CN101864139A - Light-weight wear-resisting thermoplastic elastomer foaming sole material - Google Patents
Light-weight wear-resisting thermoplastic elastomer foaming sole material Download PDFInfo
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- CN101864139A CN101864139A CN200910082104A CN200910082104A CN101864139A CN 101864139 A CN101864139 A CN 101864139A CN 200910082104 A CN200910082104 A CN 200910082104A CN 200910082104 A CN200910082104 A CN 200910082104A CN 101864139 A CN101864139 A CN 101864139A
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Abstract
The invention relates to a sole material, in particular to a thermoplastic elastomer foaming sole material which is added with alpha-methyl styrol copolymer serving as a high foaming resin aid and ultrahigh molecular weight polyethylene (UHMWPE) serving as a macromolecular wear-resisting modifier. The thermoplastic elastomer foaming sole material comprises the following components: styrol-butadiene-styrene block copolymer (SBS), softening oil, alpha-methyl styrol copolymer, UHMWPE, fillings, a parting agent, a foaming agent, a foaming aid and a cross-linking agent. The foaming material with high foaming (the density of the foaming material is between 0.30 and 0.50g/cm<3>) and excellent wear-resisting performance (the length of grinding crack is between 5.0 and 9.0 millimeters) is prepared by adding the UHMWPE and the alpha-methyl styrol copolymer into the SBS, the softening oil, the fillings and the like. In a mixed formula, other components and content are also adjusted, and a preparation process of the foaming material is adjusted and improved; and thus the foaming multiplying power of the sole material and the wear-resisting performance of soles are improved greatly, the production cost is reduced obviously, the environment is protected, and the energy is saved.
Description
(1) technical field
The present invention relates to a kind of material for sole of shoe, especially a kind of thermoplastic elastomer foaming sole material that adds α-Jia Jibenyixigongjuwu and ultrahigh molecular weight polyethylene(UHMWPE).
(2) background technology
Along with the progress of development of science and technology and society, people's standard of living improves constantly, and improves the quality and the performance of all kinds of shoes, allow the wearer more safety and comfort be the ultimate aim and the direction of the development of whole shoe-making industry.According to the literature, every increase by 100 grams of shoes weight, wearer's physical consumption will increase by 1%.In order to reduce physical consumption, to improve snugness of fit, the light weight foam material has become the main direction that material for sole of shoe is developed.
The material that is applicable to sole has rubber, thermoplastic elastomer, plastics etc., wherein adopt the sole of elastomeric material preparation to have advantages such as excellent in abrasion resistance, yet its manufacturing procedure is many, and the waste material of generation can't be recycled; Advantages such as that thermoplastic elastomer has is easy to process, technology is simple, waste material is recyclable, therefore the thermoplastic elastic material application based on styrene-butadiene-styrene block copolymer (SBS) is very extensive.Have good low-temperature, significant elasticity and anti-skid, can not cause advantages such as pin is smelly, and scrap stock can recycle, be the ideal material for sole of shoe.
Yet popular SBS sole mostly is the solid end (density is generally at 1.0g/cm in the market
3About) and (density is at 0.8g/cm to hang down the foaming end
3More than), otherwise its physicals especially wear resisting property severe exacerbation is difficult to reach national footwear with the wear resisting property requirement of stipulating in the outer bottom product standard.The good height foaming SBS material of preparation wear resistance can alleviate product weight, economical with materials, the lifting competitiveness of product in market.
Interim at CN1377905A and " elastomerics " 2002 the 12nd volumes the 3rd, people such as Wu Zhiyong and Liang Hongwen provides invention and the research that SBS (model YH-788) is foamed, in SBS, add Zinic stearas, zinc oxide, polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), naphthenic oil, lime carbonate and Cellmic C 121 (AC) whipping agent etc., be higher than at die head temperature under 180 ℃ the condition and prepare foamed shoe sole, its concrete prescription is as follows:
Prescription 15 parts of 65 parts of 1:SBS, PS, 5 parts of EVA, 15 parts of naphthenic oils, 1.2 parts of AC, 0.8 part of Zinic stearas, 1.2 parts in zinc oxide.
Prescription 15 parts of 65 parts of 2:SBS, PS, 15 parts of EVA, 15 parts of naphthenic oils, 5 parts in lime carbonate, 1.2 parts of AC, 0.8 part of Zinic stearas, 1.2 parts in zinc oxide.
The foaming sole material density that adopts above-mentioned prescription 1 and 2 to prepare respectively is respectively 0.66g/cm
3, 0.78g/cm
3Appoint Xiang in CN1161984A, to provide thermoplastic foaming composition to reach and prepare the method for sole with it, the vinylbenzene matrix high molecular elasticity triblock copolymer of employing anionoid polymerization, PS, activation azodicarbonamide whipping agent etc. are main raw material, and the density of material of preparation is 0.69g/cm
3Yang Fanwen and Dai Lizong etc. provide thermoplastic elastomer foaming material and preparation method thereof in CN1544523A, its composition (mass ratio) is: 40 parts of 100 parts of SBS, PS, 20 parts of EMA, 40 parts of naphthenic oils, 4.0 parts of DNA, 1.0 parts of foam nucleators, 15 parts in lime carbonate, 2.0 parts of Zinic stearass, 0.5 part in oxidation inhibitor.Adopt above-mentioned ratio of components weighing, carry out blend, granulation in screw extrusion press, adopting forcing machine injection molding then is sheet material, and the density of material of preparation is 0.60g/cm
3
In addition, the preparation about super wear resistance SBS material for sole of shoe also has report.Yang Fanwen provides a kind of preparation method of super wear-resisting SBS material for sole of shoe in CN1454928.Its composition (mass ratio) is: 25 parts of 100 parts of SBS, PS, 5 parts in lime carbonate, 0 part of silica 1,15 parts of naphthenic oils, 50 parts of UHMWPE, 2.0 parts of Zinic stearass, 3.5 parts of antioxidant 1076s, 10104.5 parts of thermo-stabilizers, 3.5 parts of photostabilizers, AC whipping agent 1.0.By the said ratio weighing, the employing mixing machine goes out to carry out blend, granulation, drying, injection moulding machine injection molding then in machine or the Banbury mixer at the screw rod machine after being pre-mixed evenly.Prepared sole wear resisting property test result is polishing scratch length 5.3mm.
There are following deficiency in foregoing invention and research: 1) about the research of light weight SBS foam material, the least density of foam material is 0.60g/cm
3, so big proportion has limited its range of application.As the end in slippers and sandal sole, the sports shoes and the interior end.2) about the research of super wear-resisting SBS material for sole of shoe,, in system, introduced too much UHMWPE (50 parts), can reduce SBS foam material " feel " like this in order to improve its wear resisting property.3) above-mentioned research has unicity, the tool light weight, does not wear-resistingly appear in the newspapers for the SBS foam material of one.
(3) summary of the invention
The present invention is directed to the shortcoming of existing SBS foam material, aim to provide a kind of light weight, wear resisting property is good, production cost is low, the thermoplastic elastic body shoe bottom material of environmental protection, save energy and preparation method thereof.
The component of the said thermoplastic elastomer foaming material of the present invention and content (mass ratio) are:
Styrene-butadiene-styrene block copolymer (SBS) 100
Softening oil 10～45
Filler 0～40
High foaming resin additive 1～35
High molecular abrasion-proof properties-correcting agent 1～35
Releasing agent 0.5～2.0
Whipping agent 0～2
Foamed promoter 0～5
Linking agent 0～3
The styrene-butadiene block copolymer that the present invention adopts is styrene-butadiene-styrene triblock copolymer (SBS), and its molecular structure is a hub-and-spoke configuration.
The whipping agent that the present invention adopts is the composition of Cellmic C 121 (AC) or AC and inorganic foaming agent, and inorganic foaming agent can be selected sodium bicarbonate for use, perhaps its modifier.
The said foamed promoter of the present invention is a zinc oxide.
The filler that the present invention adopts can be selected at least a in lime carbonate, talcum powder, silicon-dioxide, the wollastonite for use.Here said softening oil is a naphthenic oil.Said releasing agent adopts at least a in Zinic stearas, calcium stearate or the Magnesium Stearate.Said linking agent is at least a in dicumyl peroxide (DCP) or the benzoyl peroxide (BPO).
Said high molecular abrasion-proof properties-correcting agent is ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), and molecular weight is 100～8,000,000.
Said high foaming resin additive is at least a in α-Jia Jibenyixigongjuwu, divinyl-(alpha-methyl styrene) multipolymer.
The present invention can also add this area other processing aids commonly used, as pigment, photostabilizer etc.
The said thermoplastic elastomer foaming material preparation method of the present invention is: adopt two kinds of preparation technologies, i) single stage method: SBS is earlier fully oil-filled, tablet forming in mill, add UHMWPE, high foaming resin additive, whipping agent, frothing aid, linking agent then, after playing the triangle bag and mixing, add filler then, thorough mixing is the back slice evenly, and last moulded from foam makes foam material.Ii) two-step approach: according to the said ratio weighing, adopt high-speed mixer to be pre-mixed evenly, in screw extrusion press, carry out melt blending, granulation then in 110 ℃～150 ℃; Then mixing in mill or Banbury mixer, mold pressing or calendering, the preparation foam material.
Advantage of the present invention: the present invention prepares a kind of light weight (density is 0.30～0.50g/cm by adding a kind of lower molecular weight α-Jia Jibenyixigongjuwu on SBS, softening oil, filler and ultrahigh molecular weight polyethylene(UHMWPE) basis
3), the wear resisting property (material for sole of shoe that polishing scratch length 5.0～9.0mm) is good.By reducing the density of foam material, can enlarge the range of application of SBS foam material on the one hand, as be used at the bottom of sandals sole, the sports shoes and the end etc. in the footwear.Can obviously reduce production costs save energy on the other hand.
The present invention can adopt mill, Banbury mixer, forcing machine etc. to carry out blend, granulation.Adopt injection moulding, extrude, method processing such as mold pressing, calendering, its Application Areas relates to sole, tubing and sheet material etc.
(4) embodiment
Embodiment 1:
Forming (mass ratio) is: 100 parts of SBS, 40 parts of naphthenic oils, 15 parts in lime carbonate, 1.5 parts of AC, 3.0 parts in zinc oxide, 1.0 parts of Zinic stearass, 1.0 parts of crosslink agent DCPs.
By the said ratio weighing, the employing mixing machine carries out blend, granulation after being pre-mixed evenly in forcing machine, soak type at 160 ℃～170 ℃ condition counterdie Hair Fixers then, and the density that records foam material is 0.40g/cm
3Sample is pressed its wear resistance of GB/T 3903.2-1994 standard testing after placing 24 hours under 22.0 ℃ of conditions of room temperature, its polishing scratch length is 9.4mm.
Embodiment 2:
Forming (mass ratio) is: 100 parts of SBS, 40 parts of naphthenic oils, high 5 parts of resin additives of foaming, AC1.5 part, 3.0 parts in zinc oxide, 15 parts in lime carbonate, 1.0 parts of Zinic stearass, 1.0 parts of crosslink agent DCPs.
By the said ratio weighing, the employing mixing machine carries out blend, granulation after being pre-mixed evenly at forcing machine or in Banbury mixer, soak type at 150 ℃～170 ℃ condition counterdie Hair Fixers then, and the density that records foam material is 0.21g/cm
3Sample is pressed its wear resistance of GB/T 3903.2-1994 standard testing after placing 24 hours under 22.0 ℃ of conditions of room temperature, its polishing scratch length is 12.7mm.
Embodiment 3～6
The component of desired raw material and content and preparation method see Table 1, and its manufacturing process and embodiment 1,2 are similar.
Table 1
| Component | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| ??SBS | ??100 | ??100 | ??100 | ??100 |
| Naphthenic oil | ??35 | ??35 | ??40 | ??40 |
| ??UHMWPE | ??25 | ??25 | ??25 | ??25 |
| α-Jia Jibenyixigongjuwu | ??5 | ??5 | ??5 | ??5 |
| Component | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Lime carbonate | ??0 | ??0 | ??10 | ??10 |
| Talcum powder | ??15 | ??15 | ??0 | ??0 |
| ??AC | ??1.0 | ??1.0 | ??1.5 | ??1.5 |
| Sodium bicarbonate | ??0.2 | ??0.2 | ??0 | ??0 |
| Zinc oxide | ??2.5 | ??2.5 | ??3.0 | ??3.0 |
| Zinic stearas | ??1.5 | ??1.5 | ??1.0 | ??1.0 |
| Crosslink agent DCP | ??1.0 | ??1.0 | ??1.0 | ??1.0 |
| Processing condition | Single stage method | Two-step approach | Two-step approach | Two-step approach |
| Density (g/cm 3) | ??0.43 | ??0.36 | ??0.30 | ??0.49 |
| Polishing scratch length (mm) | ??7.4 | ??7.6 | ??8.2 | ??5.2 |
Embodiment 1 and embodiment 2 add high foaming resin additive α-Jia Jibenyixigongjuwu more as can be known in the SBS foaming system, can increase substantially the expansion ratio of SBS, and density obviously reduces (from 0.40g/cm
3Be reduced to 0.21g/cm
3).Yet the decline of foam material density causes its wear resisting property severe exacerbation (polishing scratch length is from 9.4mm to 12.7mm).
In order to improve the wear resisting property of material, add high molecular abrasion-proof properties-correcting agent UHMWPE, and adopt two kinds of complete processings to prepare foam material.Can find out with embodiment 4 by comparing embodiment 3, compare, with the easier foam material that obtains the high physicals of high foaming of two-step approach with single stage method.Embodiment 5 and embodiment 1 more as can be seen, by introducing high frothing aid α-Jia Jibenyixigongjuwu and wear-resisting properties-correcting agent UHMWPE simultaneously, (density only is 0.30g/cm to adopt two-step approach to prepare light weight
3), the thermoplastic elastomer foaming material for shoes of wear resisting property good (polishing scratch length 8.2mm), this foam material can be used in slippers and sandal sole, the sports shoes at the end and footwear the end etc.Embodiment 6 prepared material wear-resistant performance excellences (polishing scratch length 5.2mm), its density only is 0.49g/cm
3Under this density, the wear resisting property of this material has reached the wear resisting property (polishing scratch length is less than 7mm) at the bottom of rubber soles and the polyurethane shoe, and price is starkly lower than rubber and polyurethane material, and alternative rubber and polyurethane material are made sole, and its cost performance is higher than rubber and polyurethane material.
Advantage of the present invention is that the wear resisting property of material is significantly improved than general T PR material for sole of shoe, and the density of foam material is well below existing TPR sole simultaneously.This invention prepared light weight, wear-resisting, production cost is low, the thermoplastic elastic body shoe bottom material of recyclable utilization, save energy.
The used starting material of the present invention are commercial prod.The styrene-butadiene-styrene block copolymer (SBS) that the present invention adopts is that petrochemical complex limited-liability company Beijing, Beijing Yanshan Mountain branch office produces, and the trade mark is SBS4402.In addition, the trades mark such as strange U.S. 5302 produced of the YH-788 that produces of Yueyang general petrochemicals factory and Taiwan Qi Mei company also are applicable to the preparation of this material.
Claims (10)
1. light weight wear-resistant thermoplastic elastomer material for sole of shoe is characterized in that its component and mass ratio are:
Styrene-butadiene-styrene block copolymer (SBS) 100
Softening oil 10～45
Filler 0～40
High foaming resin additive 1～35
High molecular abrasion-proof properties-correcting agent 1～35
Releasing agent 0.5～2.0
Whipping agent 0～2
Foamed promoter 0～5
Linking agent 0～3
2. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that filler can select at least a in lime carbonate, talcum powder, silicon-dioxide, the wollastonite for use.
3. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said softening oil can adopt naphthenic oil.
4. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said releasing agent adopts at least a in Zinic stearas, calcium stearate, the Magnesium Stearate.
5. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said linking agent is at least a in dicumyl peroxide (DCP) or the benzoyl peroxide (BPO).
6. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1, it is characterized in that said whipping agent adopts the composition of Cellmic C 121 (AC) or AC and inorganic foaming agent, inorganic foaming agent can be selected sodium bicarbonate for use, perhaps its modifier.
7. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said foamed promoter adopts zinc oxide.
8. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said high molecular abrasion-proof properties-correcting agent is ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE).
9. a kind of light weight wear-resistant thermoplastic elastomer material for sole of shoe as claimed in claim 1 is characterized in that said high foaming resin additive adopts at least a in α-Jia Jibenyixigongjuwu, divinyl-(alpha-methyl styrene) multipolymer.
10. light weight wear-resisting thermoplastic elastomer foaming material preparation method adopts two kinds of preparation technologies, it is characterized in that its preparation process is:
I) single stage method: SBS is earlier fully oil-filled, tablet forming in mill, add UHMWPE, high foaming resin additive, whipping agent, frothing aid, linking agent then, after playing the triangle bag and mixing, add filler then, thorough mixing is the back slice evenly, and last vulcanizing press patrix Hair Fixer infusion gets foam material; Ii) two-step approach: according to the said ratio weighing, adopt high-speed mixer to be pre-mixed evenly after, in screw extrusion press, carry out melt blending, granulation in 110 ℃～150 ℃; Mixing in mill or Banbury mixer, mold pressing or calendering then, the preparation foam material.
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| CN2009100821040A CN101864139B (en) | 2009-04-15 | 2009-04-15 | Light-weight wear-resisting thermoplastic elastomer foaming sole material |
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| CN2009100821040A CN101864139B (en) | 2009-04-15 | 2009-04-15 | Light-weight wear-resisting thermoplastic elastomer foaming sole material |
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| CN103254545A (en) * | 2012-10-16 | 2013-08-21 | 张云鹏 | Thermoplastic composite rubber adding foaming material and preparation method thereof |
| CN103483759A (en) * | 2013-09-24 | 2014-01-01 | 吴江市董鑫塑料包装厂 | SBS shoe plastic |
| CN104231419A (en) * | 2014-10-16 | 2014-12-24 | 中国皮革和制鞋工业研究院 | High shock-absorbing ethylene-vinyl acetate rubber foam material for shoes and preparation method of material |
| CN105295171A (en) * | 2015-10-29 | 2016-02-03 | 安徽省腾越铝塑有限公司 | SBS-modified ultrahigh molecular weight polyethylene composite material |
| CN105331036A (en) * | 2015-12-01 | 2016-02-17 | 吴江市风尚鞋厂 | Wear-resisting anti-static shoe material and preparation method thereof |
| CN105860172A (en) * | 2016-05-25 | 2016-08-17 | 泉州集友鞋业有限公司 | Wear-resistant sole material and preparing method thereof |
| CN106221113A (en) * | 2016-08-18 | 2016-12-14 | 泉州福达纳米科技发展有限公司 | The material for sole of shoe that in rubber pattern, the processing method of expanded material and the method prepare |
| CN106263271A (en) * | 2016-08-31 | 2017-01-04 | 中国皮革和制鞋工业研究院 | Shoe pad and preparation method thereof and the footwear comprising this shoe pad |
| CN107242640A (en) * | 2016-03-11 | 2017-10-13 | 硕数技术国际股份有限公司 | Inner sole |
| CN107698828A (en) * | 2017-10-08 | 2018-02-16 | 界首市旭升塑胶制品有限公司 | A kind of preparation method of the hard sole of wear-resisting height |
| CN109288193A (en) * | 2018-09-28 | 2019-02-01 | 瑞安市军中鞋业有限公司 | A kind of high-risk chemical industry place safety shoe corrosion-resistant high-temperature boots and preparation method thereof |
| CN110326845A (en) * | 2019-08-14 | 2019-10-15 | 安踏（中国）有限公司 | A kind of sole elastomeric material, athletic shoe sole and sport footwear |
| CN112592568A (en) * | 2020-12-15 | 2021-04-02 | 衡阳丰泰鞋业有限公司 | Light-weight high-wear-resistance sports shoe sole material and preparation method thereof |
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| US4503187A (en) * | 1983-12-05 | 1985-03-05 | Mobil Oil Corporation | P-Methylstyrene copolymer blends |
| CN1161984A (en) * | 1996-04-08 | 1997-10-15 | 彰昱实业股份有限公司 | Thermoplastic foaming composition and method for making shoe-sole by using same |
| CN100412130C (en) * | 2003-05-14 | 2008-08-20 | 阳范文 | Ultrahigh wear-resistant thermoplastic elastomer material for shoe-sole |
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| CN103254545A (en) * | 2012-10-16 | 2013-08-21 | 张云鹏 | Thermoplastic composite rubber adding foaming material and preparation method thereof |
| CN103483759A (en) * | 2013-09-24 | 2014-01-01 | 吴江市董鑫塑料包装厂 | SBS shoe plastic |
| CN104231419B (en) * | 2014-10-16 | 2017-07-07 | 中国皮革和制鞋工业研究院 | Damping ethylene vinyl acetate rubber pange material for shoes high and preparation method thereof |
| CN104231419A (en) * | 2014-10-16 | 2014-12-24 | 中国皮革和制鞋工业研究院 | High shock-absorbing ethylene-vinyl acetate rubber foam material for shoes and preparation method of material |
| CN105295171A (en) * | 2015-10-29 | 2016-02-03 | 安徽省腾越铝塑有限公司 | SBS-modified ultrahigh molecular weight polyethylene composite material |
| CN105331036A (en) * | 2015-12-01 | 2016-02-17 | 吴江市风尚鞋厂 | Wear-resisting anti-static shoe material and preparation method thereof |
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| CN107242640A (en) * | 2016-03-11 | 2017-10-13 | 硕数技术国际股份有限公司 | Inner sole |
| CN105860172B (en) * | 2016-05-25 | 2017-12-01 | 泉州集友鞋业有限公司 | A kind of Wear-resistant sole material and preparation method thereof |
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| CN106221113A (en) * | 2016-08-18 | 2016-12-14 | 泉州福达纳米科技发展有限公司 | The material for sole of shoe that in rubber pattern, the processing method of expanded material and the method prepare |
| CN106263271A (en) * | 2016-08-31 | 2017-01-04 | 中国皮革和制鞋工业研究院 | Shoe pad and preparation method thereof and the footwear comprising this shoe pad |
| CN107698828A (en) * | 2017-10-08 | 2018-02-16 | 界首市旭升塑胶制品有限公司 | A kind of preparation method of the hard sole of wear-resisting height |
| CN109288193A (en) * | 2018-09-28 | 2019-02-01 | 瑞安市军中鞋业有限公司 | A kind of high-risk chemical industry place safety shoe corrosion-resistant high-temperature boots and preparation method thereof |
| CN110326845A (en) * | 2019-08-14 | 2019-10-15 | 安踏（中国）有限公司 | A kind of sole elastomeric material, athletic shoe sole and sport footwear |
| CN112592568A (en) * | 2020-12-15 | 2021-04-02 | 衡阳丰泰鞋业有限公司 | Light-weight high-wear-resistance sports shoe sole material and preparation method thereof |
| CN112592568B (en) * | 2020-12-15 | 2022-09-02 | 莆田市城厢区恒鑫鞋材有限公司 | Light-weight high-wear-resistance sports shoe sole material and preparation method thereof |
| CN114031884A (en) * | 2021-10-26 | 2022-02-11 | 中国石油化工股份有限公司 | Cracking-resistant children shoe sole material and preparation method thereof |
| CN114031884B (en) * | 2021-10-26 | 2024-02-23 | 中国石油化工股份有限公司 | Crack-resistant children's shoe sole material and preparation method thereof |
| CN114031886A (en) * | 2021-11-15 | 2022-02-11 | 温州奕诚鞋材有限公司 | Anti-aging sole material and preparation process thereof |
| CN114031886B (en) * | 2021-11-15 | 2023-09-26 | 温州奕诚鞋材有限公司 | Anti-aging sole material and preparation process thereof |
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Application publication date: 20101020 Assignee: Huachuan Macromolecular Material Ltd. Assignor: China Leather and Shoe-making Industry Inst. Contract record no.: 2012990000880 Denomination of invention: Light-weight wear-resisting thermoplastic elastomer foaming sole material Granted publication date: 20120321 License type: Exclusive License Record date: 20121212 |
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