CN102627846A - Sole material and preparation method thereof - Google Patents
Sole material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sole material. The sole material is characterized in that the sole material is prepared from 50-150 parts of TPU, 10-50 parts of PVC, 10-30 parts of a plasticizer, 3-6 parts of a stabilizer, 2-20 parts of a compatilizer, 0-1 part of a crosslinking agent, 0-50 parts of a filler, and 0-1 part of a lubricant, wherein the compatilizer is one of chlorinated polyethylene and ethylene-vinyl acetate grafted maleic anhydride. According to the invention, after adopting above technical scheme, the compatibility of a blend of the TPU and the PVC is improved, so a problem of bad compatibility of blends treating the TPU as a primary material and the PVC as an auxiliary material in the prior art is solved, thereby the utilization of excellent characteristics of the TPU and the PVC makes the sole material of the invention have the advantages of good wear resistance and low production cost.
Description
Technical field
The present invention relates to field of materials, particularly a kind of material for sole of shoe and preparation method thereof.
Background technology
TPUE (TPU) is as the exotic materials of the forming process property of a kind of snappiness that integrates rubber and plastics, and over-all properties is very excellent; Compare with other thermoplastic elastomer, TPU has the intensity height, and good toughness is wear-resisting; Cold-resistant, oil resistant, acid and alkali-resistance, hydrolysis; Ageing-resistant, excellent properties such as weather, Ginkgo Biloba Leaf Extract, environmental protection be widely used in fields such as industry, automobile industry, shoe industry, electric wire and cable, but TPU also exist the processing temperature narrow range; The forming process difficulty, production cost is high, and hardness is regulated difficulty; Defectives such as thermotolerance is relatively poor, these drawbacks limit further applying of TPU, it is imperative that the physicals of then improving TPU through modification improves processibility and reduces material cost.
PVC is one of common engineering plastics, and it is one of maximum plastic prod of output in the world, and low price is widely used, though have thermoplasticity, water insoluble, gasoline and ethanol, rotproofness is strong, light weight, advantages of high strength; But also there are defectives such as poor heat stability, notched Izod impact strength is low, melt viscosity is big.
China is that the first in the world is produced footwear big country, produces about 5,000,000,000 pairs of footwear per year, accounts for 42% of global footwear output.The traditional material for sole of shoe of China is main with rubber and EVA mainly, though rubber has good abrasion resistance, quality is too heavy, and cost is too high, thereby more and more is out of favour.Though the EVA light weight, wear resisting property is general.In recent years, the tempo at the bottom of China's polyurethane shoe is very fast, and annual growth is more than 12%, but kind is dull, is confined to leather shoes sole and athletic shoe sole basically, and price is higher, generally only is applied to high-grade footwear material.Thereby it is good to develop a kind of wear resistance, light weight, and the material for sole of shoe that production cost is lower becomes the target that many colleges and universities and enterprise are pursued.
The present invention selects TPU and PVC blend; Make TPU/PVC alloy elastomerics; Just be well positioned to meet the requirement of above-mentioned sole material, both kept the various good characteristics of TPU, reduced the cost of material again; Make it to become good material for sole of shoe, and do not find also that at present relevant TPU and PVC blend process the report of material for sole of shoe.
Summary of the invention
The object of the present invention is to provide a kind of wear resistance good, material for sole of shoe that production cost is lower and preparation method thereof.
In order to achieve the above object, technical scheme of the present invention is: a kind of material for sole of shoe, and mainly the preparation of raw material by following weight part forms:
50～100 parts of TPU; 10～50 parts of PVC; 10～30 parts in softening agent; 3～6 parts of stablizers; 2～20 parts of compatilizers; 0～1 part of linking agent; 0～50 part of filler; 0～1 part of lubricant; Above-mentioned compatilizer is a kind of in chlorinatedpolyethylene and the ethylene-vinyl acetate grafted maleic anhydride.
Above-mentioned PVC is that the trade mark is the SG-5 type, and glutinous number is 118～107ml/g, and the K value is 68～66, and mean polymerisation degree is 1135～981 resin-oatmeal.
Above-mentioned TPU is polyester type TPU or polyether-type TPU, and the hardness of above-mentioned TPU is 75 degree～95 degree.
Above-mentioned softening agent is a kind of in fatty acid butyl ester and the triethyl citrate.
The aforementioned stable agent is the mixture of calcium-zinc composite stabilizing agent and barium stearate, and optimum weight part of aforementioned stable agent is 6 parts, and the weight ratio of above-mentioned calcium-zinc composite stabilizing agent and above-mentioned barium stearate is 2: 1.
Optimum weight part of above-mentioned compatilizer is 4 parts.
Above-mentioned linking agent is a Di Cumyl Peroxide 99, and optimum weight part of above-mentioned linking agent is 0.6 part;
Above-mentioned filler comprises a kind of in talcum powder, WHITE CARBON BLACK, ultrawhite calcium carbonate superfine powder, nm-class active calcium carbonate and the surface treatment lime carbonate, and optimum weight part of above-mentioned filler is 20～30 parts; Above-mentioned lubricant is one or both in Triple Pressed Stearic Acid, PE wax, calcium stearate, the Z 150PH.
A kind of preparation method of material for sole of shoe, realize through following steps:
(1) takes by weighing above-mentioned weight part raw material;
(2) the above-mentioned TPU that takes by weighing in the step (1) is dropped into the vacuum drying oven inner drying, drying temperature is 50～80 ℃, and be 5～8 hours time of drying, obtains the TPU particle;
(3) preplasticizing: the above-mentioned PVC that takes by weighing in the step (1), above-mentioned softening agent, aforementioned stable agent, above-mentioned compatilizer, above-mentioned linking agent, above-mentioned filler, above-mentioned lubricant are dropped in the high mixer and mediate at a high speed, obtain the PVC mixture of preplasticizing;
(4) the TPU particle of the PVC mixture of the preplasticizing of step (3) and step (2) was dropped in the high mixer mixed at high speed 6-7 minute, obtain blend;
(5) blend with step (4) drops into extruding pelletization in the twin screw extruder, obtains material for sole of shoe.
In the above-mentioned steps (3): earlier PVC is added the high-speed mixer high speed and mediated 5 minutes; Remove the small amount of moisture among the PVC; When treating that temperature reaches 60 ℃, stablizer, compatilizer, linking agent, filler, lubricant dropped in the high-speed mixer mediate at a high speed, when treating that temperature reaches 80 ℃ softening agent dropped in the high-speed mixer and mediate at a high speed; Discharging when treating that temperature reaches 105 ℃ obtains PVC preformed mixture;
Above-mentioned steps (5) comprising: the temperature of extruding is 150 ℃～230 ℃.
After adopting technique scheme; Because main raw material is TPU; Auxiliary material is PVC, and compatilizer is a kind of in chlorinatedpolyethylene and the ethylene-vinyl acetate grafted maleic anhydride, and wherein a large amount of polarity chlorine atoms in the molecular chain of chlorinatedpolyethylene can form hydrogen bond with the Wasserstoffatoms of amino in the TPU molecular structure; Make to have certain consistency between the two, and the SP of chlorinatedpolyethylene is between TPU and PVC; Simultaneously, the anhydride group in the ethylene-vinyl acetate grafted maleic anhydride can with the ester group generation chemical reaction among the TPU, can strengthen the consistency between the polymkeric substance interface; Then add the wherein a kind of consistency that can improve the blend of TPU and PVC in chlorinatedpolyethylene and the ethylene-vinyl acetate grafted maleic anhydride; Having solved in the prior art with TPU is major ingredient; PVC is the problem of consistency difference of the blend of auxiliary material; It is good to utilize the excellent specific property of TPU and PVC to make material for sole of shoe of the present invention have wear resistance like this, the advantage that production cost is lower.
Embodiment
Specific embodiments more of the present invention below are provided, understand the present invention to help further, but protection scope of the present invention are not limited in these embodiment.
Embodiment one
A kind of material for sole of shoe of the present invention, mainly the preparation of raw material by following weight part forms: the TPU of 50 weight parts (TPUE plastic cement), the PVC of 50 weight parts (SE); The chlorinatedpolyethylene of 4 weight parts; The softening agent of 20 weight parts, the stablizer of 6 weight parts, 0.6 parts by weight of cross-linking agent; 0.2 the lubricant of weight part, the filler of 20 weight parts.
Wherein TPU is a polyether-type, and the hardness of TPU is 75 degree; PVC is that the trade mark is the SG-5 type, and glutinous number is 118～107ml/g, and the K value is 68～66, and mean polymerisation degree is 1135～981 resin-oatmeal; Softening agent is a fatty acid butyl ester; Stablizer is the mixture of calcium-zinc composite stabilizing agent and barium stearate, and the weight ratio of calcium-zinc composite stabilizing agent and barium stearate is 2: 1; Linking agent is a Di Cumyl Peroxide 99; Lubricant is a PE wax; Filler is a surface treatment lime carbonate; This surface treatment lime carbonate is for through lime carbonate that silane treatment is crossed, through lime carbonate that rare earth was handled and a kind of in the lime carbonate that titanic acid ester was handled, and present embodiment is to handle and lime carbonate is example through titanic acid ester with surface treatment lime carbonate.
The preparation method of present embodiment raw material, realize through following steps:
(1) takes by weighing above-mentioned weight part raw material;
(2) TPU that takes by weighing in the step (1) is dropped into the vacuum drying oven inner drying, drying temperature is 50～80 ℃, and be 5～8 hours time of drying, obtains the TPU particle;
(3) preplasticizing:
Earlier PVC being added the high-speed mixer high speed mediated 5 minutes; Remove the small amount of moisture among the PVC; When treating that temperature reaches 60 ℃, stablizer, compatilizer, linking agent, filler, lubricant dropped in the high-speed mixer mediate at a high speed, when treating that temperature reaches 80 ℃ softening agent dropped in the high-speed mixer and mediate at a high speed; Discharging when treating that temperature reaches 105 ℃ obtains PVC preformed mixture;
(4) the TPU particle of the PVC mixture of the preplasticizing of step (3) and step (2) is dropped in the high mixer mixed at high speed 5 minutes, obtain blend;
(5) blend with step (4) drops into extruding pelletization in the twin screw extruder, and the temperature of extruding is 150 ℃～230 ℃.
Detected result data through the prepared material for sole of shoe of above-mentioned steps are as shown in table 1.
Table 1
| Project | Testing standard | Unit | Performance |
| Shore hardness | GB/T531-1992 | SHOREA | 90 |
| Tensile strength | GB/T1040.2-2006 | MPa | 15 |
| Elongation at break | GB/T1040.2-2006 | ％ | 680 |
Beneficial effect of the present invention is following:
(1) because softening agent is fatty acid butyl ester or triethyl citrate, and fatty acid butyl ester or triethyl citrate all are the new green environment protection plastic plasticizer, and be nonpoisonous and tasteless, good with the polyvinyl chloride resin consistency, plasticizing efficiency is high; Simultaneously, stablizer is the mixture of calcium-zinc composite stabilizing agent and barium stearate, and calcium-zinc composite stabilizing agent is a kind of novel nontoxic one package stabilizer, do not have in it contain deleterious restriction heavy metal lead, at a distance from etc., it is nontoxic that material for sole of shoe promptly of the present invention has, the characteristic of environmental protection;
(2) because the mixing and after the preplasticizing process, can obtain PVC properties-correcting agent of PVC and stablizer, compatilizer, linking agent, filler, lubricant and softening agent; Be processing characteristics and the flame retardant properties that the adding of PVC properties-correcting agent can improve TPU, also reduced production cost; Filler adopts mineral filler further to reduce production costs simultaneously;
(3) because compatilizer is a chlorinatedpolyethylene; Wherein a large amount of polarity chlorine atoms in the molecular chain of chlorinatedpolyethylene can form hydrogen bond with the Wasserstoffatoms of amino in the TPU molecular structure; Make to have certain consistency between the two, and the SP of chlorinatedpolyethylene is between TPU and PVC; Then chlorinatedpolyethylene has produced bridge linking effect between TPU and PVC; Improved the consistency of the blend of TPU and PVC; Having solved in the prior art with TPU is major ingredient; PVC is the problem of consistency difference of the blend of auxiliary material, utilizes the excellent specific property of TPU and PVC can improve mechanical properties such as the hardness of material for sole of shoe, tensile strength, elongation at break greatly like this;
(4) simple, the safety of preparation technology of the present invention, condition is easy to control, is easy to realize industriallization and large-scale production;
(5) material for sole of shoe of the present invention have that good thermostability, environmental protection, elasticity are high, tensile strength is big, good toughness, wear-resisting, anti-solvent, characteristic such as fire-retardant.
Embodiment two
A kind of material for sole of shoe of the present invention, its preparation method is identical with embodiment one, and compare its difference with embodiment one and be prescription: this prescription is mainly formed by the preparation of raw material of following weight part: the TPU of 70 weight parts (TPUE plastic cement); The PVC of 30 weight parts (SE); The softening agent of 20 weight parts, the ethylene-vinyl acetate grafted maleic anhydride of 4 weight parts, the stablizer of 6 weight parts; 0.3 the lubricant of weight part, the filler of 30 weight parts.
Wherein TPU is a polyester type, and the hardness of TPU is 85 degree; The trade mark of PVC is the SG-5 type, and glutinous number is 118～107ml/g, and the K value is 68～66, and mean polymerisation degree is 1135～981 resin-oatmeal; Softening agent is a triethyl citrate; Stablizer is the mixture of calcium-zinc composite stabilizing agent and barium stearate, and the weight ratio of calcium-zinc composite stabilizing agent and barium stearate is 2: 1; Lubricant is a Triple Pressed Stearic Acid; Filler is a nm-class active calcium carbonate.
The material for sole of shoe of present embodiment; Because compatilizer is the ethylene-vinyl acetate grafted maleic anhydride; Anhydride group in this ethylene-vinyl acetate grafted maleic anhydride can with the ester group generation chemical reaction among the TPU; Between TPU and PVC, having produced bridge linking effect, strengthened the consistency between TPU and the PVC polymkeric substance interface like this, is major ingredient thereby solved in the prior art with TPU; PVC is the problem of consistency difference of the blend of auxiliary material, utilizes the excellent specific property of TPU and PVC can improve mechanical properties such as the hardness of material for sole of shoe, tensile strength, elongation at break greatly like this.
The test result data of the material for sole of shoe of present embodiment two gained is as shown in table 2.
Table 2
| Project | Testing standard | Unit | Performance |
| Shore hardness | GB/T531-1992 | SHOREA | 95 |
| Tensile strength | GB/T1040.2-2006 | MPa | 25 |
| Elongation at break | GB/T1040.2-2006 | ％ | 1000 |
Among the present invention, filler can be by talcum powder, WHITE CARBON BLACK, ultrawhite calcium carbonate superfine powder, through lime carbonate that silane treatment is crossed and a kind of lime carbonate that substitutes nm-class active calcium carbonate and handled through titanic acid ester in the lime carbonate that rare earth was handled; The filling effect of the lime carbonate of wherein handling through titanic acid ester is superior to lime carbonate of crossing through silane treatment and the lime carbonate of handling through rare earth, and the WHITE CARBON BLACK filling effect is superior to talcum powder, ultrawhite calcium carbonate superfine powder, nm-class active calcium carbonate.
Among the present invention, lubricant also can be come for low Triple Pressed Stearic Acid or PE wax by in calcium stearate, the Z 150PH one or both.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. material for sole of shoe is characterized in that mainly being formed by the preparation of raw material of following weight part:
50～100 parts of TPU; 10～50 parts of PVC; 10～30 parts in softening agent; 3～6 parts of stablizers; 2～20 parts of compatilizers; 0～1 part of linking agent; 0～50 part of filler; 0～1 part of lubricant; Above-mentioned compatilizer is a kind of in chlorinatedpolyethylene and the ethylene-vinyl acetate grafted maleic anhydride.
2. a kind of material for sole of shoe according to claim 1 is characterized in that: above-mentioned PVC is that the trade mark is the SG-5 type, and glutinous number is 118～107ml/g, and the K value is 68～66, and mean polymerisation degree is 1135～981 resin-oatmeal.
3. a kind of material for sole of shoe according to claim 1 is characterized in that: above-mentioned TPU is polyester type TPU or polyether-type TPU, and the hardness of above-mentioned TPU is 75 degree～95 degree.
4. a kind of material for sole of shoe according to claim 1 is characterized in that: above-mentioned softening agent is a kind of in fatty acid butyl ester and the triethyl citrate.
5. a kind of material for sole of shoe according to claim 1; It is characterized in that: the aforementioned stable agent is the mixture of calcium-zinc composite stabilizing agent and barium stearate; Optimum weight part of aforementioned stable agent is 6 parts, and the weight ratio of above-mentioned calcium-zinc composite stabilizing agent and above-mentioned barium stearate is 2: 1.
6. a kind of material for sole of shoe according to claim 1 is characterized in that: optimum weight part of above-mentioned compatilizer is 4 parts.
7. a kind of material for sole of shoe according to claim 1 is characterized in that: above-mentioned linking agent is a Di Cumyl Peroxide 99, and optimum weight part of above-mentioned linking agent is 0.6 part; Above-mentioned filler comprises a kind of in talcum powder, WHITE CARBON BLACK, ultrawhite calcium carbonate superfine powder, nm-class active calcium carbonate and the surface treatment lime carbonate, and optimum weight part of above-mentioned filler is 20～30 parts; Above-mentioned lubricant is one or both in Triple Pressed Stearic Acid, PE wax, calcium stearate, the Z 150PH.
8. preparation method like each described material for sole of shoe among the claim 1-7 is characterized in that realizing through following steps:
(1) takes by weighing above-mentioned weight part raw material;
(2) the above-mentioned TPU that takes by weighing in the step (1) is dropped into the vacuum drying oven inner drying, drying temperature is 50～80 ℃, and be 5～8 hours time of drying, obtains the TPU particle;
(3) preplasticizing: the above-mentioned PVC that takes by weighing in the step (1), above-mentioned softening agent, aforementioned stable agent, above-mentioned compatilizer, above-mentioned linking agent, above-mentioned filler, above-mentioned lubricant are dropped in the high mixer and mediate at a high speed, obtain the PVC mixture of preplasticizing;
(4) the TPU particle of the PVC mixture of the preplasticizing of step (3) and step (2) is dropped in the high mixer mixed at high speed 5 minutes, obtain the TPU/PVC blend;
(5) the TPU/PVC blend with step (4) drops into extruding pelletization in the twin screw extruder, obtains material for sole of shoe.
9. the preparation method of the described a kind of material for sole of shoe of claim 8; It is characterized in that: in the above-mentioned steps (3): mediated 4-6 minute carrying out high speed in the above-mentioned PVC adding high-speed mixer earlier; When treating that temperature reaches 55-65 ℃, stablizer, compatilizer, linking agent, filler, lubricant are dropped in the high-speed mixer and mediate at a high speed, treat to add when temperature reaches 75-85 ℃ softening agent and drop in the high-speed mixer; Discharging when temperature reaches 100-110 ℃ obtains PVC preformed mixture..
10. the preparation method of the described a kind of material for sole of shoe of claim 8, it is characterized in that: above-mentioned steps (5) comprising: the temperature of extruding is 150 ℃～230 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898804A (en) * | 2012-09-24 | 2013-01-30 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of high temperature resistant sole material |
| CN103242584A (en) * | 2013-04-27 | 2013-08-14 | 上虞市佳华高分子材料有限公司 | Wear-resistant EVA (Ethylene-Vinyl-Acetate) sole material |
| CN103275480A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU sole material with high polymerization degree |
| CN103275439A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | Ageing-resistant HPVC foaming sole material |
| CN103275478A (en) * | 2013-05-31 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU (Silylated Polyurethane) sole material with antistatic property |
| CN103665720A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for generating and processing hybrid waste plastic net/wire/thread materials and usage method |
| CN104262825A (en) * | 2014-09-04 | 2015-01-07 | 苏州市景荣科技有限公司 | PVC (polyvinyl chloride) foamed shoe sole material with high folding resistance and manufacturing method thereof |
| CN105255156A (en) * | 2015-11-18 | 2016-01-20 | 吴江市风尚鞋厂 | Wear-resisting high-strength PU shoe material and preparation method thereof |
| CN106243370A (en) * | 2016-07-31 | 2016-12-21 | 马爱芬 | A kind of PVC sole shoemaking surface conditioning agent and preparation method thereof and using method |
| CN108047691A (en) * | 2018-01-15 | 2018-05-18 | 苏州晶樱光电科技股份有限公司 | A kind of wear-resistant plastic and manufacture the method for contact wheel in diamond cutting line slicing machine, wire-crossing wheel with it |
| CN108047692A (en) * | 2017-12-14 | 2018-05-18 | 巢湖市新泉鞋帽服饰有限公司 | A kind of ageing-resistant wear-resisting sole and preparation method thereof |
| CN108102241A (en) * | 2017-11-23 | 2018-06-01 | 丁妙严 | TPU, PVC blending formula |
| CN110328902A (en) * | 2019-07-04 | 2019-10-15 | 东莞市中鼎塑料制品有限公司 | A kind of damping, buffering material product of compages |
| CN111004410A (en) * | 2019-12-30 | 2020-04-14 | 揭阳市越兴实业有限公司 | Production process of high-performance plastic shoe composite material |
| CN111873511A (en) * | 2020-07-28 | 2020-11-03 | 泉州鑫泰鞋材有限公司 | Environment-friendly degradable sole forming process |
| CN112239597A (en) * | 2019-07-19 | 2021-01-19 | 施建辉 | Flexible noise reduction pad for dice shaking device of automatic mahjong table |
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| CN101914281A (en) * | 2010-08-03 | 2010-12-15 | 营口巨成教学科技开发有限公司 | Thermoplastic elastomer composition |
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| CN101914281A (en) * | 2010-08-03 | 2010-12-15 | 营口巨成教学科技开发有限公司 | Thermoplastic elastomer composition |
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| CN102898804A (en) * | 2012-09-24 | 2013-01-30 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of high temperature resistant sole material |
| CN103242584A (en) * | 2013-04-27 | 2013-08-14 | 上虞市佳华高分子材料有限公司 | Wear-resistant EVA (Ethylene-Vinyl-Acetate) sole material |
| CN103242584B (en) * | 2013-04-27 | 2015-10-28 | 绍兴佳华高分子材料股份有限公司 | A kind of antiwear EVA shoes bed material |
| CN103275478A (en) * | 2013-05-31 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU (Silylated Polyurethane) sole material with antistatic property |
| CN103275480A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU sole material with high polymerization degree |
| CN103275439A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | Ageing-resistant HPVC foaming sole material |
| CN103665720A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for generating and processing hybrid waste plastic net/wire/thread materials and usage method |
| CN104262825A (en) * | 2014-09-04 | 2015-01-07 | 苏州市景荣科技有限公司 | PVC (polyvinyl chloride) foamed shoe sole material with high folding resistance and manufacturing method thereof |
| CN105255156A (en) * | 2015-11-18 | 2016-01-20 | 吴江市风尚鞋厂 | Wear-resisting high-strength PU shoe material and preparation method thereof |
| CN106243370A (en) * | 2016-07-31 | 2016-12-21 | 马爱芬 | A kind of PVC sole shoemaking surface conditioning agent and preparation method thereof and using method |
| CN106243370B (en) * | 2016-07-31 | 2019-02-15 | 瑞安市霹雳虎鞋业有限公司 | A kind of PVC sole shoemaking surface treating agent and preparation method thereof and application method |
| CN108102241A (en) * | 2017-11-23 | 2018-06-01 | 丁妙严 | TPU, PVC blending formula |
| CN108047692A (en) * | 2017-12-14 | 2018-05-18 | 巢湖市新泉鞋帽服饰有限公司 | A kind of ageing-resistant wear-resisting sole and preparation method thereof |
| CN108047691A (en) * | 2018-01-15 | 2018-05-18 | 苏州晶樱光电科技股份有限公司 | A kind of wear-resistant plastic and manufacture the method for contact wheel in diamond cutting line slicing machine, wire-crossing wheel with it |
| CN110328902A (en) * | 2019-07-04 | 2019-10-15 | 东莞市中鼎塑料制品有限公司 | A kind of damping, buffering material product of compages |
| CN112239597A (en) * | 2019-07-19 | 2021-01-19 | 施建辉 | Flexible noise reduction pad for dice shaking device of automatic mahjong table |
| CN111004410A (en) * | 2019-12-30 | 2020-04-14 | 揭阳市越兴实业有限公司 | Production process of high-performance plastic shoe composite material |
| CN111873511A (en) * | 2020-07-28 | 2020-11-03 | 泉州鑫泰鞋材有限公司 | Environment-friendly degradable sole forming process |
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