CN105670198A - Waterproof SBS foaming sole material and preparation method thereof - Google Patents
Waterproof SBS foaming sole material and preparation method thereof Download PDFInfo
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- CN105670198A CN105670198A CN201610039012.4A CN201610039012A CN105670198A CN 105670198 A CN105670198 A CN 105670198A CN 201610039012 A CN201610039012 A CN 201610039012A CN 105670198 A CN105670198 A CN 105670198A
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a waterproof SBS foaming sole material.The waterproof SBS foaming sole material is prepared from, by weight, 36-58 parts of SBS, 1-2 parts of foamer, 10-15 parts of softening oil, 1-3 parts of mold release agent, 1-2 parts of cross-linking agent, 1-2 parts of thermal stabilizer, 0.2-0.4 part of light stabilizer, 0.5-1 part of antioxidant, 14-18 parts of boron carbide fiber, 8-12 parts of PPSS and 5-10 parts of compatilizer.The invention further provides a preparation method of the foaming sole material.The waterproof SBS foaming sole material has high waterproofness and long service life.
Description
Technical field:
The present invention relates to a kind of material for sole of shoe, particularly relate to a kind of water-resisting type SBS foaming sole material and its preparation method.
Background technology:
SBS is that catalyzer carries out the obtained a kind of thermoplastic elastomer of anionoid polymerization by vinylbenzene and divinyl taking lithium alkylide, compared with other thermoplastic elastomer, SBS has the features such as intensity height, softness, tension set be little, and there is caoutchouc elasticity, it is applicable to melt tackiness agent and the sealing material of processing as heat, having a wide range of applications in shoe industry, polymer modification, asphalt modification, waterproof paint, liquid sealant, electric wire, cable, trolley part, medical device element, household electrical appliance, office automation and tackiness agent etc., exploitation prospect is wide. At present, China SBS product is mainly used in the aspects such as shoemaking, asphalt modification, polymer modification and tackiness agent. SBS sole style can be translucent shoe with beef tendon sole or double-colored sole bright in luster, it is possible to producing foamed sole. The inexpensive integral die canvas shoes rope soled shoes made with SBS, its weight ratio polyvinyl chloride (PVC) RESINS footwear are light by 15～25%, and frictional coefficient is high by 30%, has excellent wear resistance and low-temperature pliability.
Such as, publication number is CN102964768B, publication date is 2014.11.05, apply for the Chinese patent of the state-run Science and Technology Ltd. of artificial Dongguan City discloses " a kind of rubber plastic modified environment-friendly materials and its preparation method ", comprise calculate by weight oil-extended SBS 25～35 parts, SBS20～30 part, butadiene-styrene copolymer 5～10 parts, vinylbenzene 3～8 parts, oil 5～15 parts, fiber 20～30 parts, Zinic stearas 0.1～0.5 part, and at different temperatures in batches add preparation and obtain; The present invention is light weight not only, and ageing-resistant, wear-resisting, heat-resisting, especially employs renewable vegetable fibre, with low cost, simultaneously environmentally friendly, and its discarded material degradation time is short. The defect that this material exists is: water tolerance is undesirable, and the puzzlement that material can be hydrolyzed in often rainy, moist environment, degradation is obvious, causes the life-span to shorten.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of water-resisting type SBS foaming sole material, has good water tolerance, it may also be useful to the life-span is longer.
For solving the problems of the technologies described above, the technical scheme of the present invention is:
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS36～58 part, whipping agent 1～2 part, softening oil 10～15 parts, releasing agent 1～3 part, linking agent 1～2 part, thermo-stabilizer 1～2 part, photostabilizer 0.2～0.4 part, 0.5～1 part, oxidation inhibitor, boron carbide fibre 14～18 parts, PPSS8～12 part, compatilizer 5～10 parts.
Preferably, whipping agent of the present invention is AC whipping agent.
Preferably, softening oil of the present invention is naphthenic oil.
Preferably, releasing agent of the present invention is calcium stearate or Magnesium Stearate.
Preferably, linking agent of the present invention is DCP.
Preferably, thermo-stabilizer of the present invention is rare-earth stabilizer.
Preferably, photostabilizer of the present invention is triphenyl phosphite.
Preferably, oxidation inhibitor of the present invention is oxidation inhibitor GM.
Preferably, compatilizer of the present invention is SBS-g-MAH.
Another technical problem that the present invention to be solved is to provide the preparation method of above-mentioned water-resisting type SBS foaming sole material.
For solving the problems of the technologies described above, technical scheme is:
A preparation method for water-resisting type SBS foaming sole material, its step is as follows:
(1) by boron carbide fibre ethanolic extraction 40 hours to remove surface impurity, clean with deionized water after extracting, add after dry in nitric acid and stir 3 hours at 90 DEG C, clean with deionized water after taking-up, obtain oxidation boron carbide fibre;
(2) the oxidation boron carbide fibre that step (1) obtains is added in the earth solution that massfraction is 0.4%, take out after soaking 5 hours under room temperature, be dried to constant weight at being placed in vacuum drying oven 90 DEG C, obtain modified carbonize boron fibre;
(3) modified carbonize silica fibre step (1) obtained and the group part except whipping agent add Banbury mixer 105 DEG C at mixing 10 minutes, continue at 120 DEG C after adding whipping agent to obtain compound in mixing 20 minutes, compound is sent into mill and opens refining 3 times, obtain the sheet material that thickness is 2mm, sheet material is moved to extruding pelletization at forcing machine 110 DEG C, water-resisting type SBS foaming sole material will be obtained after the granulate cooling obtained.
Therefore, compared with prior art, the present invention has following useful effect:
(1) PPSS is that the English of PPSS is write a Chinese character in simplified form, containing thiophenyl in its molecular structure, there is excellent water tolerance, under the effect of compatilizer, PPSS and SBS matrix defines the blended phase of friendly interface, SBS matrix introduces thiophenyl, adds the degree of crosslinking between molecular chain, effectively improve the water tolerance of material for sole of shoe.
(2) boron carbide fibre is the inorganic fibre of a kind of extreme hardness, it is insoluble to water, water tolerance is fine, but its surface is in wetting ability, incompatible with the lipophilicity of SBS matrix, so it is first oxidized by the present invention by nitric acid, a lot of groove is produced on boron carbide fibre surface, considerably increase surfaceness, surface modification is carried out again by earth solution, the groove on boron carbide fibre surface is conducive to the absorption to rare earth element and creates distortion district, substantially improve the consistency between boron carbide fibre and SBS matrix, the rare earth element of the two interface can play riveted effect, effectively increase interface binding power therebetween, thus effectively improve the mechanical property of material for sole of shoe, effectively reduce the degradation that material for sole of shoe causes because being subject to hydrolytic action, further increase the water tolerance of material for sole of shoe, in addition, boron carbide fibre also has good thermotolerance and wear resistance, therefore also can effectively improve thermotolerance and the wear resistance of material for sole of shoe.
Embodiment:
Below in conjunction with specific embodiment, the present invention being described in detail, illustrative examples and explanation in this present invention are used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS36 part, AC whipping agent 1.5 parts, naphthenic oil 14 parts, Magnesium Stearate 1.5 parts, DCP2 part, rare-earth stabilizer 1.8 parts, triphenyl phosphite 0.3 part, oxidation inhibitor GM0.6 part, boron carbide fibre 15 parts, PPSS8.5 part, SBS-g-MAH6 part.
The step of its preparation method is as follows:
(1) by boron carbide fibre ethanolic extraction 40 hours to remove surface impurity, clean with deionized water after extracting, add after dry in nitric acid and stir 3 hours at 90 DEG C, clean with deionized water after taking-up, obtain oxidation boron carbide fibre;
(2) the oxidation boron carbide fibre that step (1) obtains is added in the earth solution that massfraction is 0.4%, take out after soaking 5 hours under room temperature, be dried to constant weight at being placed in vacuum drying oven 90 DEG C, obtain modified carbonize boron fibre;
(3) modified carbonize silica fibre step (1) obtained and the group part except whipping agent add Banbury mixer 105 DEG C at mixing 10 minutes, continue at 120 DEG C after adding whipping agent to obtain compound in mixing 20 minutes, compound is sent into mill and opens refining 3 times, obtain the sheet material that thickness is 2mm, sheet material is moved to extruding pelletization at forcing machine 110 DEG C, water-resisting type SBS foaming sole material will be obtained after the granulate cooling obtained.
Embodiment 2
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS50 part, AC whipping agent 1.8 parts, naphthenic oil 11 parts, calcium stearate 2.5 parts, DCP1.5 part, rare-earth stabilizer 1.4 parts, triphenyl phosphite 0.4 part, oxidation inhibitor GM0.8 part, boron carbide fibre 14 parts, PPSS8 part, SBS-g-MAH10 part.
Its preparation method is in the same manner as in Example 1.
Embodiment 3
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS58 part, AC whipping agent 1.4 parts, naphthenic oil 15 parts, calcium stearate 2 parts, DCP1.8 part, rare-earth stabilizer 2 parts, triphenyl phosphite 0.4 part, oxidation inhibitor GM1 part, boron carbide fibre 14.5 parts, PPSS10 part, SBS-g-MAH7 part.
Its preparation method is in the same manner as in Example 1.
Embodiment 4
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS55 part, AC whipping agent 2 parts, naphthenic oil 10 parts, Magnesium Stearate 1 part, DCP1.2 part, rare-earth stabilizer 1.8 parts, triphenyl phosphite 0.3 part, oxidation inhibitor GM0.5 part, boron carbide fibre 17 parts, PPSS12 part, SBS-g-MAH9 part.
Its preparation method is in the same manner as in Example 1.
Embodiment 5
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS40 part, AC whipping agent 1.2 parts, naphthenic oil 13 parts, Magnesium Stearate 1.4 parts, DCP1 part, rare-earth stabilizer 1.6 parts, triphenyl phosphite 0.2 part, oxidation inhibitor GM0.7 part, boron carbide fibre 16 parts, PPSS11 part, SBS-g-MAH5 part.
Its preparation method is in the same manner as in Example 1.
Embodiment 6
A kind of water-resisting type SBS foaming sole material, by weight, is made up of following group of part: SBS45 part, AC whipping agent 1 part, naphthenic oil 12 parts, Magnesium Stearate 3 parts, DCP1.4 part, rare-earth stabilizer 1 part, triphenyl phosphite 0.2 part, oxidation inhibitor GM0.9 part, boron carbide fibre 18 parts, PPSS9 part, SBS-g-MAH8 part.
Its preparation method is in the same manner as in Example 1.
After tested, the water tolerance of embodiment 1-6 and comparative example is as shown in the table, wherein,
Comparative example is publication number is the Chinese patent of CN102964768B;
Water tolerance test process is: be soaked in by determinand in the water of 50 DEG C, takes out dry after 1 month, and the mechanical property maintenance rate of test determinand, mechanical property maintenance rate is more high shows that water tolerance is more good.
As seen from the above table, the stretching strength retentivity of the present invention and flexural strength maintenance rate are all obviously higher than comparative example, and water tolerance is better.
Above-described embodiment is the principle of illustrative the present invention and effect thereof only, but not for limiting the present invention. Above-described embodiment all under the spirit not running counter to the present invention and category, can be modified or change by any person skilled in the art scholar. Therefore, in art, tool usually intellectual, not departing under disclosed spirit and technological thought all the equivalence modifications completed or change, must be contained by the claim of the present invention such as.
Claims (10)
1. a water-resisting type SBS foaming sole material, it is characterised in that: by weight, it is made up of following group of part: SBS36～58 part, whipping agent 1～2 part, softening oil 10～15 parts, releasing agent 1～3 part, linking agent 1～2 part, thermo-stabilizer 1～2 part, photostabilizer 0.2～0.4 part, 0.5～1 part, oxidation inhibitor, boron carbide fibre 14～18 parts, PPSS8～12 part, compatilizer 5～10 parts.
2. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described whipping agent is AC whipping agent.
3. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described softening oil is naphthenic oil.
4. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described releasing agent is calcium stearate or Magnesium Stearate.
5. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described linking agent is DCP.
6. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described thermo-stabilizer is rare-earth stabilizer.
7. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described photostabilizer is triphenyl phosphite.
8. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described oxidation inhibitor is oxidation inhibitor GM.
9. a kind of water-resisting type SBS foaming sole material according to claim 1, it is characterised in that: described compatilizer is SBS-g-MAH.
10. the preparation method of a kind of water-resisting type SBS foaming sole material according to claim 1～9 any one, it is characterised in that: its step is as follows:
(1) by boron carbide fibre ethanolic extraction 40 hours to remove surface impurity, clean with deionized water after extracting, add after dry in nitric acid and stir 3 hours at 90 DEG C, clean with deionized water after taking-up, obtain oxidation boron carbide fibre;
(2) the oxidation boron carbide fibre that step (1) obtains is added in the earth solution that massfraction is 0.4%, take out after soaking 5 hours under room temperature, be dried to constant weight at being placed in vacuum drying oven 90 DEG C, obtain modified carbonize boron fibre;
(3) modified carbonize silica fibre step (1) obtained and the group part except whipping agent add Banbury mixer 105 DEG C at mixing 10 minutes, continue at 120 DEG C after adding whipping agent to obtain compound in mixing 20 minutes, compound is sent into mill and opens refining 3 times, obtain the sheet material that thickness is 2mm, sheet material is moved to extruding pelletization at forcing machine 110 DEG C, water-resisting type SBS foaming sole material will be obtained after the granulate cooling obtained.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610039012.4A CN105670198B (en) | 2016-01-21 | 2016-01-21 | A kind of water-resistant type SBS foaming sole material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610039012.4A CN105670198B (en) | 2016-01-21 | 2016-01-21 | A kind of water-resistant type SBS foaming sole material and preparation method thereof |
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| CN105670198A true CN105670198A (en) | 2016-06-15 |
| CN105670198B CN105670198B (en) | 2019-01-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109463843A (en) * | 2018-12-13 | 2019-03-15 | 盐城市吉成鞋业有限公司 | A kind of ski-proof snow land boots that heat-preservation ventilating effect is good |
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| CN1115484A (en) * | 1993-07-30 | 1996-01-24 | 青岛橡胶制品六厂 | Protecting material for fast neutron radiation |
| CN1544523A (en) * | 2003-11-20 | 2004-11-10 | 福建宏玮鞋塑有限公司 | Thermoplastic elastomeric foaming material and its preparation method |
| CN101245170A (en) * | 2007-02-14 | 2008-08-20 | 福建宏玮鞋塑有限公司 | Thermoplastic elastic body shoe material and production method |
| CN104356582A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Mico-crosslinking thermoplastic elastomer and preparation method thereof |
| CN104804358A (en) * | 2015-04-24 | 2015-07-29 | 茂泰(福建)鞋材有限公司 | Light-weight anti-aging shoe sole and preparation method thereof |
-
2016
- 2016-01-21 CN CN201610039012.4A patent/CN105670198B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1115484A (en) * | 1993-07-30 | 1996-01-24 | 青岛橡胶制品六厂 | Protecting material for fast neutron radiation |
| CN1544523A (en) * | 2003-11-20 | 2004-11-10 | 福建宏玮鞋塑有限公司 | Thermoplastic elastomeric foaming material and its preparation method |
| CN101245170A (en) * | 2007-02-14 | 2008-08-20 | 福建宏玮鞋塑有限公司 | Thermoplastic elastic body shoe material and production method |
| CN104356582A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Mico-crosslinking thermoplastic elastomer and preparation method thereof |
| CN104804358A (en) * | 2015-04-24 | 2015-07-29 | 茂泰(福建)鞋材有限公司 | Light-weight anti-aging shoe sole and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109463843A (en) * | 2018-12-13 | 2019-03-15 | 盐城市吉成鞋业有限公司 | A kind of ski-proof snow land boots that heat-preservation ventilating effect is good |
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