CN103183955B - A kind of foamed thermoplastic polyurethane elastomer material sole and preparation method thereof - Google Patents
A kind of foamed thermoplastic polyurethane elastomer material sole and preparation method thereof Download PDFInfo
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- CN103183955B CN103183955B CN201110446516.5A CN201110446516A CN103183955B CN 103183955 B CN103183955 B CN 103183955B CN 201110446516 A CN201110446516 A CN 201110446516A CN 103183955 B CN103183955 B CN 103183955B
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- tpu material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention discloses a kind of foamed thermoplastic polyurethane elastomer material (F-TPU material) preparation method of shoe pads.Comprise the steps: to heat F-TPU material granule with single screw extrusion machine and extrude, fusing F-TPU material granule also extrudes F-TPU material melt; F-TPU material melt is injected die for shoe-sole; Cooling curing is shaping.The present invention also discloses F-TPU material sole.In F-TPU material sole of the present invention and preparation method thereof, F-TPU material sole intensity is high, good springiness, light weight, wear-resisting, comfortable, anti-skidding, to the impact on ground, there is shock absorption, also can be made into multiple color, many hardness sole, in sole the end and outer bottom one-body molded, have simultaneously pollution-free, cost is low and the simple advantage of technique.
Description
Technical field
The present invention relates to organic polymer chemical technology field, particularly relate to a kind of foamed thermoplastic polyurethane elastomer material (F-TPU material) sole and preparation method thereof.
Background technology
As everyone knows, conventional footwear material uses rubber to do sole mostly, and its gel content is at most about 40%, and low-grade footwear gel content is lower, and due to the existence of a large amount of stopping composition, make the intensity of rubber soles low, use properties is poor.In sole, the end, adopts EVA foaming (one step foaming) and PHYION foaming (second time of foaming).Wherein in PHYION, the end, uses many, have light, good springiness and have good damping performance, but in PHYION, the wear resisting property at the end is poor.And in EVA in the end and PHYION the end similar, just through one step foaming, cost compare is low, but simultaneously elasticity and wear resisting property all poor than the end in PHYION.Following shortcoming is there is: EVA or other materials sole are adopted different hot melt adhesive binding agents bonding, various different hot melt adhesive product has certain toxicity all in varying degrees, and some work must by manually completing when making EVA microporous foam material for shoes.This causes one to be that the toxicity of sizing agent can have a huge impact personnel health, also directly increases cost on the other hand.During foaming can not 1: 1 foaming, cause the size of sole and the not of uniform size of die for shoe-sole to cause; Raw materials consumption amount used during foaming is high, and raw materials cost is high, and foaming proportion is generally between 0.5 ~ 0.8.
At present, thermoplastic polyurethane material (TPU) is because having high abrasion, and snappiness, antifatigue, the plurality of advantages such as chemical resistant properties, therefore in a lot of industry, are widely used, and wherein sole market is particularly considerable.But during current material employing multigraph press injection technique, can not once shaped.How the aspects such as TPU sole also has some shortcomings, and such as weight is large, and hardness is high, damping performance difference, therefore improve the shortcoming of TPU sole, allow TPU sole collection many merits with all over the body, just become a main research class of current TPU sole industry.
Summary of the invention
For the weak point existed in above-mentioned technology, the embodiment of the present invention provides F-TPU material sole preparation method, comprises the steps:
Heating F-TPU material granule with single screw extrusion machine and extrude, fusing F-TPU material granule also extrudes F-TPU material melt;
F-TPU material melt is injected die for shoe-sole;
Cooling curing is shaping;
Wherein, the preparation process of described F-TPU material is specially: the feed end that component A introduces the first single screw extrusion machine respectively by test tank is carried out prepolymerization, add B component at the discharge end of the first single screw extrusion machine and introduce the feed end of the second single screw extrusion machine with reacted component A, the component A and the B component that enter the feed end of the second single screw extrusion machine fully carry out polyreaction under the second single screw extrusion machine extruding, fully extrude from the discharge end of the second single screw extrusion machine after reaction; Described component A comprises polyester polyol, linking agent and isocyanic ester further, and polyester polyol accounts for component A weight ratio is 50% ~ 70%, and it is 6% ~ 9% that linking agent accounts for component A weight ratio, and isocyanic ester accounts for component A weight ratio 18% ~ 50%; Described B component comprises: catalyzer, frothing aid, water, tensio-active agent, triisocyanate, help sulphur agent and whipping agent, catalyzer and component A weight ratio are 1 ‰ ~ 3 ‰, frothing aid and component A weight ratio are 4 ‰ ~ 5 ‰, water and component A weight ratio are 0.9 ‰ ~ 2 ‰, tensio-active agent and component A weight ratio are 1 ‰ ~ 10 ‰, triisocyanate and component A weight ratio are 1 ‰ ~ 4 ‰, and help sulphur agent and component A weight ratio to be 1 ‰ ~ 3 ‰, whipping agent and component A weight ratio are 2% ~ 4%.
According to one preferred embodiment of the present invention, single screw extrusion machine comprises feed zone, compression section and homogenizing zone, and feed zone temperature controls at 140 ~ 145 DEG C.
According to one preferred embodiment of the present invention, compression section temperature controls at 150 ~ 160 DEG C.
According to one preferred embodiment of the present invention, homogenizing zone temperature controls at 145 ~ 150 DEG C.
According to one preferred embodiment of the present invention, when F-TPU material melt injects die for shoe-sole, injection pressure is 90 ~ 140bar, and injection speed is 75mm/s, and the injecting glue time is 1.7 ~ 2.0s.
According to one preferred embodiment of the present invention, when F-TPU material melt injects die for shoe-sole, injection pressure is 90 ~ 140bar, and injection speed is 75mm/s, and the injecting glue time is 1.7 ~ 2.0s.
According to one preferred embodiment of the present invention, when F-TPU material melt injects die for shoe-sole, inject time is 3 ~ 5min.
According to one preferred embodiment of the present invention, when cooling curing is shaping, cooling time is 60 ~ 80s.
According to one preferred embodiment of the present invention, to comprise bottom die and outsole molds in middle bottom die and outsole molds one-body molded for die for shoe-sole.
According to one preferred embodiment of the present invention, when cooling curing is shaping, the middle end and outer bottom one-body molded.
The embodiment of the present invention also provides F-TPU material sole, and F-TPU material sole comprises the middle end and outer bottom, the middle end and outer bottom one-body molded.
In F-TPU material sole of the present invention and preparation method thereof, adopt disk injection method, can arrive mold closing 1: 1 foam, once shaped, free bonding, waste material can reuse, have pollution-free, cost is low and the simple advantage of technique.
Accompanying drawing explanation
Fig. 1 is the schema of F-TPU material preparation method first embodiment of the present invention;
Fig. 2 is the schema of F-TPU material preparation method second embodiment of the present invention;
Fig. 3 is the process flow sheet of F-TPU material preparation method second embodiment of the present invention;
Fig. 4 is the schema of F-TPU material sole preparation method one of the present invention preferred embodiment.
Embodiment
Refer to Fig. 1, Fig. 1 is the schema of F-TPU material preparation method first embodiment of the present invention.F-TPU material preparation method comprises the following steps:
Step S21, the feed end that component A introduces the first single screw extrusion machine respectively by test tank is carried out prepolymerization, and component A comprises polyester polyol, linking agent and isocyanic ester;
Step S22, add B component at the discharge end of the first single screw extrusion machine and introduce the feed end of the second screw extrusion press with reacted component A, wherein B component comprises: catalyzer, frothing aid, water, tensio-active agent, triisocyanate, help sulphur agent and whipping agent;
Step S23, component A and B component polyreaction under the second screw extrusion press extruding, fully extrude from the discharge end of the second spiral shell screw extrusion press after reaction.
See also Fig. 2 and Fig. 3, Fig. 2 is the schema of F-TPU material preparation method second embodiment of the present invention, and Fig. 3 is the process flow sheet of F-TPU material preparation method second embodiment of the present invention.Specifically, component A is introduced the feed end 101 of the first single screw extrusion machine 10 from material tank 1 by header tank 4 and test tank 7 respectively and carries out prepolymerization at the first single screw extrusion machine 10, first single screw extrusion machine 10 temperature of reaction controls, 90 DEG C ~ 110 DEG C time, reacted component A to be introduced the feed end 131 of the second screw extrusion press 13.Component A comprises polyester polyol, linking agent and isocyanic ester, and polyester polyol accounts for component A weight ratio is 50% ~ 70%, and it is 6% ~ 9% that linking agent accounts for component A weight ratio, and it is 18% ~ 50% that isocyanic ester accounts for component A weight ratio.It is 65% that polyester polyol accounts for component A optimum weight ratio, and it is 8% that linking agent accounts for component A optimum weight ratio, and it is 27% that isocyanic ester accounts for component A optimum weight ratio.
B component is metered into by powder body feeding machine 11 by weight-loss type powder metering device 12 at the discharge end 103 of the first single screw extrusion machine 10, when adding B component, temperature of reaction controls at 100 DEG C, and then B component and component A together enter 13 feed ends 131 of the second single screw extrusion machine.Wherein B component comprises: catalyzer, frothing aid, water, tensio-active agent, triisocyanate, help sulphur agent and whipping agent.Catalyzer and component A weight ratio are 1 ‰ ~ 3 ‰, frothing aid and component A weight ratio are 4 ‰ ~ 5 ‰, water and component A weight ratio are 0.9 ‰ ~ 2 ‰, tensio-active agent and component A weight ratio are 1 ‰ ~ 10 ‰, triisocyanate and component A weight ratio are 1 ‰ ~ 4 ‰, help sulphur agent and component A weight ratio to be 1 ‰ ~ 3 ‰, whipping agent and component A weight ratio are 2% ~ 4%.Catalyzer and component A optimum weight ratio are 1.5 ‰, frothing aid and component A optimum weight ratio are 4 ‰, water and component A optimum weight ratio are 1 ‰, tensio-active agent and component A optimum weight ratio are 3 ‰, triisocyanate and component A optimum weight ratio are 3 ‰, help sulphur agent and component A optimum weight ratio to be 1.5 ‰, whipping agent and component A optimum weight ratio are 3%.
In addition to the components described above, B component also comprises interior lubrication prescription, outer lubrication prescription and tinting material, and interior lubrication prescription and component A weight ratio are 1 ‰ ~ 3 ‰, and outer lubrication prescription and component A weight ratio are 2 ‰ ~ 3 ‰, and tinting material and component A weight ratio are 1 ‰ ~ 10 ‰.Interior lubrication prescription and component A optimum weight ratio are 1.5 ‰, and outer lubrication prescription and component A optimum weight ratio are 2.1 ‰.
Wherein, enter component A and B component polyreaction under the second single screw extrusion machine 13 extrudes of 13 feed ends 131 of the second single screw extrusion machine, fully extrude from the discharge end 133 of the second single screw extrusion machine 13 after reaction.Then the F-TPU material extruded is entered underwater pelletizer 14, the temperature of imderwater cutting controls at 25 DEG C ~ 30 DEG C.Cutting completes, and utilize water separator 15 to carry out being separated of water and F-TPU material granule again, the F-TPU material granule obtained enters the air-dry last introducing material-storage jar 17 of air dryer 15.
Also can add component C when the discharge end 101 of the first single screw extrusion machine 10 adds B component, component C and B component, by after powder body feeding machine 11 fully mixing, enter the discharge end 103 of the first single screw extrusion machine 10 simultaneously.Component C comprises toughner, softening agent and toughener, and toughner and component A weight ratio are 3% ~ 8%, and softening agent and component A weight ratio are 1% ~ 10%, and toughener and component A weight ratio are 1% ~ 10%.Toughner and component A optimum weight ratio are 4%, and softening agent and component A optimum weight ratio are 7%, and toughener and component A optimum weight ratio are 3% ~ 5%.
In the present embodiment, isocyanic ester main component is diphenylmethanediisocyanate, whipping agent is Cellmic C 121 or sodium bicarbonate, linking agent is 1,4 butyleneglycols or hexylene glycol or 4 hydroxyethyl oxygen ethyl 1 hydroxyethylbenzene diether, catalyzer is metal species: stannous octoate or dibutyltin dilaurate or mercuric acetate, or be non-metal kind: three own tin diamino or dimethylethanolamines, interior lubrication prescription is amine hydroxybenzene, sulphur agent is helped to be Si Liaodengji dicalcium phosphate feed grade, outer lubrication prescription is ethylenebisstearamide, and tinting material is that toner or look female.
Refer to Fig. 4, Fig. 4 is the schema of F-TPU material sole preparation method one of the present invention preferred embodiment.F-TPU material sole is preparation method comprise the following steps:
Step S31, to heat F-TPU material granule with single screw extrusion machine and extrudes, and fusing F-TPU material granule also extrudes F-TPU material melt;
Step S32, injects die for shoe-sole by F-TPU material melt;
Step S33, cooling curing is shaping.
Specifically, single screw extrusion machine comprises feed zone, compression section and homogenizing zone, when F-TPU material granule being heated and is extruded with single screw extrusion machine, first F-TPU material granule is introduced into the feed zone of single screw extrusion machine and successively enters compression section and homogenizing zone, wherein feed zone temperature controls at 140 ~ 145 DEG C, compression section temperature controls at 150 ~ 160 DEG C, and homogenizing zone temperature controls at 145 ~ 150 DEG C.
After single screw extrusion machine fully melts F-TPU material granule, extrude F-TPU material melt inject die for shoe-sole, wherein, die for shoe-sole comprises middle bottom die and outsole molds, middle bottom die and outsole molds one-body molded.
When the F-TPU material melt extruded from single screw extrusion machine injects die for shoe-sole, it is 90 ~ 140bar that injection pressure controls, and injection speed controls as 75mm/s, and injecting glue time controling is 1.7 ~ 2.0s, and inject time, control was 3 ~ 5min.
F-TPU material melt enters the air that die for shoe-sole runs into die for shoe-sole die cavity and instantaneous expansion is become large, is full of the die cavity of whole die for shoe-sole and shaping at die cavity cooling curing.When cooling curing is shaping, the middle end and outer bottom one-body molded, cooling time is 60 ~ 80s.Shaping sole reaches the foaming ratio of 1: 1, i.e. the size of sole and the in the same size of die for shoe-sole die cavity.
The embodiment of the present invention also provides F-TPU material sole, and F-TPU material sole comprises the middle end and outer bottom, the middle end and outer bottom one-body molded.
The equal toxicological harmless of all raw materials that F-TPU material sole of the present invention and preparation method thereof is selected, production process does not produce toxic gas and toxic liquid.Do not need stained agent, the middle end and outer bottom once shaped, can reduce a large amount of manual work.Waste can Reusability, and raw material availability reaches 100%, very environmental protection, and foaming degree is high, and blowing ratio focuses between 0.3 ~ 0.5, reduces raw materials cost.
In the embodiment of the present invention, F-TPU material can be adopted to carry out one-shot forming production technology, not only avoid drawback and the shortcoming of material toxicity and manual production in original production technique, F-TPU material sole product in the present invention simultaneously not only has the various advantages of traditional TPU material, also have that sole intensity is high simultaneously, good springiness, light weight, wear-resisting, comfortable, anti-skidding, to the impact on ground, there is shock absorption, can be made into the advantage such as multiple color, many hardness sole, will be the use road that Chinese sole industry opens up a type material and novel production process.
In sum, F-TPU material sole of the present invention and preparation method thereof, have pollution-free, cost is low and technique is simple, the advantage of excellent property.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a foamed thermoplastic polyurethane elastomer material preparation method of shoe pads, is characterized in that, comprises the steps:
Heating F-TPU material granule with single screw extrusion machine and extrude, fusing F-TPU material granule also extrudes F-TPU material melt;
F-TPU material melt is injected die for shoe-sole;
Cooling curing is shaping;
Wherein, the preparation process of described F-TPU material is specially: the feed end that component A introduces the first single screw extrusion machine respectively by test tank is carried out prepolymerization, add B component at the discharge end of the first single screw extrusion machine and introduce the feed end of the second single screw extrusion machine with reacted component A, the component A and the B component that enter the feed end of the second single screw extrusion machine fully carry out polyreaction under the second single screw extrusion machine extruding, fully extrude from the discharge end of the second single screw extrusion machine after reaction; Described component A comprises polyester polyol, linking agent and isocyanic ester, and polyester polyol accounts for component A weight ratio is 50% ~ 70%, and it is 6% ~ 9% that linking agent accounts for component A weight ratio, and isocyanic ester accounts for component A weight ratio 18% ~ 50%; Described B component comprises: catalyzer, frothing aid, water, tensio-active agent, triisocyanate, help sulphur agent and whipping agent, catalyzer and component A weight ratio are 1 ‰ ~ 3 ‰, frothing aid and component A weight ratio are 4 ‰ ~ 5 ‰, water and component A weight ratio are 0.9 ‰ ~ 2 ‰, tensio-active agent and component A weight ratio are 1 ‰ ~ 10 ‰, triisocyanate and component A weight ratio are 1 ‰ ~ 4 ‰, and help sulphur agent and component A weight ratio to be 1 ‰ ~ 3 ‰, whipping agent and component A weight ratio are 2% ~ 4%.
2. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 1, it is characterized in that, single screw extrusion machine comprises feed zone, compression section and homogenizing zone, and feed zone temperature controls at 140 ~ 145 DEG C.
3. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 2, it is characterized in that, compression section temperature controls at 150 ~ 160 DEG C.
4. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 2, it is characterized in that, homogenizing zone temperature controls at 145 ~ 150 DEG C.
5. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 1, is characterized in that, when F-TPU material melt injects die for shoe-sole, injection pressure is 90 ~ 140bar, and injection speed is 75mm/s, and the injecting glue time is 1.7 ~ 2.0s.
6. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 1, is characterized in that, when F-TPU material melt injects die for shoe-sole, inject time is 3 ~ 5min.
7. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 1, is characterized in that, when cooling curing is shaping, cooling time is 60 ~ 80s.
8. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 1, it is characterized in that, described die for shoe-sole comprises middle bottom die and outsole molds, described middle bottom die and described outsole molds one-body molded.
9. foamed thermoplastic polyurethane elastomer material preparation method of shoe pads according to claim 8, is characterized in that, when cooling curing is shaping, the middle end and outer bottom one-body molded.
10. the foamed thermoplastic polyurethane elastomer material sole utilizing the foamed thermoplastic polyurethane elastomer material preparation method of shoe pads described in any one of claim 1-9 obtained, it is characterized in that, described F-TPU material sole comprises the middle end and outer bottom, the described middle end and described outer bottom one-body molded.
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| CN201110446516.5A CN103183955B (en) | 2011-12-28 | 2011-12-28 | A kind of foamed thermoplastic polyurethane elastomer material sole and preparation method thereof |
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| CN201110446516.5A CN103183955B (en) | 2011-12-28 | 2011-12-28 | A kind of foamed thermoplastic polyurethane elastomer material sole and preparation method thereof |
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| CN103183955B true CN103183955B (en) | 2015-08-19 |
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| TWI656153B (en) | 2013-10-11 | 2019-04-11 | 巴斯夫歐洲公司 | Manufacture of expanded thermoplastic elastomer beads |
| CN104799477A (en) * | 2014-01-24 | 2015-07-29 | 三晃股份有限公司 | Integrally-formed shoe material and manufacturing method thereof |
| CN103804890B (en) | 2014-02-18 | 2016-01-27 | 山东美瑞新材料有限公司 | A kind of extrusion foaming Polyurethane Thermoplastic Elastomer particle and preparation method thereof |
| CN104441409A (en) * | 2014-11-04 | 2015-03-25 | 林仔孺 | Production process of foamed TPU (Thermoplastic polyurethane) sole |
| CN104626454A (en) * | 2014-12-24 | 2015-05-20 | 东莞智标鞋业科技有限公司 | Preparation method and product of double-density-layer middle sole |
| CN104774433A (en) * | 2015-04-14 | 2015-07-15 | 江苏绿艳高分子材料有限公司 | TUP large sole and preparation method thereof |
| CN106349681B (en) * | 2016-08-22 | 2018-01-23 | 东莞芳言新材料科技有限公司 | A kind of PUR sock and preparation method thereof |
| CN106380824A (en) * | 2016-09-05 | 2017-02-08 | 万家鑫（福建）皮塑鞋材有限公司 | ETPU luminous shoe material and preparation process thereof |
| CN108095245A (en) * | 2017-12-15 | 2018-06-01 | 清远市广硕鞋业有限公司 | Wear-resisting anti-slip sole structure |
| US11020922B2 (en) | 2018-07-27 | 2021-06-01 | Adidas Ag | Footwear with padding and midsole structures and the method of making the same |
| JP7499229B2 (en) * | 2018-09-03 | 2024-06-13 | コベストロ （ネザーランズ） ビー．ブイ． | SHOES COMPRISING THERMOPLASTIC MATERIAL SOLES AND METHODS OF USE IN MANUFACTURING SUCH SHOES - Patent application |
| CN109262935B (en) * | 2018-09-12 | 2021-07-20 | 广东昂斯新材料技术有限公司 | Foaming injection molding system for manufacturing thermoplastic polyurethane soles and shoes |
| CN113068898A (en) * | 2020-01-06 | 2021-07-06 | 广东昂斯新材料技术有限公司 | Thermoplastic polyurethane foamed sole with injection stripe lines and preparation process thereof |
| CN111802744A (en) * | 2020-07-01 | 2020-10-23 | 宏威运动用品制造(张家口)有限公司 | Plastic shoe shell and forming process and using method thereof |
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