CN106633587B - A kind of soft abrasion-resistant special material for shoes and preparation method thereof - Google Patents
A kind of soft abrasion-resistant special material for shoes and preparation method thereof Download PDFInfo
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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
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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
- 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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- 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
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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
- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of soft abrasion-resistant special material for shoes, and using compounding collaboration SBS systems as base material, by weight percentage, composition includes：75~85wt% of high molecular weight SBS；10~20wt% of high styrenic percentage SBS；1~8wt% of star-like low-styrene-content SBS；The number-average molecular weight of the high molecular weight SBS>200000, styrene-content<35%；Styrene-content in the high styrenic percentage SBS>40%；Styrene-content in the star-like low-styrene-content SBS<20%.Simple for process the invention also discloses the preparation method of the soft abrasion-resistant special material for shoes, the footwear material being prepared has soft, wear-resisting, light characteristic.
Description
Technical field
The present invention relates to the technical field of high molecular material more particularly to a kind of soft abrasion-resistant special material for shoes and its preparations
Method.
Background technology
TPR (thermoplastic elastomer (TPE)) material is to be based on SBS (Styrene-Butadiene-Styrene Block Copolymer) thermoplasticity
Elastomer simultaneously coordinates other thermoplastic materials to be modified, addition white oil, filler, processing aid etc., the side processed by similar plastics
Method is made.TPR have elasticity it is good, anti-skidding, low temperature resistant, resistant to bending, good permeability, density is small, adhesive strength is high, easy processing at
The advantages that type, waste material be recyclable and good sense of touch, is widely used as material for sole of shoe at present.
With the development of science and technology and social progress, people's living standards continue to improve, the quality of all kinds of shoes is improved
And performance, allow wearer's more light wear-resistant to be comfortably final goal and the direction of entire shoe-making industry development.And among these, it is most heavy
What is wanted is exactly material for sole of shoe, and according to statistics, at present in footwear, sole weight in whole shoe parts is maximum, about accounts for
The 50% of full shoes weight, and the quality of shoes and comfort level are also largely dependent on sole.Therefore, on the basis of existing, into
One step mitigates the weight of sole, develops the high-performance material for shoes more comfortable, wear-resisting property is excellent, is shoe-making field
Researcher's facing challenges.
And as TPR materials, due to not by the sulfurization of rubber like, on soft comfortable and wearability
There are contradiction, soft comfortable improves, it would be desirable to and the more softening white oils of filling, this will substantially reduce the wearability of material,
And in order to improve wearability, then the use for reducing white oil is needed, the hardness of material is improved, will be reduced in terms of comfort.
Therefore, the application of the application field wear-resisting in highly-flexible, conventional TPR materials is restricted.
And it is directed to the exploitation of soft abrasion-resistant footwear material at present, have focused largely on vulcanized rubber field, such as
In the patents such as CN101186723A, CN101255244A and CN102212216A, disclose using natural rubber, butadiene-styrene rubber and
The various combination of butadiene rubber etc. comes and prepares rubber soles by sulfuration process, realizes the purpose of soft abrasion-resistant.However it is sharp
The defect that sole is prepared with vulcanized rubber is very prominent：Processing technology is more, and the waste material of generation can not recycle, and vulcanized rubber
The problems such as will produce peculiar smell, causing foot odour.
And in the fields TPR, also there is patent to disclose the method for improving TPR wearabilities, for example, in patent CN1454928 and
In CN101864139, discloses and improves the wearability of TPR materials using SBS cooperation ultra-high molecular weight polyethylenes (UHMWPE),
But the disadvantage is that introducing excessive UHMWPE in system, it reduce the pliability of material and comforts.
Invention content
The present invention is directed to existing TPR material softness and the contradictory defect of wearability, provides a kind of soft comfortable, wear-resisting property
Good, simple production process TPR material for sole of shoe and preparation method thereof.
The present invention is opened for the purpose of solving the wear-resisting contradiction between soft comfortable existing for existing TPR shoes materials
The wearability that send out existing good, but the TPR footwear materials for the flexibility having had, inventor have made extensive and intensive studies thus.Needle
To the core component SBS of TPR materials, the relationship of its chemical constitution and performance is investigated, as a result, it has been found that having different molecular structures
SBS combine and can well solve this problem.
SBS belongs to styrene block copolymer, the rubber segment (fourth two with hard segment (polystyrene) and a variety of softnesses
Alkene segment) elastomer.Hard segment and rubber segment chemical bonds, are separately aggregate to form nano level two-phase distributed architecture.SBS
The crosslinking rubber of enhancing is shown as at room temperature, but is processed and recycled as conventional thermoplastic's plastics at high temperature.
By carrying out the characterization test of microstructure and macro property to SBS, can obtain：It is formed on SBS molecular structures
Block structure is the key that performance thermoplastic elastomer (TPE)；And contain double bond in rubber segment, it is the basic molecule of difference and SEBS
The presence of structure feature, double bond causes SBS sensitive to free radical, ozone and UV, is easy light aging, but the presence of the double bond makes
SBS can be crosslinked, this is the maximum difference of itself and SIS, although there is also double bonds for SIS molecular structures, cannot be changed
Learn crosslinking.By the DSC characterizations to SBS, the glass transition temperature of SBS is lower than most of thermoplastics less than -70 DEG C, approaches
Rubber material, therefore there is good low-temperature flexibility.
The principal element for influencing TPR performances in SBS microstructures has：Styrene-content, relative molecular weight, two block concentrations
And molecular configuration.The raising of styrene-content can increase SBS melt viscosities, high temperature elastomeric and cohesive force and hardness, material
Plastic can increase.And the raising of molecular weight, melt viscosity can be improved, high temperature elastomeric, solution viscosity and elongation at break.
The increase of diblock content can reduce viscosity, reduce tensile strength, improve adhesion strength.The heterogeneous linear structure of SBS molecules and star-like knot
Structure, hub-and-spoke configuration are conducive to be crosslinked and improve inorganic fill content, promote cladding ability.
And it is directed to wearability, mainly relative molecular weight size and styrene-content are influenced in by SBS molecular structures, benzene second
Alkene segment exists in SBS as hard section, and the crosslinking points for mainly acting as similar vulcanized rubber act on, and provides intensity and wear-resisting
Property, therefore in order to improve wearability, need the SBS for selecting molecular weight big for base material, while having high styrene-content.But benzene second
Alkene content is opposite to be improved, and polybutadiene soft segment content relative reduction, flexibility can reduce, and hardness improves, and needs to pass through at this time
The more softening white oils of addition, this can cause the wearability of material to reduce again, therefore this is conflict.In the formula of TPR,
The polystyrene of part would generally be added, the processing performance of material can be improved, but can also improve the hardness of material, and these
The poly styrene polymer of outer addition, molecular weight about 3 × 105, than the PS chain segment molecular weights 1 × 10 in SBS4-3×104It is big
An order of magnitude so that PS is difficult to enter the PS microcells in SBS, and the PS being added outside this part cannot play cross-linked network fulcrum
Effect, cannot improve wearability.
Inventor is according to the relationship of SBS these performances and structure, by using a variety of SBS's with different molecular structures
Compounded combination can solve the contradiction of TPR material softness and wearability, therefore by having researched and proposed following molecular structure
Compound SBS combinations：
Compounding collaboration SBS systems are base material, and by weight percentage, composition includes：
75~85wt% of high molecular weight SBS；
10~20wt% of high styrenic percentage SBS；
1~8wt% of star-like low-styrene-content SBS；
Wherein, high molecular weight SBS, it is desirable that number-average molecular weight be more than 200000, and styrene-content control 35% hereinafter,
This SBS provides high intensity and high flexibility and preferable wearability；The SBS of high styrenic percentage, styrene-content are big
In 40%, styrene segment here can into its polystyrene domains with the styrene-compatible in high molecular weight SBS
As crosslinking points, to improve wearability, simultaneously as there are polybutadiene segments on its segment, the flexibility of material is maintained,
This is entirely different with individual polystyrene, while improving wear-resisting, also maintains flexibility；Star-like low-styrene-content
SBS (styrene-contents<20%), wearability is further increased there are conducive to crosslinked generation on a small quantity.Composite S BS's
Synergistic application is the innovative point of the present invention, can effectively solve TPR material softness and wear-resisting contradiction.
Collaboration SBS systems are compounded as core using this, develop novel soft abrasion-resistant TPR material for sole of shoe, substantially composition packet
It includes：
Preferably, the modified resin is selected from least one of PS, PE, EVA；
Preferably, the liquid softener is at least one in white oil, naphthenic oil, paraffin oil, PAO, polyisobutene
Kind；
Preferably, the foaming agent is AC foaming agents.
Preferably, the cross-linking system is formed by following weight percent：
10~60wt% of crosslinking agent；
40~90wt% of assistant crosslinking agent；
The crosslinking agent is cumyl peroxide or di-tert-butyl peroxide；
The assistant crosslinking agent is sulphur or Triallyl isocyanurate.
Further preferably, the cross-linking system is to press quality by cumyl peroxide and Triallyl isocyanurate
Than being 1:1 composition.
Preferably, other auxiliary agents include at least one in antioxidant, anti-UV agent, lubricant, pigment, antiwear additive
Kind.
On the basis of above-mentioned preferred raw material, further preferably, by weight percentage, raw material composition includes：
In the compounding collaboration SBS systems, the number-average molecular weight of the high molecular weight SBS>200000, styrene-content
It is 32%, is hub-and-spoke configuration；
Styrene-content is 44% in the high styrenic percentage SBS, is linear structure；
Styrene-content is 18% in the star-like low-styrene-content SBS.
The invention also discloses the preparation methods of the soft abrasion-resistant special material for shoes, and steps are as follows：
A) compounding collaboration SBS systems, liquid softener are mixed with other auxiliary agents, is completed to compounding collaboration SBS systems
It is oil-filled, it is denoted as component A；
B) modified resin, inorganic particle filler, cross-linking system and foaming agent are sufficiently mixed, are denoted as component B；
C) after mixing component A, component B, extruded molding obtains the soft abrasion-resistant special material for shoes.
The hardness that soft abrasion-resistant special material for shoes is prepared is 40~80Shore A, and proportion is 0.6~0.8g/cm3,
Polishing scratch 5.0~9.0mm of length has soft, wear-resisting, light characteristic.
Compared with prior art, the invention has the advantages that：
The spy that the present invention is formed by using different molecular weight size, different styrene-contents and different molecular chain structure
Different SBS compound systems form soft thermoplastic elastomer material compositions by adding liquid white oil softening agent, while adding friendship
It is conjuncted system and foaming system formed it is micro- crosslinking and fretting map structure with and meanwhile improve wearability and portability.
Specific implementation mode
Embodiment 1：
(1) SBS's is oil-filled
It is proportionally added into various SBS, liquid softener and various auxiliary agents in slow mixed machine, the completion pair under stirring at low speed
SBS's is oil-filled, and oil-filled temperature 60 C or so can be arranged；
Wherein, SBS-1 is that 1186 (styrene-content 32%, number-average molecular weights about 200000, hub-and-spoke configuration) are risen by section；SBS-
2 rise KX408 (styrene-content 44%, linear structure) for section；SBS-3 is that KX222 (styrene-content 18%, star-like knot are risen by section
Structure)；
It is a gram refining 4006 that liquid softener, which uses naphthenic oil, the trade mark,；
Lubricant is silicone, antioxidant 1010；
(2) mixture of each component
In high mixer, it is proportionally added into the modified resin polystyrene (trade mark：) and inorganic particle filler carbon GPPS-500N
Sour calcium (2000 mesh), (mass ratio of di-t-butyl peroxide and Triallyl isocyanurate is 1 to cross-linking system:1), AC foams
Agent is under high velocity agitation uniformly mixed material, and dry-mixed temperature is room temperature；
(3) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature (220 DEG C of spiro rod plasticizing section maximum temperature), temperature is waited for
After stablizing 20min, the uniform TPR material systems of mixture are added from hopper, starts host and feeder, completes the extrusion of material
It is granulated.The material for having made grain is sent into feed bin by blast system, and dries.
(4) the application test of material
The material dried is molded by the standard sample of various testing standard defineds in injection molding machine, and carries out correlation
The test of material property.
Each material and proportioning are shown in Table 1 in embodiment, and obtained material properties test the results are shown in Table 2
Embodiment 2
Implementation process is same as Example 1, and the ratio adjustment of SBS-1 and SBS-2 are outer.Other materials and proportioning are shown in Table 1, institute
Obtained material the results are shown in Table 2.
Embodiment 3
Implementation process is same as Example 1, and the ratio adjustment of SBS-2 and SBS-3 are outer.Other materials and proportioning are shown in Table 1, institute
Obtained material the results are shown in Table 2.
Embodiment 4
Implementation process is same as Example 3, and the ratio adjustment of SBS-1, SBS-2 are outer.Other materials and proportioning are shown in Table 1, institute
Obtained material the results are shown in Table 2.
Embodiment 5
Implementation process is same as Example 3, and the ratio adjustment of SBS-1, SBS-3 are outer.Other materials and proportioning are shown in Table 1, institute
Obtained material the results are shown in Table 2.
Embodiment 6
Implementation process is same as Example 1, and the compound proportion of three kinds of SBS is consistent, in addition to compounding SBS ratios are adjusted to
50%, the ratio adjustment of softening oil and modified resin is outer.Other materials and proportioning are shown in Table 1, and obtained material the results are shown in Table 2.
Embodiment 7
Implementation process is same as Example 1, and the ratio adjustment of cross-linking system and softening agent is outer.Other materials and proportioning are shown in Table
1, obtained material the results are shown in Table 2.
Comparative example 1
Implementation process is same as Example 1, and other than SBS-1 is used only, other materials and proportioning and material property are shown in Table
3。
Comparative example 2
Implementation process is same as Example 1, and other than SBS-2 is used only, other materials and proportioning and material property are shown in Table
3。
Comparative example 3
Implementation process is same as Example 1, and other than SBS-3 is used only, other materials and proportioning and material property are shown in Table
3。
Comparative example 4
Implementation process is same as Example 1, other than SBS-1 and SBS-2 is used only, other materials and proportioning and material
3 can be shown in Table.
Comparative example 5
Implementation process is same as Example 1, other than SBS-1 and SBS-3 is used only, other materials and proportioning and material
3 can be shown in Table.
Table 1
Table 2
Table 3
Claims (7)
1. a kind of soft abrasion-resistant special material for shoes, which is characterized in that using compounding collaboration SBS systems as base material, by weight percentage
Meter, raw material composition include：
The compounding cooperates with SBS systems, and by weight percentage, composition includes：
75~85wt% of high molecular weight SBS；
10~20wt% of high styrenic percentage SBS；
1~8wt% of star-like low-styrene-content SBS；
The number-average molecular weight of the high molecular weight SBS>200000, styrene-content<35%；
Styrene-content in the high styrenic percentage SBS>40%；
Styrene-content in the star-like low-styrene-content SBS<20%.
2. soft abrasion-resistant special material for shoes according to claim 1, which is characterized in that the modified resin be selected from PS,
At least one of PE, EVA；
The liquid softener is selected from least one of white oil, naphthenic oil, paraffin oil, PAO, polyisobutene；
The foaming agent is AC foaming agents.
3. soft abrasion-resistant special material for shoes according to claim 1, which is characterized in that the cross-linking system is by following heavy
Measure percentage composition：
10~60wt% of crosslinking agent；
40~90wt% of assistant crosslinking agent；
The crosslinking agent is cumyl peroxide or di-tert-butyl peroxide；
The assistant crosslinking agent is sulphur or Triallyl isocyanurate.
4. soft abrasion-resistant special material for shoes according to claim 3, which is characterized in that the cross-linking system is by peroxidating
Diisopropylbenzene (DIPB) and Triallyl isocyanurate composition.
5. soft abrasion-resistant special material for shoes according to claim 1, which is characterized in that other auxiliary agents include antioxygen
At least one of agent, anti-UV agent, lubricant, pigment, antiwear additive.
6. the soft abrasion-resistant special material for shoes according to Claims 1 to 5 any claim, which is characterized in that by weight
Percentages, raw material composition include：
In the compounding collaboration SBS systems, the number-average molecular weight of the high molecular weight SBS>200000, styrene-content is
32%, it is hub-and-spoke configuration；
Styrene-content is 44% in the high styrenic percentage SBS, is linear structure；
Styrene-content is 18% in the star-like low-styrene-content SBS.
7. a kind of preparation method of soft abrasion-resistant special material for shoes according to claim 1~6 any claim, special
Sign is that steps are as follows：
A) compounding collaboration SBS systems, liquid softener are mixed with other auxiliary agents, are completed to the oil-filled of compounding collaboration SBS systems,
It is denoted as component A；
B) modified resin, inorganic particle filler, cross-linking system and foaming agent are sufficiently mixed, are denoted as component B；
C) after mixing component A, component B, extruded molding obtains the soft abrasion-resistant special material for shoes.
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| CN116355348A (en) * | 2017-06-06 | 2023-06-30 | 顶级手套全球私人有限公司 | Crosslinked styrenic block copolymers |
| CN109367091A (en) * | 2018-09-30 | 2019-02-22 | 沈丹 | A kind of manufacture craft and healthy shoe of sole |
| EP3663355A1 (en) * | 2018-12-04 | 2020-06-10 | Top Glove International SDN. BHD. | Crosslinked styrenic block copolymer |
| CN110028714A (en) * | 2019-04-30 | 2019-07-19 | 温州市宜和鞋材有限公司 | A kind of formula and preparation process of ultralight one-pass molding composite sole |
| CN110326845B (en) * | 2019-08-14 | 2022-08-02 | 安踏（中国）有限公司 | Elastomer material for sole, sneaker sole and sneaker |
| CN110408161B (en) * | 2019-09-12 | 2022-02-11 | 东莞市兴茂橡塑科技有限公司 | High-permeability high-elasticity material, and preparation method and application thereof |
| CN110643133A (en) * | 2019-10-25 | 2020-01-03 | 温州市胜帆鞋材有限公司 | TPR sole and preparation method thereof |
| CN112679903B (en) * | 2020-12-23 | 2022-09-13 | 宁波市青湖弹性体科技有限公司 | TPE environment-friendly building material and preparation method thereof |
| CN115216107A (en) * | 2022-09-05 | 2022-10-21 | 温州市丰盛鞋业有限公司 | Wear-resistant and yellow-deformation-resistant TPR (thermal Plastic rubber) sole material and preparation method thereof |
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| CN101845195B (en) * | 2010-05-07 | 2011-11-02 | 浙江俊尔新材料有限公司 | Wear-resistant thermoplastic elastomer and preparation method thereof |
| US9394414B2 (en) * | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
| CN102391606B (en) * | 2011-09-07 | 2012-12-12 | 安踏（中国）有限公司 | Elastomer composition for soles of sports shoes, and manufacturing method thereof |
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