CN111117049B - Shoe with yellowing-resistant sole and preparation method thereof - Google Patents
Shoe with yellowing-resistant sole and preparation method thereof Download PDFInfo
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- CN111117049B CN111117049B CN201911357478.9A CN201911357478A CN111117049B CN 111117049 B CN111117049 B CN 111117049B CN 201911357478 A CN201911357478 A CN 201911357478A CN 111117049 B CN111117049 B CN 111117049B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of shoes, and discloses a shoe with a yellowing-resistant sole, which comprises a vamp and a sole, wherein the sole comprises the following components in parts by weight: 60-80 parts of EVA; 2-3 parts of nano titanium dioxide; 8-10 parts of acrylic resin; 3-4 parts of stearamide; 1-2 parts of a catalyst; 1-2 parts of an anti-aging agent; 1-2 parts of light stabilizer. The invention has the following advantages and effects: the yellowing resistance of the acrylic resin is better, and the stearamide can improve the surface lubricity of the nano titanium dioxide, the acrylic resin and the EVA, so that the nano titanium dioxide and the acrylic resin can be stably and uniformly dispersed among the EVA, the compatibility among the components is improved, and the yellowing resistance is enhanced; in the presence of a catalyst, stearamide can generate a synergistic effect with acrylic resin; the light stabilizer can shield or absorb the energy of ultraviolet rays, so that the EVA sole can eliminate or slow down the possibility of photochemical reaction under the radiation of light, and the photo-aging process is prevented or delayed, thereby improving the yellowing resistance of the EVA sole.
Description
Technical Field
The invention relates to the technical field of shoes, in particular to a shoe with a yellowing-resistant sole and a preparation method thereof.
Background
EVA shoe soles refer to shoe soles made using an ethylene/vinyl acetate copolymer (also known as ethylene-vinyl acetate copolymer) material, made by copolymerizing ethylene and vinyl acetate. The EVA sole has high resilience, high tensile strength, high toughness, good shock resistance and buffering performance, excellent heat insulation, heat preservation, cold protection and low temperature performance, good water resistance, resistance to corrosion of chemicals such as seawater, grease, acid, alkali and the like, antibiosis, no toxicity, no odor and no pollution.
At present, a patent with publication number CN103242584B discloses a wear-resistant EVA shoe sole material, the formula of which comprises the following raw materials and weight fractions: 65-85% of ethylene-vinyl acetate copolymer, 5-10% of wear-resistant agent, 0.5-5% of light stabilizer, 5-20% of inorganic filler with the particle size of less than or equal to 200nm, 1-3% of foaming agent, 0.5-2% of cross-linking agent and 1-3% of dispersing lubricant.
The above prior art solutions have the following drawbacks: the above-mentioned EVA soles are often yellowed during use and storage, which easily affects the use of the soles, and thus, still need to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a shoe with a yellowing-resistant sole, which can solve the problem that the EVA sole often has yellowing in the using and storing processes and avoid the problem that a consumer discards or puts the shoe due to yellowing of the sole to cause resource waste.
In order to achieve the purpose, the invention provides the following technical scheme:
a shoe with an anti-yellowing sole comprises a vamp and the sole, wherein the sole comprises the following components in parts by weight:
60-80 parts of EVA;
2-3 parts of nano titanium dioxide;
8-10 parts of acrylic resin;
3-4 parts of stearamide;
1-2 parts of a catalyst;
1-2 parts of an anti-aging agent;
1-2 parts of light stabilizer.
By adopting the technical scheme, the yellowing resistance of the acrylic resin is better, and the stearamide can improve the surface lubricity of the nano titanium dioxide, the acrylic resin and the EVA, so that the nano titanium dioxide and the acrylic resin can be uniformly dispersed among the EVA and obtain a stable dispersion state, and the compatibility of the nano titanium dioxide, the acrylic resin and the EVA is improved, thereby improving the yellowing resistance; under the catalytic action of the catalyst, stearamide can generate a synergistic effect with acrylic resin, so that the yellowing resistance of the EVA sole can be improved, and accordingly, the yellowing resistance of the EVA sole can be improved by mixing EVA, the acrylic resin and the stearamide; the light stabilizer can shield or absorb the energy of ultraviolet rays, quench singlet oxygen, decompose hydroperoxide into inactive substances and the like, so that the possibility of photochemical reaction can be eliminated or slowed down and the photo-aging process can be prevented or delayed under the radiation of light of the EVA sole, thereby improving the yellowing resistance of the EVA sole.
The present invention in a preferred example may be further configured to: the sole also comprises 3-4 parts of octadecyl heptamethyl trisiloxane according to the parts by weight.
By adopting the technical scheme, the siloxane group contains continuously repeated siloxane bonds with high bond energy and is not influenced by sunlight and ultraviolet rays; and the silicon-oxygen bond is oxidized and is not influenced by oxygen in the atmosphere and most of oxidizing substances; the octadecyl groups have large polarity and regular distribution, so that the EVA and the octadecyl heptamethyl trisiloxane are blended, the strength of the EVA sole is favorably increased, and the EVA sole has excellent yellowing resistance.
The present invention in a preferred example may be further configured to: the sole also comprises 2-4 parts of isoamyl alcohol and 0.2-1.6 parts of ammonium stearate according to parts by weight.
By adopting the technical scheme, the octadecyl heptamethyl trisiloxane, the isoamyl alcohol and the ammonium stearate are blended to form an emulsion, so that the compatibility between the octadecyl heptamethyl trisiloxane and each component is improved on one hand, and the emulsion is coated on the surface of the mixed material of the EVA and the acrylic resin to form a compact protective film, thereby reducing the direct influence of external factors on the EVA and further improving the yellowing resistance.
The present invention in a preferred example may be further configured to: the ammonium stearate accounts for 25-30% of the isoamyl alcohol in parts by weight.
By adopting the technical scheme, experiments prove that the yellowing resistance of the EVA sole is better when ammonium stearate accounts for 20-30% of isoamylol in parts by weight.
The present invention in a preferred example may be further configured to: the anti-aging agent is N-phenyl-2-naphthylamine.
By adopting the technical scheme, the anti-aging performance is improved by the anti-aging agent, so that the problem of yellowing of the sole due to aging can be solved.
The present invention in a preferred example may be further configured to: the light stabilizer is isopropyl salicylate.
By adopting the technical scheme, the isopropyl salicylate can absorb the energy of ultraviolet rays, so that the possibility of photochemical reaction can be eliminated or slowed down and the photo-aging process can be prevented or delayed under the irradiation of light on the EVA sole, thereby achieving the purposes of enhancing the yellowing resistance of the EVA sole and prolonging the service life of the EVA sole.
The present invention in a preferred example may be further configured to: the catalyst is sodium methoxide.
By adopting the technical scheme, under the catalytic action of sodium methoxide, the stearamide and the acrylic resin generate a synergistic effect, so that the yellowing resistance of the EVA sole is improved.
The second purpose of the invention is to provide a preparation method of shoes with yellowing-resistant soles.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of shoes with yellowing-resistant soles comprises the following steps:
s1, firstly adding EVA, nano titanium dioxide, stearamide, an anti-aging agent and a light stabilizer into an internal mixer for blending, stirring for 10-15min at the temperature of 40-50 ℃, then adding acrylic resin and a catalyst, heating to 60-75 ℃, stirring for 25-30min, cooling to room temperature, adding a water separator to evaporate methanol, and reacting for 2-3h at the temperature of 80-90 ℃ to obtain a mixture;
s2, injecting the mixture in the S1 into a mold at 45-55 ℃ for reaction for 5-7min for molding, demolding, and curing in an oven at 75-80 ℃ for 22-24h to obtain the EVA sole;
s3, pre-sewing the vamp by using leather or cloth;
s4, directly covering the vamp on the EVA sole obtained in the step S2, and sewing the edge of the vamp on the side wall of the sole in a side sewing mode to obtain a finished shoe product.
The present invention in a preferred example may be further configured to: octadecyl heptamethyl trisiloxane and EVA can be added simultaneously in the S1; the isoamyl alcohol and ammonium stearate may be added simultaneously with the acrylic resin and the catalyst.
By adopting the technical scheme, the EVA and the octadecyl heptamethyl trisiloxane are firstly blended, which is beneficial to increasing the strength of the EVA sole and enabling the EVA sole to have excellent yellowing resistance; and then adding isoamyl alcohol and ammonium stearate to be blended with octadecyl heptamethyl trisiloxane to form an emulsion, so that on one hand, the compatibility between octadecyl heptamethyl trisiloxane and each component is improved, and on the other hand, the emulsion is coated on the surface of the mixed material of EVA and acrylic resin to form a compact protective film, thereby reducing the direct influence of external factors on EVA and further improving the yellowing resistance.
In summary, the present invention includes at least one of the following beneficial effects:
1. the yellowing resistance of the acrylic resin is better, and the stearamide can improve the surface lubricity of the nano titanium dioxide, the acrylic resin and the EVA, so that the nano titanium dioxide and the acrylic resin can be uniformly dispersed among the EVA and obtain a stable dispersion state, and the compatibility of the nano titanium dioxide, the acrylic resin and the EVA is improved, so that the yellowing resistance is improved; under the catalytic action of the catalyst, the stearamide can generate a synergistic effect with the acrylic resin, so that the yellowing resistance of the EVA sole can be improved, and accordingly, the yellowing resistance of the EVA sole can be improved by mixing the EVA, the acrylic resin and the stearamide; the light stabilizer can shield or absorb the energy of ultraviolet rays, quench singlet oxygen, decompose hydroperoxide into inactive substances and the like, so that the possibility of photochemical reaction can be eliminated or slowed down and the photo-aging process can be prevented or delayed under the radiation of light of the EVA sole, thereby improving the yellowing resistance of the EVA sole;
2. the octadecyl group has large polarity and regular distribution, so that the strength of the EVA sole is favorably increased and the EVA sole has excellent yellowing resistance through the blending of the EVA and the octadecyl heptamethyl trisiloxane; and the emulsion formed by blending octadecyl heptamethyl trisiloxane, isoamyl alcohol and ammonium stearate can improve the compatibility among all components on one hand, and the emulsion is coated on the surface of the mixed material of EVA and acrylic resin to form a compact protective film on the other hand, so that the direct influence of external factors on the EVA can be reduced, and the yellowing resistance can be improved.
Drawings
Fig. 1 is a process flow diagram of a method for manufacturing a shoe with a yellowing-resistant sole according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Examples
Example 1
Referring to fig. 1, the invention discloses a method for preparing shoes with yellowing-resistant soles, which comprises the following steps:
s1, firstly adding EVA, nano titanium dioxide, stearamide, octadecyl heptamethyl trisiloxane, an anti-aging agent and a light stabilizer into an internal mixer for blending, stirring for 10min at the temperature of 40 ℃, then adding isoamyl alcohol, ammonium stearate, acrylic resin and a catalyst, heating to 60 ℃, stirring for 25min, cooling to room temperature, adding a water separator to evaporate methanol, and reacting for 2h at the temperature of 80 ℃ to obtain a mixture;
s2, injecting the mixture in the S1 into a 45 ℃ mold for reaction for 5min for molding, demolding, and curing in a 75 ℃ oven for 22h to obtain the EVA sole;
s3, pre-sewing the vamp by using leather or cloth;
s4, directly covering the vamp on the EVA sole obtained in the step S2, and sewing the edge of the vamp on the side wall of the sole in a side sewing mode to obtain a finished shoe product.
In example 1, ammonium stearate accounts for 25% of the weight of isoamyl alcohol, and the content of each component is shown in table 1 below.
Example 2
Referring to fig. 1, the invention discloses a method for preparing shoes with yellowing-resistant soles, which comprises the following steps:
s1, firstly, adding EVA, nano titanium dioxide, stearamide, octadecyl heptamethyl trisiloxane, an anti-aging agent and a light stabilizer into an internal mixer for mixing, stirring for 15min at the temperature of 50 ℃, then adding isoamyl alcohol, ammonium stearate, acrylic resin and a catalyst, heating to 75 ℃, stirring for 30min, cooling to room temperature, adding a water separator to evaporate methanol, and reacting for 3h at the temperature of 90 ℃ to obtain a mixture;
s2, injecting the mixture in the S1 into a 55 ℃ mold for reaction for 7min for molding, demolding, and curing in an 80 ℃ oven for 24h to obtain the EVA sole;
s3, pre-sewing the vamp by using leather or cloth;
s4, directly covering the vamp on the EVA sole obtained in the step S2, and sewing the edge of the vamp on the side wall of the sole in a side sewing mode to obtain a finished shoe product.
In example 2, ammonium stearate accounts for 30% of the isoamyl alcohol in parts by weight, and the content of each component is shown in table 1 below.
Example 3
Referring to fig. 1, the invention discloses a method for preparing shoes with yellowing-resistant soles, which comprises the following steps:
s1, firstly adding EVA, nano titanium dioxide, stearamide, octadecyl heptamethyl trisiloxane, an anti-aging agent and a light stabilizer into an internal mixer for blending, stirring for 14min at the temperature of 46 ℃, then adding isoamyl alcohol, ammonium stearate, acrylic resin and a catalyst, heating to 70 ℃, stirring for 28min, cooling to room temperature, adding a water separator to evaporate methanol, and reacting for 2h at the temperature of 88 ℃ to obtain a mixture;
s2, injecting the mixture obtained in the step S1 into a die at 49 ℃ for reaction for 7min for molding, demolding, and curing in an oven at 77 ℃ for 24h to obtain the EVA sole;
s3, pre-sewing the vamp by using leather or cloth;
s4, directly covering the vamp on the EVA sole obtained in the step S2, and sewing the edge of the vamp on the side wall of the sole in a side sewing mode to obtain a finished shoe product.
In example 3, ammonium stearate accounts for 24% of isoamyl alcohol by weight, and the content of each component is shown in table 1 below.
Comparative example 1
The difference from example 1 is that only EVA, an anti-aging agent and a light stabilizer were added, and the contents of the respective components are shown in Table 2 below.
Comparative example 2
The difference from example 1 is that the acrylic resin is replaced with the epoxy resin, and the contents of the components are shown in table 2 below.
Comparative example 3
The difference from example 1 is that stearamide was replaced with benzamide and the contents of the respective components are shown in table 2 below.
Comparative example 4
The difference from example 1 is that octadecyl heptamethyltrisiloxane was replaced with polysiloxane, and the contents of each component are shown in table 2 below.
Comparative example 5
The difference from example 1 is that octadecyl heptamethyl trisiloxane is replaced by sodium dodecylbenzene sulfonate, and the contents of each component are shown in table 2 below.
Comparative example 6
The difference from example 1 is that octadecyl heptamethyltrisiloxane was not added, and the contents of the components are shown in table 2 below.
Comparative example 7
The difference from example 1 is that no ammonium stearate was added and the contents of the respective components are shown in table 2 below.
Comparative example 8
The difference from example 1 is that octadecyl heptamethyltrisiloxane, isoamyl alcohol, and ammonium stearate were not added, and the contents of the respective components are shown in table 2 below.
Comparative example 9
The difference from example 1 is that ammonium stearate accounts for 16% of the weight of isoamyl alcohol, and the content of each component is shown in the following table 2.
Comparative example 10
The difference from example 1 is that ammonium stearate accounts for 33% of the weight of isoamyl alcohol, and the content of each component is shown in the following table 2.
TABLE 1 ingredient content Table for each example
TABLE 2 ingredient content in each proportion
Performance test
Testing by using HG/T3689-2001, namely 'shoe yellowing resistance test method', placing a sample into an yellowing resistance testing machine, irradiating for a certain time by using an ultraviolet lamp, grading by referring to 5-grade color (color card) gradual change standard formulated by the American textile color chemistry Association and the standard color card thereof, wherein the higher the grade is, the better the yellowing resistance is; the test results of each example and comparative example are shown in table 3 below.
TABLE 3 yellowing resistance test results of examples and comparative examples
In summary, the following conclusions can be drawn:
1. as can be seen from the comparison of example 1 and comparative example 1, the added components of this example have significant yellowing resistance compared to the conventional EVA shoe sole.
2. As can be seen from the comparison of example 1 and comparative examples 2-3, the blending of EVA and acrylic resin can significantly improve the yellowing resistance of the EVA shoe sole; and the stearamide and the acrylic resin have a synergistic effect on improving the yellowing resistance of the EVA sole.
3. As is clear from a comparison between example 1 and comparative examples 4 to 5, the addition of octadecyl heptamethyltrisiloxane in the present invention has a specific effect of improving the yellowing resistance of EVA shoe soles.
4. It is clear from the comparison of example 1 and comparative examples 6 to 8 that octadecyl heptamethyltrisiloxane, isoamyl alcohol, and ammonium stearate have a synergistic effect to improve the yellowing resistance of EVA shoe soles.
5. As can be seen from the comparison of examples 1-3 and comparative examples 9-10, the yellowing resistance of EVA is best when ammonium stearate is present in an amount of 20-30% by weight of isoamyl alcohol.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (4)
1. A shoe with an anti-yellowing sole comprises a vamp and the sole, and is characterized in that: the sole is prepared from the following raw materials in parts by weight:
60-80 parts of EVA;
2-3 parts of nano titanium dioxide;
8-10 parts of acrylic resin;
3-4 parts of stearamide;
1-2 parts of sodium methoxide;
1-2 parts of an anti-aging agent;
1-2 parts of light stabilizer;
3-4 parts of octadecyl heptamethyl trisiloxane;
2-4 parts of isoamyl alcohol;
0.2-1.6 parts of ammonium stearate.
2. The shoe with the yellowing-resistant sole according to claim 1, wherein: the ammonium stearate accounts for 25-30% of the isoamyl alcohol in parts by weight.
3. The shoe with the yellowing-resistant sole according to claim 1, wherein: the anti-aging agent is N-phenyl-2-naphthylamine.
4. The shoe with the yellowing-resistant sole according to claim 1, wherein: the light stabilizer is isopropyl salicylate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911357478.9A CN111117049B (en) | 2019-12-25 | 2019-12-25 | Shoe with yellowing-resistant sole and preparation method thereof |
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| CN201911357478.9A CN111117049B (en) | 2019-12-25 | 2019-12-25 | Shoe with yellowing-resistant sole and preparation method thereof |
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| CN111117049A CN111117049A (en) | 2020-05-08 |
| CN111117049B true CN111117049B (en) | 2022-08-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205054A (en) * | 2013-04-28 | 2013-07-17 | 泰亚鞋业股份有限公司 | Soles of ejection foamed rubber-plastic sports shoes and manufacturing method of soles |
| WO2014053037A1 (en) * | 2012-10-02 | 2014-04-10 | Braskem S.A. | Non-expanded elastomer composition based on ethylene-vinyl acetate copolymer, and use thereof for manufacturing footwear |
| CN104844917A (en) * | 2015-05-11 | 2015-08-19 | 湖州福泽鞋业有限公司 | Non-gumming wear-resistant sole and preparation method thereof |
| CN109370037A (en) * | 2018-10-30 | 2019-02-22 | 温州薪然鞋业有限公司 | One kind not degumming wear-resisting sole and preparation method thereof |
-
2019
- 2019-12-25 CN CN201911357478.9A patent/CN111117049B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014053037A1 (en) * | 2012-10-02 | 2014-04-10 | Braskem S.A. | Non-expanded elastomer composition based on ethylene-vinyl acetate copolymer, and use thereof for manufacturing footwear |
| CN103205054A (en) * | 2013-04-28 | 2013-07-17 | 泰亚鞋业股份有限公司 | Soles of ejection foamed rubber-plastic sports shoes and manufacturing method of soles |
| CN104844917A (en) * | 2015-05-11 | 2015-08-19 | 湖州福泽鞋业有限公司 | Non-gumming wear-resistant sole and preparation method thereof |
| CN109370037A (en) * | 2018-10-30 | 2019-02-22 | 温州薪然鞋业有限公司 | One kind not degumming wear-resisting sole and preparation method thereof |
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