CN103183873A - Ultrahigh-wear-resistant sole material and manufacturing method thereof - Google Patents
Ultrahigh-wear-resistant sole material and manufacturing method thereof Download PDFInfo
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- CN103183873A CN103183873A CN2011104544608A CN201110454460A CN103183873A CN 103183873 A CN103183873 A CN 103183873A CN 2011104544608 A CN2011104544608 A CN 2011104544608A CN 201110454460 A CN201110454460 A CN 201110454460A CN 103183873 A CN103183873 A CN 103183873A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to an ultrahigh-wear-resistant sole material and a manufacturing method thereof. The material is composed of 65-70 parts of ethylene propylene diene monomer, 25-30 parts of melting plastic, 30-40 parts of white carbon black, 5-10 parts of softening oil, 1.5-2 parts of stearic acid, 3-4 parts of polyethylene glycol, 0.5 parts of an antioxidant, 15-20 parts of carbon masterbatch, 4-6 parts of a high-performance wear-resisting agent, 4-5 parts of zinc oxide powder, 1.5-2 parts of dicumyl peroxide, and 5-7 parts of an assistant crosslinking agent. The melting plastic is composed of 10 parts of homopolymer polypropylene 300M, 40 parts of copolymer polypropylene, and 50 parts of ethylene-octene copolymer. The high-performance wear-resisting agent is composed of 28 parts of white carbon black, 72 parts of a silane coupling agent, and 50 parts of silica gel. The material provided by the invention has the advantages of high wear resistance, high elasticity, and light weight. Also, the invention provides a manufacturing method of the high-wear-resistant material. The industrial process is simple, and cost is low.
Description
Technical field
The present invention relates to super wear-resisting material for sole of shoe and manufacture method thereof.
Background technology
At present the main material for sole of shoe that adopts is the TPR(thermoplastic elastomer), EVA, rubber, urethane etc.Wherein, big bottom material mainly adopts rubber (butylbenzene, along fourth, mark glue), has on-slip, advantage such as wear-resisting after these sulfuration finished product use.Adopt in a large number in fields such as athletic shoe sole, playshoes, color make-up footwear, slippers and sandals for domestic many producers at present.But this product also exists when wearing than great, weakness such as color and luster is not distinct, the difficult recycling of starting material, rebound resilience deficiency.In addition, from the angle of synthesized polymer material, polypropylene is lower than the synthetic cost of rubber, and source of supply is also more sufficient.
Modified polypropene foaming material for shoes is at the existing deficiency of rubber soles material and a kind of novel material for shoes of special exploitation.Compare with traditional elastomeric material, its rebound resilience, anti-complications, low-temperature performance are better, wear more comfortable, light.
Summary of the invention
At the defective that exists in the prior art and deficiency, the objective of the invention is to propose a kind of ultrawear-resistant material, have the advantage of high-wear resistance, snappiness, light weight; The present invention simultaneously also proposes a kind of manufacture method of high abrasion resisting material, and commercial run is simple and cost is low.
In order to achieve the above object, the present invention proposes a kind of high abrasion resisting material, include but not limited to the raw material of following weight part composition part:
Terpolymer EP rubber: 65-70 part;
Melting glue: 25-30 part;
White carbon black: 30-40 part;
Softening oil: 5-10 part;
Stearic acid: 1.5-2 part;
Polyethylene glycol: 3-4 part;
Antioxidant: 0.5 part;
Black smoke glue: 15-20 part;
High-performance abrasion-proof agent: 4-6 part;
Zinc white: 4-5 part
Dicumyl peroxide: 1.5-2 part;
Additional crosslinker: 5-7 part.
Wherein melting glue composition part is:
Homo-polypropylene 300M:10 part;
Co-polypropylene: 40 parts;
POE: 50 parts.
Wherein part is formed in the high-performance abrasion-proof agent:
White carbon black: 28 parts;
Silane coupling agent: 72 parts;
Silica gel: 50 parts;
As preferably, the super wear-resisting material for sole of shoe that the present invention proposes includes but not limited to the raw material that following weight part is formed part:
Terpolymer EP rubber: 70 parts;
Melting glue: 30 parts;
White carbon black: 40 parts;
Softening oil: 10 parts;
Stearic acid: 2 parts;
Polyethylene glycol: 4 parts;
Antioxidant: 0.5 part;
Black smoke glue: 20 parts;
High-performance abrasion-proof agent: 6 parts;
Zinc white: 5 parts
Dicumyl peroxide: 2 parts;
Additional crosslinker: 7 parts.
Wherein melting glue is formed part:
Homo-polypropylene 300M:10 part;
Co-polypropylene: 40 parts;
POE: 50 parts.
Wherein part is formed in the high-performance abrasion-proof agent:
White carbon black: 28 parts;
Silane coupling agent: 72 parts;
Silica gel: 50 parts.
The invention allows for a kind of manufacture method of super wear-resisting material for sole of shoe simultaneously, comprising:
Step 1, homo-polypropylene, block copolymerization polypropylene, POE are extruded the blend granulation, make melting glue;
Step 2, high-performance abrasion-proof agent preparation;
Step 3, with step 1,2 gained mixtures and EPDM, high-performance abrasion-proof agent, various processing aid, carry out mixing mixing by specific feeding sequence;
Step 4, mill mix;
Step 5, slice;
Step 6, the gained film is carried out removal moisture drying;
Step 7, film is carried out sulfidization molding.
Embodiment
In the super wear-resisting material for sole of shoe preferred embodiment that the present invention proposes, make the raw material that this super wear-resisting material for sole of shoe can include but not limited to following weight part composition part:
Terpolymer EP rubber: 65-70 part;
Melting glue: 25-30 part;
White carbon black: 30-40 part;
Softening oil: 5-10 part;
Stearic acid: 1.5-2 part;
Polyethylene glycol: 3-4 part;
Antioxidant: 0.5 part;
Black smoke glue: 15-20 part;
High-performance abrasion-proof agent: 4-6 part;
Zinc white: 4-5 part
Dicumyl peroxide: 1.5-2 part;
Additional crosslinker: 5-7 part.
Wherein melting glue is formed part:
10 parts of homo-polypropylene: 300M;
Block copolymerization polypropylene: 40 parts;
POE: 50 parts.
Wherein part is formed in the high-performance abrasion-proof agent:
White carbon black: 28 parts;
Silane coupling agent: 72 parts;
Silica gel: 50 parts.
As preferably, the high-wearing feature material that the present invention proposes includes but not limited to the raw material that following weight part is formed part:
Terpolymer EP rubber: 70 parts;
Melting glue: 30 parts;
White carbon black: 40 parts;
Softening oil: 10 parts;
Stearic acid: 2 parts;
Polyethylene glycol: 4 parts;
Antioxidant: 0.5 part;
Black smoke glue: 20 parts;
High-performance abrasion-proof agent: 6 parts;
Zinc white: 5 parts
Dicumyl peroxide: 2 parts;
Additional crosslinker: 7 parts.
Above-mentioned raw materials can adopt the raw material of following model:
Homo-polypropylene: model 300M refines from good fortune;
Block copolymerization polypropylene: model VM3000 is from the Ai Kesen chemical industry;
Polyolefin elastomer: model 8003 is from DOW Chemical;
Terpolymer EP rubber: model 4010 is from the Mitsui chemical industry;
Organic oxygen compound: model DCP is from the Shanghai Gaoqiao chemical plant;
Additional crosslinker: model TMPTA is from sky, Jiangsu roc chemical industry.
The high-wearing feature material for sole of shoe that the present invention proposes can be realized following technique effect: compare with other material for sole of shoe, this material for sole of shoe has the advantage of high-wear resistance, snappiness and light weight, its material after tested, every performance index are as shown in the table:
Remarks: above-mentioned performance index data are obtained by the test of footwear quality supervision and test center, Fujian Province, numbering 2001-XSW-0059.
The manufacture method preferred embodiment of a kind of high abrasion resisting material that the present invention proposes may further comprise the steps:
Step 1, homo-polypropylene, block copolymerization polypropylene, POE are extruded the blend granulation, make melting glue;
Step 2, high-performance abrasion-proof agent preparation;
Step 3, with step 1,2 gained mixtures and EPDM, high-performance abrasion-proof agent, various processing aid, carry out banburying by specific feeding sequence and mix, use Banbury mixer that step 1,2 gained mixtures were carried out mixing 13 minutes, blanking temperature is 125 ℃;
Material rate is as shown in table 1:
 | Chemical name | Supplier/name of an article | The chemistry name of an article | Percentage ratio of component PHR | Weight percent w/w% |
| Base material (one) | Melting glue | Self-control | 30 | 15.3 | |
| Base material (two) | Terpolymer EP rubber | The Mitsui chemical industry | EPDM | 70 | 35.8 |
| Strengthening agent | White carbon black | Longyan chemical industry | SIO2 | 40 | 20.5 |
| Tenderizer | Naphthenic oil | The Kelamayi, Xinjiang | Fatty oil | 10 | 5.1 |
| Colorant | Black smoke glue | Commercially available | 20 | 10.2 | |
| Antioxidant | Bisphenols | Commercially available | SP1010 | 0.5 | 0.2 |
| Activator | Polyethylene glycol | Commercially available | PEG4000 | 4 | 2.0 |
| Anti-wear agent | The high-efficiency abrasion-proof agent | Self-control | AR | 7 | 3.6 |
| Promotor | Active zinc white | The prosperous chemical industry 1AA of anticlise | ZnO | 5 | 2.6 |
| Bridging agent | The superoxide diisopropylbenzene(DIPB) | The Shanghai Gaoqiao petrochemical industry | DCP | 2 | 1.0 |
| Additional crosslinker | TM | Sky, Jiangsu roc chemical industry | TM | 7 | 3.6 |
| Add up to | 195.5 | 100 |
Step 4, utilize mill to carry out remix 12 minutes, and restraint (0.5 micron of thickness) thin 2 times;
Step 5, section;
Step 6, use dehumidifying heat pump were 64 ℃ of removal moisture drying 2 hours;
Step 7, use molded vulcanization machine temperature are set 165 ℃.
The base material that adopts and the following expression of basic physical properties it:
Table 2
The melting glue of one of formulating of recipe component: being to be carried out melt blendedly after twin screw extruder is heated to molten state (230 ℃ of temperature) by homo-polypropylene, third, ethylene block copolymer (block copolymerization polypropylene) and ethene-three kinds of polymkeric substance of octane alkene copolymerization elasticity (polyolefin elastomer), is to be fusion or mechanical blending.Three kinds of basic multipolymers of this epoxy glue, polar phase seemingly, surface tension is little, and diffusion mutually is moistening easily, be uniformly dispersed, and the raising mechanical property, block copolymerization polypropylene has identical isotatic polypropylene crystallization with Co-polypropylene, and the big geode that polypropylene (CO-PP) is produced is dwindled or is reduced (compatible), and the polypropene blended polymkeric substance of polyolefin elastomer (POE) thermoplastic toughening, tensile strength and compressive strength improve.Described each quality of melting glue is divided 10:40:50 preparation; Because POE and PP blend can obtain littler disperse phase particle diameter and narrower size distribution, the POE particle that disperses is as a large amount of focal point of stress, when being subjected to powerful external impacts, can in PP, cause crazing and shear zone and cladodification, thereby absorb a large amount of striking energys.Simultaneously, stress field phase mutual interference between a large amount of crazings has reduced the stress between crazing, and the toughness amplitude of material promotes in a large number.This POE with irregularly shaped being distributed among the PP such as sheet or strips, being conducive to absorb more energy when shear yielding, thereby the toughness of PP is increased substantially in the PP/Poe system.The phase structure of PP/POE belongs to " sea-island ", and marine facies are PP, and island phase (disperse phase) is POE.The size of disperse phase in the blend, partition ratio are very big for the performance impact of blend.Ethene or ethylene copolymer, its solubility parameter (6-8) are nonpolar or few polarity, the three infinitely mix and with other Synergist S-421 95s such as zinc white, when whipping agent etc. mix, all can disperse, and the existence of distribution good order and condition.
The anti-wear agent of one of formulating of recipe component: be that organic silica gel divides and auxiliary agent 50 quality branch blend in Banbury mixer with 50 quality, being extruded into pellet is (AR) anti-wear agent, the dimethyl silicone oil that auxiliary agent is divided by active silica (SIO2) and 5% quality of 25% mass parts respectively, and the silane coupling agent that 70% quality is divided is formed.The preparation of cross-linked rubber is according to designed prescription, comprises base mateiral terpolymer EP rubber and melting glue optimized choice, and various Synergist S-421 95s are according to the quality weighing of each component and definite technology and carry out sulfidization molding; A kind of elastomeric important performance indexes that the work-ing life of the abrasion resistance of cross-linked rubber and sole goods is closely bound up.In order to increase the wear resistance of polypropylene sole, introduce part high-abrasive material (AR) by particular technology in the material system, improve the wear resisting property of modified polypropene foam material preferably.
AR reagent is made: major ingredient is that organic silica gel (SHO160U) is wear-resisting master batch for 50 parts, 50 parts of auxiliary agents, and in the Banbury mixer blend, extruding pelletization uses.Wherein auxiliary agent is carrier by 25% active SiO2 respectively, 70% silane coupling agent, 5% dimethyl silicone oil.
The wear-resisting mechanism of AR reagent: silane coupling agent contains reactive active group alkoxyl group is combined with the alkane hydroxyl on SiO2 surface, the other end and polymer organic silica gel (SHO160U) form covalent linkage or hydrogen bond, thereby the interface of inorganic materials and organic materials is organically coupled together, become firm network structure, thereby improve the wear resisting property of material.
One of this formulating of recipe component peroxide cross-linking agent:
High-efficiency abrasion-proof agent of the present invention is carrier with silicon rubber, be dimethyl silicone rubber and methyl vinyl silicone rubber, developing structure from above molecular formula finds out, when dimethylsilane contains a spot of vinyl, vinyl group pendant also can participate in reaction and form crosslinking structure, namely run through the cross-linking effect that reticulated structure can improve material greatly mutually with what peroxide cross-linking system formed, thereby improve the antiwear characteristic of material.
One of component EPDM in the present embodiment: for impact property, the low temperature brittleness of improving PP, can mix a certain amount of ethylene-propylene copolymer therein, produce the PP/EPDM blend.The employing of the ethylene propylene rubber of this saturated creep properties (EPDM), utilize mechanically milling processing, it can be fractured into very firm little branch in particle, and little whole system Shen that is distributed to becomes and the dynamic crosslinking method makes and forms cocrystallization between internal elastomeric and the polypropylene by sulphur.The characteristic of this fusion creep makes the richer low rigidity of sole, the characteristic of all bent rich property of highly-flexible.
The TM crosslinking coagent of one of this formulating of recipe component: polypropylene (PP) is that kind of crystal polymer thing is similar to polyethylene, flows hardly below crystalline melt point, and more than the crystalline melt point, its melt viscosity sharply diminishes.Additional crosslinker is the compound of multifunctional group, and its function is ruptured at the radical that prevents polymkeric substance, to improve cross-linking effect, improves the physicals and operation processing characteristics of polymkeric substance.The polymer radical macromole that produces when crosslinked is very unstable, β-cracking takes place easily, and make degradation of polypropylene, generates little branch in polymkeric substance, and viscosity is sharply descended.Fundamentally be difficult to curing molding.Therefore, add the modification of various auxiliary agents, PP melt flow rate (MFR) (MFR) is descended, adopt PP control degradation method, it is constant to make the MFR increase of PP can also keep relative molecular mass to divide, thereby improves flowability, the processing characteristics of PP.
Claims (6)
1. super wear-resisting material for sole of shoe, it is characterized in that: the weight part composition comprises
Terpolymer EP rubber: 65-70 part; Melting glue: 25-30 part;
White carbon black: 30-40 part; Softening oil: 5-10 part;
Stearic acid: 1.5-2 part; Polyethylene glycol: 3-4 part;
Antioxidant: 0.5 part; Black smoke glue: 15-20 part;
High-performance abrasion-proof agent: 4-6 part; Zinc white: 4-5 part
Dicumyl peroxide: 1.5-2 part; Additional crosslinker: 5-7 part;
Wherein melting glue composition part is: homo-polypropylene 300M:10 part; Co-polypropylene: 40 parts; POE: 50 parts;
Wherein part is formed in the high-performance abrasion-proof agent: white carbon black: 28 parts; Silane coupling agent: 72 parts; Silica gel: 50 parts.
2. a kind of super wear-resisting material for sole of shoe according to claim 1 is characterized in that: comprise that following weight part forms part:
Terpolymer EP rubber: 70 parts; Melting glue: 30 parts;
White carbon black: 40 parts; Softening oil: 10 parts;
Stearic acid: 2 parts; Polyethylene glycol: 4 parts;
Antioxidant: 0.5 part; Black smoke glue: 20 parts;
High-performance abrasion-proof agent: 6 parts; Zinc white: 5 parts;
Dicumyl peroxide: 2 parts; Additional crosslinker: 7 parts;
Wherein melting glue is formed part: homo-polypropylene 300M:10 part; Co-polypropylene: 40 parts; POE: 50 parts;
Wherein part is formed in the high-performance abrasion-proof agent:
White carbon black: 28 parts; Silane coupling agent: 72 parts; Silica gel: 50 parts.
3. the manufacture method of a kind of super wear-resisting material for sole of shoe according to claim 1 is characterized in that: may further comprise the steps,
Step 1, homo-polypropylene, block copolymerization polypropylene, POE are extruded the blend granulation, make melting glue;
Step 2, high-performance abrasion-proof agent preparation;
Step 3, with step 1,2 gained mixtures and EPDM, high-performance abrasion-proof agent, various processing aid, carry out mixing mixing by specific feeding sequence;
Step 4, mill mix;
Step 5, slice;
Step 6, the gained film is carried out removal moisture drying;
Step 7, film is carried out sulfidization molding.
4. the manufacture method of a kind of super wear-resisting material for sole of shoe according to claim 3 is characterized in that: the anti-wear agent in the step 2 is that organic silica gel divides and auxiliary agent 50 quality branch blend in Banbury mixer with 50 quality, and being extruded into pellet is the AR anti-wear agent.
5. the manufacture method of a kind of super wear-resisting material for sole of shoe according to claim 4 is characterized in that: the dimethyl silicone oil that auxiliary agent is divided by active silica and 5% quality of 25% mass parts respectively, and the silane coupling agent composition of 70% quality branch.
6. the manufacture method of a kind of super wear-resisting material for sole of shoe according to claim 3, it is characterized in that: melting glue is to be heated to 230 ℃ of molten state temperature by homo-polypropylene, third, ethylene block copolymer and ethene-three kinds of polymkeric substance of octane alkene copolymerization elasticity in twin screw extruder, after carry out melt blendedly, be to be fusion or mechanical blending; Block copolymerization polypropylene has identical isotatic polypropylene crystallization with Co-polypropylene, and the big geode that polypropylene is produced is dwindled or reduced, and the polypropene blended polymkeric substance of polyolefin elastomer thermoplastic toughening, tensile strength and compressive strength improve.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483701A (en) * | 2013-10-11 | 2014-01-01 | 昆山纯柏精密五金有限公司 | Wear-resistant sole material |
| CN104910487A (en) * | 2015-06-01 | 2015-09-16 | 浙江大学 | High-wearability sole material and preparation method thereof |
| CN105273276A (en) * | 2015-11-17 | 2016-01-27 | 永嘉县伟诚橡胶工贸有限公司 | Wear-resisting auxiliary formula for rubber and preparation method thereof |
| CN105670135A (en) * | 2016-03-21 | 2016-06-15 | 苏州越湖海绵复合厂 | Waterproof and abrasion-resistant shoe material and method for preparing same |
| CN106009213A (en) * | 2016-05-30 | 2016-10-12 | 泉州市晋科技术检测有限公司 | Wear resisting agent used for shoes, and preparation method thereof |
| CN107603033A (en) * | 2017-09-19 | 2018-01-19 | 莆田市龙翔鞋业有限公司 | A kind of high transparency ethylene-propylene-diene monomer rubber sole and preparation method thereof |
| CN108359096A (en) * | 2018-03-16 | 2018-08-03 | 厦门汉旭硅材料科技有限公司 | A kind of organic silicon wear resistant cream applied to sole |
| CN108359099A (en) * | 2018-03-16 | 2018-08-03 | 厦门汉旭硅材料科技有限公司 | A kind of organic silicon wear resistant cream and the preparation method and application thereof |
| CN111303541A (en) * | 2018-12-12 | 2020-06-19 | 上海宜珂橡胶科技有限公司 | Wear-resistant rubber particle capable of being formed by injection molding and preparation method and application thereof |
| CN111675836A (en) * | 2020-06-17 | 2020-09-18 | 安踏（中国）有限公司 | Color-changing composite foaming material based on expandable elastomer, and preparation method and application thereof |
| CN112961427A (en) * | 2021-03-30 | 2021-06-15 | 泉州师范学院 | Wear-resisting agent for shoes and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483701A (en) * | 2013-10-11 | 2014-01-01 | 昆山纯柏精密五金有限公司 | Wear-resistant sole material |
| CN104910487A (en) * | 2015-06-01 | 2015-09-16 | 浙江大学 | High-wearability sole material and preparation method thereof |
| CN105273276A (en) * | 2015-11-17 | 2016-01-27 | 永嘉县伟诚橡胶工贸有限公司 | Wear-resisting auxiliary formula for rubber and preparation method thereof |
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| CN106009213A (en) * | 2016-05-30 | 2016-10-12 | 泉州市晋科技术检测有限公司 | Wear resisting agent used for shoes, and preparation method thereof |
| CN107603033A (en) * | 2017-09-19 | 2018-01-19 | 莆田市龙翔鞋业有限公司 | A kind of high transparency ethylene-propylene-diene monomer rubber sole and preparation method thereof |
| CN107603033B (en) * | 2017-09-19 | 2020-08-11 | 莆田市龙翔鞋业有限公司 | High-transparency ethylene propylene diene monomer sole and manufacturing method thereof |
| CN108359096A (en) * | 2018-03-16 | 2018-08-03 | 厦门汉旭硅材料科技有限公司 | A kind of organic silicon wear resistant cream applied to sole |
| CN108359099A (en) * | 2018-03-16 | 2018-08-03 | 厦门汉旭硅材料科技有限公司 | A kind of organic silicon wear resistant cream and the preparation method and application thereof |
| CN111303541A (en) * | 2018-12-12 | 2020-06-19 | 上海宜珂橡胶科技有限公司 | Wear-resistant rubber particle capable of being formed by injection molding and preparation method and application thereof |
| CN111675836A (en) * | 2020-06-17 | 2020-09-18 | 安踏（中国）有限公司 | Color-changing composite foaming material based on expandable elastomer, and preparation method and application thereof |
| CN112961427A (en) * | 2021-03-30 | 2021-06-15 | 泉州师范学院 | Wear-resisting agent for shoes and preparation method and application thereof |
| CN112961427B (en) * | 2021-03-30 | 2023-10-27 | 泉州师范学院 | Wear-resistant agent for shoes and preparation method and application thereof |
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Application publication date: 20130703 |