is improved.
Through the selective compounding of the natural rubber, the styrene butadiene rubber and the polyurethane rubber, the wear resistance of the sole can be increased, the elasticity of the sole can be guaranteed, the modulus of the sole material can be improved, the dispersion effect of the anti-tearing agent in the sole material can be improved, and the anti-tearing effect of the sole can be synergistically improved according to actual requirements.
Preferably, the mixed fiber material is a chopped fiber structure.
By adopting the technical scheme, the mixed fiber material is in a chopped fiber structure, so that the dispersion effect of the anti-tearing agent in the sole material is further improved, and the sole can obtain a uniform anti-tearing effect. Meanwhile, the aramid pulp has more active groups, so that the carbon fiber is easy to perform a crosslinking reaction with the aramid pulp, the anti-tearing agent forms a dispersed structure, and meanwhile, the short-cut fiber structure is short in length, so that the base material in the anti-tearing agent material is not easy to agglomerate, the anti-tearing agent is stably connected with the base material in the sole material, the anti-tearing effect of the sole is improved, and the service life of the sole is prolonged.
Preferably, the tear resistance agent further comprises phenolic resin, and the mass ratio of the carbon fiber to the aramid pulp to the phenolic resin is 4-6: 4-6: 1-3.
By adopting the technical scheme, as the phenolic resin is provided with active groups such as phenolic hydroxyl groups and the like, and the aramid pulp is provided with more active groups, the phenolic resin can react with the aramid pulp, and meanwhile, the phenolic resin can coat the carbon fibers in a molten state, so that a cross-linked net structure can be formed among the elastic fibers, the aramid pulp and the phenolic resin, the bonding effect between the anti-tearing agent and the sole material is further enhanced, and the sole obtains stable anti-tearing strength.
Preferably, the tear resistance agent is a modified tear resistance agent, and the modification treatment comprises the following steps: (1) the following materials were weighed separately: 80-100 parts of a tear resistance agent, 1-3 parts of blocked polyisocyanate, 0.5-1 part of epoxy resin, 1-5 parts of pentaerythritol stearate, 80-100 parts of polyisoprene and 5-10 parts of water; (2) weighing the weighed blocked polyisocyanate, epoxy resin and water, stirring and mixing to prepare a modified liquid, stirring and mixing the modified liquid and a tear-resistant agent for 20-30min, filtering, retaining a filter cake, drying at 60-80 ℃, and continuing heat treatment to prepare an intermediate product; (3) and stirring and mixing the intermediate product and pentaerythritol stearate, heating to 60-100 ℃ to obtain a secondary product, and stirring and mixing the secondary product and polyisoprene to obtain the modified anti-tearing agent.
By adopting the technical scheme, the epoxy resin, the blocked polyisocyanate and the anti-tearing agent are mixed, a cross-linked structure is added on the anti-tearing agent, and then the anti-tearing agent is mixed with the pentaerythritol stearate, so that the pentaerythritol stearate can be grafted on the anti-tearing agent, the lubricating effect of the anti-tearing agent is improved, namely the dispersion effect of the anti-tearing agent in the sole material is improved, and the sole obtains a relatively uniform anti-tearing effect. And then the anti-tearing agent is mixed with polyisoprene for permeation and isolation, so that the anti-tearing agent structures are isolated from each other, the possibility of agglomeration among anti-tearing agent base materials is reduced, the dispersion effect of the anti-tearing agent in the sole material is further improved, and the anti-tearing effect of the sole is improved.
Preferably, the temperature of the heat treatment in the step (2) is 150-200 ℃.
By adopting the technical scheme, the blocked poly-diisocyanate is subjected to heat treatment at a proper temperature, so that the blocked poly-diisocyanate is unblocked and reacts with the anti-tearing agent, the anti-tearing agent is stably connected with the epoxy resin, the anti-tearing agent and pentaerythritol stearate crosslinking effect are improved, the dispersion effect of the anti-tearing agent in the sole material is guaranteed, and the sole obtains a relatively uniform anti-tearing effect.
Preferably, the tear resistance agent is a surface treated tear resistance agent, the surface treatment comprising the steps of: and sequentially placing the anti-tearing agent into a hydrochloric acid aqueous solution and a sodium hydroxide aqueous solution, respectively continuing for 1-2min, taking out the anti-tearing agent, washing, and drying at 60-80 ℃ to obtain the surface-treated anti-tearing agent.
By adopting the technical scheme, the acid etching and the alkali etching are adopted to cooperate with the anti-tearing agent for modification, so that the specific surface area and the roughness of the anti-tearing agent are increased, the cross-linking and combining effect between the anti-tearing agent base materials is enhanced, a relatively divergent structure is formed, and the combining effect between the anti-tearing agent and the rubber is further improved; the bonding strength of the anti-tearing agent and the epoxy resin under the initiation of the blocked poly diisocyanate is improved, the stability of connecting pentaerythritol stearate through the epoxy resin is guaranteed, namely the anti-tearing agent has better dispersibility, and the sole can obtain a more uniform anti-tearing effect.
In a second aspect, the present application provides a tear resistant sole, which adopts the following technical scheme:
a tear-resistant sole comprises the tear-resistant sole material, and is manufactured by adopting the following scheme:
s1, crushing: according to the formula, taking rubber, crushing the rubber and sieving to obtain rubber particles; s2, once cutting: performing thin-pass treatment on rubber particles, adjusting the thickness of the rubber sheet to be 0.1-0.2mm, circulating for 4-6 times, performing thickening treatment again, adjusting the thickness of the rubber sheet to be 4-6mm, and circulating for 2-4 times to obtain a next sheet material; s3, mixing and extruding: mixing and extruding the primary lower sheet material, the anti-tearing agent, the zinc oxide, the stearic acid and the accelerator according to a formula to prepare an extruded material; s4, packaging: mixing the extruded material and dicumyl peroxide according to a formula, packaging, and repeating for 10 times to obtain a composite material; s5, preparing the sole: and (3) conveying the composite material into a mold, and carrying out mold closing, drying, demolding and post curing to obtain the sole.
Through adopting above-mentioned technical scheme, carry out breakage, lower piece processing with multiple rubber earlier for misce bene between the multiple rubber, and then add anti tearing agent in the rubber again, through unloading, lower piece, compounding extrusion many times, make anti tearing agent homodisperse in sole material, and then the sole obtains the anti effect of tearing of preferred.
Preferably, the rubber particles have a particle size of 0.1 to 1 mm.
Through adopting above-mentioned technical scheme, the particle diameter of rubber granule is less for the mixture between the multiple rubber is comparatively even, and the effect that increases natural rubber's wearability or polyurethane rubber through butadiene styrene rubber increases natural rubber's elasticity is stable, makes the wholeness ability of sole better, prolongs the life of sole.
In summary, the present application has the following beneficial effects:
1. because the carbon fiber and aramid pulp are compounded to be used as the anti-tearing agent, the aramid pulp has a good dispersion effect in the sole material due to the similar modulus of the aramid pulp and rubber, and the anti-tearing agent has a good dispersion effect among the rubber through the entanglement structure of the carbon fiber and aramid pulp, so that the sole can obtain a uniform anti-tearing effect; meanwhile, due to the linear structure of the fibers, the base materials of the rubber can be connected, and the possibility of cracks of the sole is reduced, so that the prepared sole obtains a relatively uniform anti-tearing effect.
2. In the application, the anti-tearing agent is preferably adopted for modification treatment, the epoxy resin, the blocked polyisocyanate and the anti-tearing agent are mixed, so that the anti-tearing agent is grafted with the epoxy resin under the initiation of the blocked polyisocyanate, and then is connected with the pentaerythritol stearate through the epoxy resin, so that the anti-tearing agent obtains a better dispersion effect, the anti-tearing agent grafted with the pentaerythritol stearate is mixed with the polyisoprene, the anti-tearing agent is subjected to permeation isolation, the possibility of agglomeration of base materials in the anti-tearing agent is reduced, the anti-tearing agent is uniformly dispersed in the sole, and a uniform anti-tearing effect is provided for the sole.
3. The utility model provides a tear-resistant sole through carrying out the broken mixture to rubber earlier, adds tear-resistant agent after carrying out thin expert for each component misce bene in the rubber, and then rubber obtains the wear-resisting effect and the elasticity of preferred, makes the modulus of rubber comparatively unified simultaneously, and the dispersion effect of tear-resistant agent in the sole material of guarantee has consequently obtained the tear-resistant effect of comparatively homogeneous at the sole.
Detailed Description
The present application will be described in further detail with reference to examples.
In the embodiment of the present application, the selected apparatuses are as follows, but not limited thereto:
the instrument comprises the following steps: the type 800 crusher of Zhengzhou Yuxiang mechanical equipment Limited company, the billion Xiang rubber and plastic machinery Limited company X (S) N150 internal mixer, the extruder with the goods number of 051 of Wei county branch company of rubber mechanical equipment Limited company of New originality of Hebei, the HY900 type cutter of aerospace machinery Limited company of Qingzhou city, and the H0347 type drying box of the Cechentai Zhiguan mechanical science and technology Limited company of Qingzhou city.
Medicine preparation: the high-performance epoxy resin comprises natural rubber with a product number of 01 of Jinan Lu storage rubber chemical industry Co., Ltd, LA-A03 type silane coupling agent of Shandong Li ang new material science Co., Ltd, LA-7Q type carbon black of Shandong Li ang new material science Co., Ltd, aramid pulp with a product number of yd20-200 of Yudun special fiber Co., Ltd, 14S-FL type dicumyl peroxide of Dongguan City Changhe chemical industry Co., Ltd, TETD type accelerant CZ of Guangzhou Li product rubber raw material trade Co., Ltd, IMPRAEIX2794 type blocked polyisocyanate of Coxipolymer Co., Ltd, Korean SK chemical EJ-190 type epoxy resin, pentaerythritol stearate with a product number of PETS-3 of Dongguan camphorwood head constant plastic raw material Co., Ltd, and LA-7A type phenolic resin of Shandong Li Oang Yuan high material science Co., Ltd.
Preparation examples
Examples of rubber preparation
Preparation examples 1 to 5
The natural rubber, styrene butadiene rubber and polyurethane rubber were weighed respectively, and the specific mass is shown in table 1. And mixing the weighed natural rubber, styrene butadiene rubber and polyurethane rubber to prepare the rubber 1-5.
TABLE 1 Components of rubbers in preparation examples 1 to 5
Preparation of tear resistance agent
Preparation examples 6 to 10
The carbon fiber, aramid pulp and phenolic resin were weighed separately, and the specific mass is shown in table 2. Stirring and mixing carbon fiber, aramid pulp and phenolic resin to prepare mixed fiber material with an entangled structure 1-5, namely a tear resistance agent 1-5
TABLE 2 Components of rubbers in preparation examples 6 to 10
Examples
Examples 1 to 4
Rubber 1, anti-tearing agent 1, zinc oxide, stearic acid, dicumyl peroxide and accelerator were weighed respectively, and the specific mass is shown in table 3.
According to the formula, putting the rubber 1 into a crusher, crushing, repeating for 3 times, and sieving to obtain rubber particles, wherein the particle size of the rubber particles is controlled to be 0.1 mm. Taking rubber particles, performing thin-pass treatment, adjusting the thickness of the rubber sheet to be 0.15mm, circulating for 5 times, performing thickening treatment again, adjusting the thickness of the rubber sheet to be 5mm, circulating for 3 times, and performing flaking to obtain primary flaking material. According to the formula, the primary lower sheet material, the anti-tearing agent, the zinc oxide, the stearic acid and the accelerator are placed into an internal mixer, mixed together and extruded by an extruder to prepare the extruded material. According to the formula, the extruded material and dicumyl peroxide are placed in a packaging machine, and packaging treatment is carried out together and repeated for 10 times to obtain the composite material. And (3) conveying the composite material into a mold, and performing mold closing, drying, mold stripping and post curing to obtain the sole 1-4.
Table 3 composition of soles in examples 1-4
Examples 5 to 8
The difference from example 3 is that: soles 5 to 8 were prepared using rubbers 2 to 5 in place of rubber 1 in example 3, and the other preparation conditions and preparation environments were the same as in example 3.
Examples 9 to 12
The difference from example 7 is that: soles 9-12 were prepared using 2-5 tear resistance agents instead of tear resistance agent 1 in example 7, and the remaining preparation conditions and preparation environment were the same as in example 7.
Example 13
The differences from example 11 are: the mixed fiber material is placed in a fiber cutting machine, the length of the mixed fiber material is controlled to be 10mm, a tear resistant agent 6 is prepared to replace the tear resistant agent 5 in the example 12, a sole 13 is prepared, and the rest of the preparation conditions and the preparation environment are the same as those in the example 12.
Example 14
The difference from example 13 is that: placing the anti-tearing agent in a hydrochloric acid aqueous solution with the mass fraction of 5% and a sodium hydroxide aqueous solution with the mass fraction of 5% in sequence, respectively rinsing for 1min, taking out the anti-tearing agent, rinsing with deionized water until the washing liquid is neutral, placing in an oven, and drying at 70 ℃ to prepare a surface-treated anti-tearing agent 7 to replace the anti-tearing agent 6 in the example 13 and prepare a sole 13, wherein the rest preparation conditions and the preparation environment are the same as those in the example 13.
Examples 15 to 17
The difference from example 14 is that: the method comprises the following steps of:
according to the formula, the anti-tearing agent, the blocked polyisocyanate, the epoxy resin, the pentaerythritol stearate, the polyisoprene and the water are respectively weighed, and the specific mass is shown in Table 4. Placing the blocked polyisocyanate, the epoxy resin and the water in a high-speed mixer, adding the anti-tearing agent into the high-speed mixer, mixing and impregnating together, filtering, keeping a filter cake of the anti-tearing agent, placing the anti-tearing agent in a drying box, drying at 80 ℃, heating to 150 ℃, and carrying out heat treatment to obtain an intermediate product. And (3) placing the intermediate product in a high-speed mixer, heating to 80 ℃, adding pentaerythritol stearate, blending for 5min to obtain a secondary product, equally dividing polyisoprene into three parts, adding the polyisoprene into the high-speed mixer in equal amount, blending with the secondary product, and blending for 10min each time to obtain the modified anti-tearing agent 8-10.
Shoe soles 15 to 17 were prepared by using 8 to 10 tear inhibitors in place of the tear inhibitor 7 in example 14, and the other preparation conditions and preparation environments were the same as in example 14.
TABLE 4 materials modified in examples 15 to 17
Examples 18 to 19
The differences from example 17 are: temperature of heat treatment was adjusted to 175 ℃ and 200 ℃ respectively, tear resistance agents 11 to 12 were prepared in place of the tear resistance agent 10 in example 17, and shoe soles 18 to 19 were prepared, and the other preparation conditions and preparation environments were the same as in example 17.
Examples 20 to 21
The difference from example 18 is that: the particle diameters of the rubbers were controlled to 0.5mm and 1mm, and soles of 20 to 21 were prepared, and the other preparation conditions and preparation environments were the same as in example 18.
Performance test
(1) Tear resistance test: the tear strength of the samples is measured according to the test of the tear strength (trouser, right-angled and crescent samples) of GB/T529-2008 vulcanized rubber or thermoplastic rubber;
(2) and (3) detecting the tensile property: detecting the tensile property of the sample according to GB/T528-2009 determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber;
(3) and (3) detecting the wear resistance: the wear-resisting property of the sole is detected according to the determination of the wear-resisting property of vulcanized rubber in GB/T1689-.
Table 5 examples 1-21 performance testing
Comparative example
Comparative example 1
The difference from example 20 is that: carbon black was selected as the tear resistant agent in place of the tear resistant agent 10 in example 20 to prepare a sole 22, and the other preparation conditions and preparation environments were the same as those in example 20.
Comparative example 2
The difference from example 20 is that: a tear-resistant agent was prepared by modifying only the tear-resistant agent to replace the tear-resistant agent 10 in example 20, and a shoe sole 23 was prepared under the same conditions and in the same production environment as in example 20.
Comparative example 3
The difference from example 20 is that: a silane coupling agent is used for modifying the anti-tearing agent to prepare the anti-tearing agent so as to replace the anti-tearing agent 10 in the example 20, and a sole 24 is prepared, wherein the rest of the preparation conditions and the preparation environment are the same as those in the example 20.
Comparative example 4
The differences from example 20 are: a tear-resistant agent was prepared without permeation isolation of the secondary product, instead of the tear-resistant agent 10 of example 20, and a shoe sole 25 was prepared, except that the preparation conditions and the preparation environment were the same as those of example 20.
Performance test
(1) Tear resistance test: the tear strength of the samples is measured according to the test of the tear strength (trouser, right-angled and crescent samples) of GB/T529-2008 vulcanized rubber or thermoplastic rubber;
(2) and (3) detecting the tensile property: detecting the tensile property of the sample according to GB/T528-2009 determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber;
(3) and (3) hardness detection: the hardness of the sole is detected according to the national standard GB/T531-1999 rubber pocket hardness tester indentation hardness test process.
TABLE 6 comparative examples 1-4 Performance test
(1) Comparing example 1-3, example 4 and comparative example 1, it can be found that: the anti-tear effect and tensile strength of the sole prepared in the embodiments 1-3 are improved, and the carbon fiber and aramid fiber pulp are adopted to prepare the anti-tear agent, the modulus of the aramid fiber pulp is similar to that of rubber, and the entanglement structure between the aramid fiber pulp and the carbon fiber improves the dispersion effect of the anti-tear agent in the sole material, so that the sole obtains a relatively uniform anti-tear effect, meanwhile, the anti-tear agent can connect the base material in the sole material through the fiber structure, the anti-tear effect and tensile strength of the sole are enhanced, and the service life of the sole is prolonged. The best tear resistance and tensile strength of the soles made in example 3 can be seen in combination with tables 5 and 6, which indicates that the proportions of the components in the soles are suitable.
(2) Combining example 3, examples 5-8, it can be found that: the shoe soles prepared in the embodiments 5 to 8 have improved tear resistance and tensile strength and improved wear resistance, which indicates that the rubber is prepared from natural rubber, styrene butadiene rubber and polyurethane rubber, and the elasticity of the shoe soles is enhanced and the tear resistance of the shoe soles is improved by compounding the natural rubber, styrene butadiene rubber and polyurethane rubber, and meanwhile, the wear resistance of the shoe soles is improved and the service life of the shoe soles is prolonged in cooperation. As can be seen from Table 5, the shoe soles prepared in example 7 exhibited the best tear resistance, tensile strength and abrasion resistance, indicating that the rubber components were present in the appropriate proportions.
(3) A comparison of example 7, examples 9 to 12 and comparative example 1 shows that: the anti-tearing effect and tensile strength of the soles prepared in examples 9 to 12 are improved, which indicates that the phenolic resin is added to the anti-tearing agent, and the anti-tearing agent can be respectively crosslinked with the aramid pulp and the carbon fiber through the active groups on the phenolic resin to form a crosslinked network structure, so that the bonding effect between the anti-tearing agent and the rubber is enhanced, and the anti-tearing agent is further stably connected with the base material in the sole material, so that the soles can obtain a relatively stable anti-tearing effect. The best tear resistance and tensile strength of the soles made in example 11 can be seen in combination with tables 5 and 6, which indicates that the tear resistance is achieved with a suitable ratio of the components.
(4) A comparison of example 12 with example 13 shows that: the tearing resistance effect and the tensile strength of the gel material prepared in the embodiment 13 are improved, which shows that the tearing resistance agent is adopted for cutting treatment, and the tearing resistance agent is cut into the chopped fibers, so that on one hand, the chopped fibers are not easy to self-agglomerate and can be uniformly dispersed in the sole material, and then the sole obtains a relatively uniform tearing resistance effect, and on the other hand, the activity of the chopped fibers is improved, so that a cross-linked network structure formed between the tearing resistance agent base materials is more stable, and the tearing resistance effect and the tensile strength of the sole are further improved.
(5) A comparison of example 13 and example 14 in combination can show that: the anti-tearing effect and tensile strength of the sole prepared in example 14 are reduced, which shows that the surface treatment with the anti-tearing agent increases the surface area of the anti-tearing agent and improves the bonding effect between the anti-tearing agent and rubber by etching the anti-tearing agent with acid and alkali respectively, so that the sole has stable anti-tearing effect and tensile strength. Meanwhile, the etched anti-tearing agent has better surface activity, improves the combination effect of all components in the anti-tearing agent, ensures the stability of a cross-linked net structure, but reduces the strength of the anti-tearing agent, so the anti-tearing effect and the tensile strength of the sole are reduced.
(6) In combination with example 14, examples 15-17 and comparative examples 2-4, it can be seen that: the anti-tearing effect and tensile strength of the soles prepared in examples 15 to 17 are improved, which shows that the anti-tearing agent is modified, and the epoxy resin, the blocked polyisocyanate and the anti-tearing agent are mixed to load the anti-tearing agent with the epoxy resin, so that the bonding effect between the anti-tearing agent and the rubber is further improved, and the sole obtains stable anti-tearing effect and tensile strength. Meanwhile, through the treatment of pentaerythritol stearate and polyisoprene, the lubricating effect of the anti-tearing agent is improved, the surface energy of the anti-tearing agent is reduced, the dispersion effect of the anti-tearing agent in the sole material is synergistically improved, the sole obtains a relatively uniform anti-tearing effect, and the anti-tearing strength and the tensile strength of the sole are improved. As can be seen from tables 5 and 6, the shoe soles obtained in example 17 exhibited the best tear resistance and tensile strength, indicating that the proportion of the materials in the modification treatment was appropriate.
(7) A comparison of example 17 with examples 18 to 19 shows that: the tear strength and tensile strength of the soles prepared in examples 18 to 19 are improved, which shows that the filter cake is subjected to heat treatment, the crosslinking effect of the tear resistance agent and the epoxy resin is improved, the connection strength of the tear resistance agent and the pentaerythritol stearate is guaranteed, that is, the dispersion effect of the tear resistance agent in the sole material is guaranteed, and the sole obtains a relatively uniform tear resistance effect. As can be seen from a combination of tables 5 and 6, the tear resistance and tensile strength of the shoe sole obtained in example 18 were the best, indicating that the temperature of the heat treatment was suitable at this time.
(8) A comparison of example 18 with examples 20 to 21 shows that: the sole prepared in examples 20 to 21 has improved tear resistance and tensile strength, which indicates that the sole obtained by the present application has a more uniform tear resistance by crushing rubber, so that the components between the rubbers can be uniformly mixed, the modulus of the rubber is improved, and the tear resistance agent is better dispersed in the sole material. The sole obtained in example 20 was found to have the best tear resistance and tensile strength as seen in tables 5 and 6, which indicates that the rubber particles are suitable in this case.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The tear-resistant sole material is characterized by comprising the following substances in parts by weight: 80-100 parts of rubber, 5-10 parts of a tear resistance agent, 3-5 parts of zinc oxide, 0.1-1 part of stearic acid, 1-2 parts of dicumyl peroxide and 1-2 parts of an accelerator, wherein the tear resistance agent is a mixed fiber material with an entangled structure, the mixed fiber material comprises carbon fiber and aramid pulp, and the rubber comprises natural rubber;
the tear resistance agent is a modified tear resistance agent, and the modification treatment comprises the following steps:
(1) the following materials were weighed separately: 80-100 parts of a tear-resistant agent, 1-3 parts of blocked polyisocyanate, 0.5-1 part of epoxy resin, 1-5 parts of pentaerythritol stearate, 80-100 parts of polyisoprene and 5-10 parts of water;
(2) weighing the weighed blocked polyisocyanate, epoxy resin and water, stirring and mixing to prepare a modified solution, stirring and mixing the modified solution and a tear resistance agent for 20-30min, filtering, keeping a filter cake, drying at 60-80 ℃, and continuously performing heat treatment to prepare an intermediate product;
(3) and stirring and mixing the intermediate product and pentaerythritol stearate, heating to 60-100 ℃ to obtain a secondary product, and stirring and mixing the secondary product and polyisoprene to obtain the modified anti-tearing agent.
2. A tear resistant sole material according to claim 1, wherein: the rubber also comprises one or two of styrene butadiene rubber and polyurethane rubber, and the mass ratio of the natural rubber to the styrene butadiene rubber to the polyurethane rubber is 2:0-2: 0-1.
3. A tear resistant sole material according to claim 1, wherein: the mixed fiber material is in a chopped fiber structure.
4. A tear resistant sole material according to claim 3, wherein: the tear resistance agent also comprises phenolic resin, and the mass ratio of the carbon fiber to the aramid pulp to the phenolic resin is 4-6: 4-6: 1-3.
5. A tear resistant sole material according to claim 1, wherein: the temperature of the heat treatment in the step (2) is 150-200 ℃.
6. A tear-resistant sole material according to claim 1, wherein the tear-resistant agent is a surface-treated tear-resistant agent, the surface treatment comprising the steps of: and sequentially placing the anti-tearing agent into a hydrochloric acid aqueous solution and a sodium hydroxide aqueous solution, respectively continuing for 1-2min, taking out the anti-tearing agent, washing, and drying at 60-80 ℃ to obtain the surface-treated anti-tearing agent.
7. A tear resistant sole comprising a tear resistant sole material according to any one of claims 1 to 6, the tear resistant sole being made by:
s1, crushing: according to the formula, taking rubber, crushing the rubber and sieving to obtain rubber particles;
s2, once sheet feeding: performing thin-pass treatment on rubber particles, adjusting the thickness of the rubber sheet to be 0.1-0.2mm, circulating for 4-6 times, performing thickening treatment again, adjusting the thickness of the rubber sheet to be 4-6mm, and circulating for 2-4 times to obtain a next sheet material;
s3, mixing and extruding: mixing and extruding the primary lower sheet material, the anti-tearing agent, the zinc oxide, the stearic acid and the accelerator according to a formula to prepare an extruded material;
s4, packaging: mixing the extruded material and dicumyl peroxide according to a formula, packaging, and repeating for 10 times to obtain a composite material;
s5, preparing the sole: and (3) conveying the composite material into a mold, and carrying out mold closing, drying, demolding and post curing to obtain the sole.
8. A tear-resistant sole as claimed in claim 7, wherein: the particle size of the rubber particles is 0.1-1 mm.
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| CN202110992514.XA CN113583308B (en) | 2021-08-27 | 2021-08-27 | Tear-resistant sole material and sole with same |
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| CN102206884A (en) * | 2011-05-24 | 2011-10-05 | 海宁苏拉纱线有限公司 | Method for developing and applying regenerated aramid fiber |
| CN104672514A (en) * | 2013-12-01 | 2015-06-03 | 朱伟萍 | Wear-resisting anti-slip mountaineering sole material and preparation method thereof |
| CN107652494B (en) * | 2017-09-30 | 2019-10-15 | 青岛科技大学 | A kind of rubber composite material and preparation method thereof of Fanglun slurry cake and short basalt fiber orientation enhancing |
| CN112940305B (en) * | 2019-12-11 | 2023-04-07 | 北京化工大学 | Preparation method of aramid pulp masterbatch, masterbatch obtained by preparation method and application of masterbatch |
| CN113087980A (en) * | 2021-05-20 | 2021-07-09 | 新泰华(惠州)制鞋科技有限公司 | Wear-resisting woman's shoe |
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