CN103102605A - Environmentally-friendly ultralight flame-retardant rubber sole material and manufacturing method thereof - Google Patents
Environmentally-friendly ultralight flame-retardant rubber sole material and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to an environmentally-friendly ultralight flame-retardant rubber sole material and a manufacturing method thereof, and particularly relates to a manufacturing method of footwear product soles with high requirements on light weight and flame retardant property. The environmentally-friendly ultralight flame-retardant rubber sole material comprises chlorosulfonated polyethylene rubbers, a reinforcing agent, an active agent, a plasticizer, a foaming agent, a synergistic foaming agent, a flame retardant, a synergistic flame retardant, a vulcanizing agent and a vulcanization accelerator. According to the invention, through the screening and optimization of a series of formulas of the reinforcing agent, the plasticizer, the vulcanizing agent, the foaming agent, the synergistic foaming agent and the synergistic flame retardant, an ultralight flame-retardant sole material with a relative density of 0.3-0.5 g/cm3 is prepared, wherein in a flame retardant property test, the limit oxygen index of the sole material is greater than or equal to 34.5%, and the UL-94 reaches level V-a. The material has the following advantages: soles are lighter in weight and excellent in flame retardant property, and abandoned soles do not release toxic nitrosamine, polybrominated dibenzo-p-dioxins (PBDD) and polybrominated diphenyl furans (PBDF) in the process of burning.
Description
(1) technical field
The present invention relates to the ultralight flame retardant rubber material for sole of shoe of a kind of environment-friendly type and manufacture method thereof.This material is applicable to lightweight, flame retardant properties are required all higher footwear.
(2) background technology
There is following shortcoming in the sole of high temperature resistant brogan in the market: 1. the package stability of body material chloroprene rubber is poor, the easy crystal hardened of low temperature.The rubber storage-life is shorter, half a year to one year, is unfavorable for preserving; 2. sole not only heavily but also hard, relative density is up to 1.2～1.4g/cm
3, easily produce medicine; 3. fire retardant used is decabromodiphynly oxide and antimonous oxide, easily produce carinogenicity many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF) under high temperature and combustion conditions, serious environment pollution threatens human health, does not meet international relevant environmental requirement.
201110203118.0 adopted in patent take chlorosulfonated polyethylene rubber as main ingredient, and adopted vulcanization system, foaming system, the flame-retardant system of environment-friendly type, preparing relative density is 0.8～1.0g/cm
3, the maximum heat rate of release≤110KW/m of taper calorimeter test
2, DIN abrasion≤120mm
3Light flame-retardant footwear soling materials.Yet the foam material of the flame retardant properties for preparing in this patent and wear resisting property excellence still belongs to little foaming, and sole is still heavier, and relative density is 0.8～1.0g/cm
3Usually, for flame-retardant expanded polymer materials, the relative relative density of material is less, and flame retardant properties is poorer.The material for sole of shoe that how to prepare lightweight more, flame retardant properties excellence becomes the challenge that the investigator of shoe-making field faces.
(3) summary of the invention
The present invention aims to provide the ultralight flame retardant rubber material for sole of shoe of a kind of environment-friendly type and manufacture method thereof.In order to realize the foregoing invention purpose, the invention provides following technical scheme: the ultralight flame retardant rubber material for sole of shoe of a kind of environment-friendly type, its component and mass ratio are:
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that strengthening agent is precipitator method hydrated SiO 2, claims again white carbon black.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that promoting agent is at least a in glycol ether (DEG), polyoxyethylene glycol (PEG), trihydroxy methyl ethane, zinc oxide (ZnO).
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type, it is characterized in that main foaming agent is Cellmic C 121 (blowing agent AC), 4,4 '-two phenylhydrazines (whipping agent OBSH) of oxo, N, at least a in N-dinitrosopentamethylene tetramine (blowing agent H).Described foaming synergist is at least a in sodium bicarbonate, inferior ammonium nitrate.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that main flame retardant is at least a in TDE (DBDPE), brominated polystyrene, microcapsule red phosphorus.Described fire retarding synergist is at least a in antimonous oxide, low-hydrate zinc borate, chlorinated paraffin-70, aluminium hydroxide.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that softening agent is at least a in naphthenic oil, paraffin oil, resin of plastification, dioctyl sebacate, trioctyl trimellitate.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that vulcanizing agent is two or more at least composition in magnesium oxide (MgO), tetramethylolmethane (PER), sulphur (S), the different phenylpropyl alcohol of peroxidation two (DCP), cyanacrylate (TAIC), epoxy resin.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type, it is characterized in that vulcanization aid be 2,2 '-dithio-bis-benzothiazole (DM), vulkacit D (DPG, D), tetramethylthiuram monosulfide (TMTM, TS), 2-benzothiazolyl mercaptan (MBT, M), tetramethyl-thiuram disulfide (TMTD, TT) in two or more at least compositions.
The ultralight flame retardant rubber material for sole of shoe of described a kind of environment-friendly type is characterized in that physical antioxidant is at least a in Microcrystalline Wax, antifog wax; Chemical antiager is N, at least a in N-nickel dibutyl dithiocarbamate (NBC), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), 2 mercapto benzimidazole (MB).
The ultralight flame retardant rubber material for sole of shoe of a kind of environment-friendly type of the present invention, its order of addition(of ingredients) and preparation technology are as follows:
(1) order of addition(of ingredients): 1. add chlorosulfonated polyethylene rubber; 2. add Zinic stearas and anti-aging agent; 3. add strengthening agent; 4. add promoting agent; 5. add whipping agent, fire retardant; 6. add softening agent; 7. add vulcanization accelerator and vulcanizing agent.
(2) preparation technology: the chlorosulfonated polyethylene rubber in above-mentioned weight proportion is plasticated with mill in 45～55 ℃ of scopes, the roll spacing of mill is adjusted into 1～2mm, when sizing material bag roller and when being translucent, disposable Zinic stearas and the anti-aging agent of adding, mixing 3～5min makes it Uniform Dispersion, and the roller temperature control is in 55～65 ℃ of scopes; Then two roller spacings are adjusted into 3～4mm, add successively strengthening agent, promoting agent, fire retardant, softening agent, whipping agent, vulcanization accelerator by above-mentioned order of addition(of ingredients), add at last vulcanizing agent, the roller temperature control is in 55～65 ℃ of scopes; The adjustment roll spacing is 0.5～1mm, thin-pass 3～5 times, various auxiliary agents are uniformly dispersed, the roller temperature still is controlled in 55～65 ℃ of scopes, and whole mixing process is controlled in 20～30min, at last roll spacing is adjusted into 1mm, thick logical 2～3 slices, and at room temperature park 24h, and carry out at last the molded vulcanization foaming on vulcanizing press, prepare the ultralight flame retardant rubber sole of environmental protection.
The present invention has mainly prepared the ultralight flame retardant rubber material for sole of shoe of a series of environment-friendly types, sees embodiment 1～7 for details.The ultralight flame retardant rubber material for sole of shoe of this environment-friendly type has following advantage: (1) lightweight more, the relative density of fire retardant material are 0.3～0.5g/cm
3(2) flame retardant properties is excellent; (3) do not discharge poisonous nitrosamine, many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF) after shoes are discarded when burning, meet the regulations of the relevant dioxin of Germany and the regulation of EPA.
The present invention can adopt mill, Banbury mixer to carry out blend, adopts the method processing such as injection moulding, mold pressing, notes pressure, and its Application Areas relates to all kinds of rubber items such as sole, sealing-ring.
(4) embodiment
Embodiment 1:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2.0 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 540s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 1.244g/cm with the moulding sample
3, hardness (Shao C) 69.4; Testing its tensile strength by GB/T1040 is 26.48MPa, and elongation at break is 558%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 59.4N/mm.
Embodiment 2:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, AC10 part, 8 parts of sodium bicarbonates, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2.0 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 403s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.443g/cm with the moulding sample
3, hardness (Shao C) 43.8; Testing its tensile strength by GB/T1040 is 6.0MPa, and elongation at break is 465%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 15.4N/mm.
Embodiment 3:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, AC10 part, 12 parts of sodium bicarbonates, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 420s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.379g/cm with the moulding sample
3, hardness (Shao C) 35.0; Testing its tensile strength by GB/T1040 is 5.0MPa, and elongation at break is 488%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 12.7N/mm.Recording percentage of open area by the method B in ASTM D2856 standard is 32.1%.The burning grade that records material through UL-94 reaches the V-0 level.
Embodiment 4:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, AC10 part, 16 parts of sodium bicarbonates, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 397s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.363g/cm with the moulding sample
3, hardness (Shao C) 39.0; Testing its tensile strength by GB/T1040 is 4.5MPa, and elongation at break is 449%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 11.2N/mm.
Embodiment 5:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, PEG3.0 part, AC10 part, 12 parts of sodium bicarbonates, DBDPE35 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 457s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.372g/cm with the moulding sample
3, hardness (Shao C) 35.6; Testing its tensile strength by GB/T1040 is 4.9MPa, and elongation at break is 404%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 11.5N/mm.The burning grade that draws material through the UL-94 test reaches the V-0 level; The limiting oxygen index(LOI) that records material by ASTM D2863 standard is 34.5%.
Embodiment 6:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, AC10 part, 12 parts of sodium bicarbonates, DBDPE35 part, ZB233510 part, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 450s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.342g/cm with the moulding sample
3, hardness (Shao C) 33.0; Testing its tensile strength by GB/T1040 is 4.1MPa, and elongation at break is 359%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 8.6N/mm.The burning grade that records material through UL-94 reaches the V-0 level; The limiting oxygen index(LOI) that records material by ASTM D2863 standard is 36.0%.
Embodiment 7:
Forming (mass ratio) is: CSM100 part, 10 parts of white carbon blacks, AC10 part, 12 parts of sodium bicarbonates, DBDPE35 part, ZB233515 part, PEG3.0 part, TOTM5.0 part, 5.0 parts, magnesium oxide, TAIC0.5 part, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 2 parts, sulphur, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By the said ratio weighing, mixing by above-mentioned technique, through shaking disc type without the technique sulfurizing time t of rotor vulkameter test rubber unvulcanizate at 160 ℃
90Be 465s, then compression molding under 160 ℃ of conditions.After placing 24 hours under room temperature (25 ℃ of left and right) condition, testing its relative density is 0.340g/cm with the moulding sample
3, hardness (Shao C) 31.8; Testing its tensile strength by GB/T1040 is 3.8MPa, and elongation at break is 359%; Angle tear strength by GB/T3903.12-2005 test cross-linked rubber is 8.7N/mm.The burning grade that records material through UL-94 reaches the V-0 level; The limiting oxygen index(LOI) that records material by ASTM D2863 standard is 35.6%.
Embodiment 1 and 2 adds the relative density of material after whipping agent by 1.244g/cm more as can be known in system
3Drop to 0.379g/cm
3, tensile strength, angle tear strength and elongation at break descend with the increase of foaming agent consumption; Embodiment 2-4 more as can be known, when the AC consumption was constant, along with the increase of sodium bicarbonate consumption, the material relative density was by 0.443g/cm
3Drop to 0.379g/cm
3, 0.363g/cm
3
Embodiment 3 and embodiment 5 add fire retardant DBDPE more as can be known in system, the relative relative density of material is by 0.379g/cm
3Become 0.372g/cm
3, limiting oxygen index(LOI) increases to 34.5% by 28.1%, and tensile strength, angle tear strength and elongation at break slightly descend.This shows, add the relative relative density of fire retardant post-foaming material not only not increase, slightly reduce on the contrary, this is favourable to obtaining high light-weighted flame-retardant expanded elastomeric material.
Embodiment 5～7 adds fire retarding synergist ZB2335 more as can be known in system, the relative density of material is by 0.372g/cm
3Drop to 0.342g/cm
3, 0.340g/cm
3, limiting oxygen index(LOI) increases to 36%, 35.6% by 34.5%, and tensile strength, angle tear strength and elongation at break change little.This shows, add the relative relative density of fire retarding synergist post-foaming material not only not increase, have significantly on the contrary to reduce, this is highly beneficial to obtaining ultralight flame-retardant expanded elastomeric material.There is optimum amount in fire retarding synergist ZB2335 in system, adds too much, and flame retardant properties begins to descend.
In the present invention, the ultralight flame retardant rubber material for sole of shoe of environment-friendly type of embodiment 5～7 preparations has following advantage: proportion is less, and relative density is at 0.3～0.5g/cm
3Between; Flame retardant properties is excellent, and limiting oxygen index(LOI) 〉=34.5%, UL-94 reach the V-0 level; Do not discharge poisonous nitrosamine, many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF) after shoes are discarded when burning, meet the regulations of the relevant dioxin of Germany and the regulation of EPA.
In sum, the ultralight flame retardant rubber material for sole of shoe of environment-friendly type that the present invention is prepared, but the market competitiveness of improving product has good Social benefit and economic benefit, and good development prospect is arranged.
The present invention's starting material used are commercial prod.In the present invention, chlorosulfonated polyethylene rubber (CSM) used is company of Du Pont (Dupont) product, and the trade mark is H-40.
The vertical combustion that the present invention carries out (UL-94) tester test condition and testing tool title, model details are as follows:
(1) sample size: long 125 ± 5mm, wide 13.0 ± 0.5mm, maximum ga(u)ge is less than 13mm.
(2) instrument title: UL-94 horizontal/vertical flame tester, model: CZF-3, manufacturer: Jiangning, Nanjing analytical instrument factory;
The limiting oxygen index(LOI) tester test condition that the present invention carries out and testing tool title, model details are as follows:
(1) sample size: long 80～150mm, wide 10 ± 0.5mm, thick 10 ± 0.5mm;
(2) instrument title: limiting oxygen index(LOI) tester, model: JF-3, manufacturer: Jiangning, Nanjing analytical instrument factory.
Claims (2)
1. ultralight flame retardant rubber material for sole of shoe of environment-friendly type is characterized in that its component and mass ratio are:
Wherein, described strengthening agent is precipitator method hydrated SiO 2, claims again white carbon black or white cigarette; Described promoting agent is at least a in glycol ether, polyoxyethylene glycol, trihydroxy methyl ethane; Described main foaming agent be Cellmic C 121,4,4 '-two phenylhydrazines of oxo, N, at least a in the N-dinitrosopentamethylene tetramine; Described synergistic whipping agent is at least a in sodium bicarbonate, inferior ammonium nitrate; Described main flame retardant is at least a in TDE, brominated polystyrene, microcapsule red phosphorus; Described synergistic flame retardant is at least a in antimonous oxide, low-hydrate zinc borate, chlorinated paraffin-70, aluminium hydroxide; Described softening agent is at least a in naphthenic oil, paraffin oil, resin of plastification, dioctyl sebacate, trioctyl trimellitate; Described vulcanizing agent is two or more at least composition in magnesium oxide, sulphur, the different phenylpropyl alcohol of peroxidation two, cyanacrylate, epoxy resin; Described vulcanization aid is 2,2 '-dithio-bis-benzothiazole, vulkacit D, tetramethylthiuram monosulfide, 2-benzothiazolyl mercaptan, tetramethyl-thiuram disulfide in two or more at least compositions.
2. the ultralight flame retardant rubber material for sole of shoe of a kind of environment-friendly type as claimed in claim 1, is characterized in that its preparation method is as follows: (1) order of addition(of ingredients): 1. add chlorosulfonated polyethylene rubber; 2. add Zinic stearas and anti-aging agent; 3. add strengthening agent; 4. add promoting agent; 5. add whipping agent, fire retardant; 6. add softening agent; 7. add vulcanization accelerator and vulcanizing agent; (2) preparation technology: the chlorosulfonated polyethylene rubber in above-mentioned weight proportion is plasticated with mill in 45～55 ℃ of scopes, the roll spacing of mill is adjusted into 1～2mm, when sizing material bag roller and when being translucent, disposable Zinic stearas and the anti-aging agent of adding, mixing 3～5min makes it Uniform Dispersion, and the roller temperature control is in 55～65 ℃ of scopes; Then two roller spacings are adjusted into 3～4mm, add successively strengthening agent, promoting agent, fire retardant, softening agent, whipping agent, vulcanization accelerator by above-mentioned order of addition(of ingredients), add at last vulcanizing agent, the roller temperature control is in 55～65 ℃ of scopes; The adjustment roll spacing is 0.5～1mm, thin-pass 3～5 times, various auxiliary agents are uniformly dispersed, the roller temperature still is controlled in 55～65 ℃ of scopes, and whole mixing process is controlled in 20～30min, at last roll spacing is adjusted into 1mm, thick logical 2～3 slices, and at room temperature park 24h, and carry out at last the molded vulcanization foaming on vulcanizing press, prepare the ultralight flame retardant rubber sole of environmental protection.
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| CN103497366A (en) * | 2013-10-11 | 2014-01-08 | 昆山纯柏精密五金有限公司 | Environment-friendly flame retardant rubber for soles and preparation method thereof |
| CN103758925A (en) * | 2014-01-21 | 2014-04-30 | 宁波裕江特种胶带有限公司 | Chlorosulfonated polyethylene automobile synchronous belt and manufacturing method thereof |
| CN103819828A (en) * | 2014-03-11 | 2014-05-28 | 浙江久运车辆部件有限公司 | Chlorosulfonated polyethylene rubber material and preparing method thereof for hydraulic oil pipe of harvester |
| CN103960816A (en) * | 2014-05-22 | 2014-08-06 | 浙江润阳新材料科技有限公司 | Shoe sole used for diabetic patient and slipper made of shoe sole |
| CN104140575A (en) * | 2014-08-10 | 2014-11-12 | 宁国市宁盛橡塑制品有限公司 | Wear-resistant shock-absorbing foaming rubber material |
| CN104945756A (en) * | 2015-07-09 | 2015-09-30 | 苏子滩 | Foaming sole material and preparation method thereof |
| CN105482184A (en) * | 2015-12-30 | 2016-04-13 | 张桂华 | Good rubber formula and preparation method thereof |
| CN107200946A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of chlorosulfonated polyethylene microcellular foam material and preparation method thereof |
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| CN112280114A (en) * | 2020-11-02 | 2021-01-29 | 际华三五三七有限责任公司 | Flame-retardant antistatic rubber substrate rubber and preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497366A (en) * | 2013-10-11 | 2014-01-08 | 昆山纯柏精密五金有限公司 | Environment-friendly flame retardant rubber for soles and preparation method thereof |
| CN103758925A (en) * | 2014-01-21 | 2014-04-30 | 宁波裕江特种胶带有限公司 | Chlorosulfonated polyethylene automobile synchronous belt and manufacturing method thereof |
| CN103819828A (en) * | 2014-03-11 | 2014-05-28 | 浙江久运车辆部件有限公司 | Chlorosulfonated polyethylene rubber material and preparing method thereof for hydraulic oil pipe of harvester |
| CN103960816A (en) * | 2014-05-22 | 2014-08-06 | 浙江润阳新材料科技有限公司 | Shoe sole used for diabetic patient and slipper made of shoe sole |
| CN104140575A (en) * | 2014-08-10 | 2014-11-12 | 宁国市宁盛橡塑制品有限公司 | Wear-resistant shock-absorbing foaming rubber material |
| CN104945756A (en) * | 2015-07-09 | 2015-09-30 | 苏子滩 | Foaming sole material and preparation method thereof |
| CN105482184A (en) * | 2015-12-30 | 2016-04-13 | 张桂华 | Good rubber formula and preparation method thereof |
| CN107200946A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of chlorosulfonated polyethylene microcellular foam material and preparation method thereof |
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Application publication date: 20130515 |