CN108659486A - A kind of degradable EVA foam shoe material and preparation method thereof - Google Patents
A kind of degradable EVA foam shoe material and preparation method thereof Download PDFInfo
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- CN108659486A CN108659486A CN201810312340.6A CN201810312340A CN108659486A CN 108659486 A CN108659486 A CN 108659486A CN 201810312340 A CN201810312340 A CN 201810312340A CN 108659486 A CN108659486 A CN 108659486A
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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
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- 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
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Abstract
The present invention relates to fluid sealant technical fields, and in particular to a kind of degradable EVA foam shoe material and preparation method thereof is made of component below：Polylactic acid, starch, EVA, POE, stearic acid, zinc oxide, bridging agent, foaming agent, filler, titanium dioxide and Masterbatch.Due to being modified to EVA and POE by polylactic acid and starch, so that modified major ingredient obtained is degradable, and since polylactic acid and starch are easy degradation, so that obtained degradable EVA foam shoe material has the advantages that be easy degradation, after discarding, it will not cause damages to natural environment.The preparation method of the degradable EVA foam shoe material, including：Step 1: cross-linking reaction；Step 2: mixing；Step 3: being granulated；Step 4: sole is processed into foaming.The preparation method have preparation method it is simple, production cost is low, and can be suitable for industrialization large-scale production the characteristics of.
Description
Technical field
The present invention relates to fluid sealant technical fields, and in particular to a kind of degradable EVA foam shoe material and preparation method thereof.
Background technology
EVA is copolymer made of being copolymerized by ethene-vinyl acetate, and abbreviation EVA, compared with polyethylene, EVA is due to dividing
Vinyl acetate monomer is introduced in subchain, to reduce high-crystallinity, improves flexibility, impact resistance, filler intermiscibility
And heat sealing performance.EVA midsoles refer to just that EVA is injected after mold through one-time formed midsole after high-temperature heating, are also cried
One step foaming midsole.EVA particles are emitted directly toward inside board mold by traditional EVA hot pressing, EVA ejaculators, and vacuum adds
Sulphur opens mold after 400 seconds or so, mould insole foaming, shapes using heat, cold formed case.The characteristics of this method is exactly
Yield is high, one-pass molding.The disadvantage is that being easily deformed, turn to be yellow, shrinks over time.
EVA foam shoe material in the prior art is mostly difficult to the material degraded, therefore is sent out using EVA in the prior art
After steeping article of footwear discarding prepared by footwear material, due to being difficult to degrade, long-term accumulation will cause damages to natural environment.
Invention content
It, should it is an object of the present invention in view of the deficiencies of the prior art, providing a kind of degradable EVA foam shoe material
Degradable EVA foam shoe material has the advantages that be easy degradation, after discarding, will not cause damages to natural environment.
The second object of the present invention is to provide a kind of degradable EVA foam shoe material in view of the deficiencies of the prior art
Preparation method.
One of to achieve the goals above, the present invention adopts the following technical scheme that：
A kind of degradable EVA foam shoe material is provided, is made of the component of following parts by weight：
Preferably, a kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
More preferably, a kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
The bridging agent is cumyl peroxide.
The foaming agent is azodicarbonamide.
The filler is calcium carbonate.
To achieve the goals above two, the present invention adopts the following technical scheme that：
A kind of preparation method of degradable EVA foam shoe material is provided, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are carried out at a certain temperature
For a period of time, degradable major ingredient is made in cross-linking reaction；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
In above-mentioned technical proposal, in the cross-linking reaction of the step 1, the temperature of cross-linking reaction is 170 DEG C~180 DEG C, is handed over
The time of connection reaction is 8min~12min.
In above-mentioned technical proposal, in the step 2, the temperature of mixing is 120 DEG C~130 DEG C, and the time of mixing is 7min
~9min.
Compared with prior art, advantageous effect is the present invention：
(1) a kind of degradable EVA foam shoe material provided by the invention, due to by polylactic acid and starch to EVA and POE
It is modified so that modified major ingredient obtained is degradable, and since polylactic acid and starch are easy degradation, so that made
The degradable EVA foam shoe material obtained has the advantages that be easy degradation, after discarding, will not cause damages to natural environment.
(2) preparation method of a kind of degradable EVA foam shoe material provided by the invention has preparation method simple, raw
Produce it is at low cost, and can be suitable for industrialization large-scale production the characteristics of.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Embodiment 1.
A kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
It is made of the component of following parts by weight：
Wherein, bridging agent is cumyl peroxide.
Wherein, foaming agent is azodicarbonamide.
Wherein, filler is calcium carbonate.
A kind of preparation method of above-mentioned degradable EVA foam shoe material, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are handed at 175 DEG C
Connection reaction 10min, is made degradable major ingredient；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；In the present embodiment, the temperature of mixing is 125 DEG C, mixing
Time be 8min；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
Embodiment 2.
A kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
It is made of the component of following parts by weight：
Wherein, bridging agent is cumyl peroxide.
Wherein, foaming agent is azodicarbonamide.
Wherein, filler is calcium carbonate.
A kind of preparation method of above-mentioned degradable EVA foam shoe material, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are handed at 170 DEG C
Connection reaction 12min, is made degradable major ingredient；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；In the present embodiment, the temperature of mixing is 120 DEG C, mixing
Time be 9min；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
Embodiment 3.
A kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
It is made of the component of following parts by weight：
Wherein, bridging agent is cumyl peroxide.
Wherein, foaming agent is azodicarbonamide.
Wherein, filler is calcium carbonate.
A kind of preparation method of above-mentioned degradable EVA foam shoe material, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are handed at 180 DEG C
Connection reaction 8min, is made degradable major ingredient；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；In the present embodiment, the temperature of mixing is 130 DEG C, mixing
Time be 7min；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
Embodiment 4.
A kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
It is made of the component of following parts by weight：
Wherein, bridging agent is cumyl peroxide.
Wherein, foaming agent is azodicarbonamide.
Wherein, filler is calcium carbonate.
A kind of preparation method of above-mentioned degradable EVA foam shoe material, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are handed at 172 DEG C
Connection reaction 11min, is made degradable major ingredient；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；In the present embodiment, the temperature of mixing is 123 DEG C, mixing
Time be 8.5min；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
Embodiment 5.
A kind of degradable EVA foam shoe material, is made of the component of following parts by weight：
It is made of the component of following parts by weight：
Wherein, bridging agent is cumyl peroxide.
Wherein, foaming agent is azodicarbonamide.
Wherein, filler is calcium carbonate.
A kind of preparation method of above-mentioned degradable EVA foam shoe material, it includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are handed at 178 DEG C
Connection reaction 9min, is made degradable major ingredient；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming
Agent, filler, titanium dioxide and Masterbatch carry out mixing, obtain mixing material；In the present embodiment, the temperature of mixing is 128 DEG C, mixing
Time be 7.5min；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
The pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole, obtained described by step 4
Degradable EVA foam shoe material.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art answer
Work as understanding, technical scheme of the present invention can be modified or replaced equivalently, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (9)
1. a kind of degradable EVA foam shoe material, it is characterised in that：It is made of the component of following parts by weight：
2. a kind of degradable EVA foam shoe material according to claim 1, it is characterised in that：By following parts by weight
Component is made：
3. a kind of degradable EVA foam shoe material according to claim 1, it is characterised in that：By following parts by weight
Component is made：
4. a kind of degradable EVA foam shoe material according to claim 1, it is characterised in that：The bridging agent is peroxide
Change diisopropylbenzene (DIPB).
5. a kind of degradable EVA foam shoe material according to claim 1, it is characterised in that：The foaming agent is azo
Diformamide.
6. a kind of degradable EVA foam shoe material according to claim 1, it is characterised in that：The filler is carbonic acid
Calcium.
7. a kind of preparation method of degradable EVA foam shoe material described in claim 1 to 6 any one, it is characterised in that：
It includes the following steps：
Step 1: cross-linking reaction：The polylactic acid of formula ratio, starch, EVA, POE and bridging agent are crosslinked at a certain temperature
Reaction a period of time, degradable major ingredient is made；
Step 2: mixing：By the stearic acid of degradable major ingredient and formula ratio made from step 1, zinc oxide, foaming agent, fill out
It fills agent, titanium dioxide and Masterbatch and carries out mixing, obtain mixing material；
Step 3: being granulated：Mixing material made from step 2 is granulated using comminutor；
Pellet that step 3 has been made is carried out foaming using footwear material ejaculator and is processed into sole by step 4, and obtaining described can drop
The EVA foam shoe material of solution.
8. a kind of preparation method of degradable EVA foam shoe material according to claim 7, it is characterised in that：The step
In rapid one cross-linking reaction, the temperature of cross-linking reaction is 170 DEG C~180 DEG C, and the time of cross-linking reaction is 8min~12min.
9. a kind of preparation method of degradable EVA foam shoe material according to claim 7, it is characterised in that：The step
In rapid two, the temperature of mixing is 120 DEG C~130 DEG C, and the time of mixing is 7min~9min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810312340.6A CN108659486A (en) | 2018-04-09 | 2018-04-09 | A kind of degradable EVA foam shoe material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810312340.6A CN108659486A (en) | 2018-04-09 | 2018-04-09 | A kind of degradable EVA foam shoe material and preparation method thereof |
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| CN108659486A true CN108659486A (en) | 2018-10-16 |
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| CN201810312340.6A Pending CN108659486A (en) | 2018-04-09 | 2018-04-09 | A kind of degradable EVA foam shoe material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824972A (en) * | 2019-03-08 | 2019-05-31 | 安踏（中国）有限公司 | Bottom material and preparation method thereof in a kind of environment-friendly foaming |
| CN111440423A (en) * | 2020-05-20 | 2020-07-24 | 安踏（中国）有限公司 | Biodegradable foamed shoe midsole material and preparation method thereof |
| CN113416361A (en) * | 2021-06-17 | 2021-09-21 | 特步(中国)有限公司 | Polylactic acid sole and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134349A (en) * | 2011-02-23 | 2011-07-27 | 安踏（中国）有限公司 | EVA material for sneaker sole and preparation method thereof |
| CN107011542A (en) * | 2017-05-31 | 2017-08-04 | 三斯达（江苏）环保科技有限公司 | A kind of biodegradable expanded material and preparation method thereof |
-
2018
- 2018-04-09 CN CN201810312340.6A patent/CN108659486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134349A (en) * | 2011-02-23 | 2011-07-27 | 安踏（中国）有限公司 | EVA material for sneaker sole and preparation method thereof |
| CN107011542A (en) * | 2017-05-31 | 2017-08-04 | 三斯达（江苏）环保科技有限公司 | A kind of biodegradable expanded material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824972A (en) * | 2019-03-08 | 2019-05-31 | 安踏（中国）有限公司 | Bottom material and preparation method thereof in a kind of environment-friendly foaming |
| CN111440423A (en) * | 2020-05-20 | 2020-07-24 | 安踏（中国）有限公司 | Biodegradable foamed shoe midsole material and preparation method thereof |
| CN113416361A (en) * | 2021-06-17 | 2021-09-21 | 特步(中国)有限公司 | Polylactic acid sole and manufacturing method thereof |
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