CN110606999A - Rubber for rubber shoe forming clamp and preparation method thereof - Google Patents
Rubber for rubber shoe forming clamp and preparation method thereof Download PDFInfo
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- CN110606999A CN110606999A CN201910926384.2A CN201910926384A CN110606999A CN 110606999 A CN110606999 A CN 110606999A CN 201910926384 A CN201910926384 A CN 201910926384A CN 110606999 A CN110606999 A CN 110606999A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses rubber shoe forming clamp rubber and a preparation method thereof, wherein the rubber shoe forming clamp rubber comprises 40-50 parts of No. 1 standard rubber, 50-60 parts of synthetic rubber, 2.0-2.6 parts of sulfur, 5.5-6.5 parts of an accelerator, 5 parts of nano zinc oxide, 7.4-8.2 parts of polyethylene glycol, 5.6-6.0 parts of an anti-aging agent, 4-5 parts of a homogenized anti-tearing agent, 40-50 parts of white carbon black, 10-12 parts of a wear-resisting agent and 3-5 parts of rubber lubricating oil. The method is simple, and the manufactured product has low cost and good use effect.
Description
Technical Field
The invention relates to rubber and a preparation method thereof, in particular to rubber for a rubber shoe forming clamp and a preparation method thereof.
Background
According to the use requirement, because the bottom plate of the clamp is made of metal, the shoe body can not be clamped due to low friction force in the direct use process, or the cloth cover of the upper is clamped and broken due to the collision between the clamping plate and the shoe tree in the shoe clamping process, the friction in the clamping process is usually realized by fixing the silicon rubber layer on the surface of the metal clamping plate by screws so as to achieve the effect of shoe clamping operation.
However, the service life of the silicon rubber on the surface layer of the splint is short due to low cohesive force, large deformation, small friction force, low wear resistance and the like, and the loosening of screws for fixing the silicon rubber layer is caused by the shaking in the running process of the rubber shoe forming machine, so that the loosened screws are finally generated to crush the upper of a shoe to generate unqualified rubber shoes, and the normal running of production is seriously influenced.
According to the actual production, the rubber layer is urgently needed to cover the running conveying clamping plate of the rubber shoe forming machine so as to replace the silicon rubber layer and achieve the purposes of high use and high quality level.
Disclosure of Invention
The purpose of the invention is: the rubber for the rubber shoe forming clamp and the preparation method thereof have the advantages of excellent friction performance and wear resistance, long service life, capability of meeting the use requirements of no shoe falling, no shoe clamping, no shoe upper crushing, good appearance quality of rubber shoes and the like in the operation of clamping the rubber shoes by the rubber shoe forming machine, and capability of overcoming the defects in the prior art.
The invention is realized by the following steps: the rubber shoe forming clamp rubber comprises, by weight, 40-50 parts of No. 1 standard rubber, 50-60 parts of synthetic rubber, 2.0-2.6 parts of sulfur, 5.5-6.5 parts of an accelerator, 5 parts of nano zinc oxide, 7.4-8.2 parts of polyethylene glycol, 5.6-6.0 parts of an anti-aging agent, 4-5 parts of a homogenized anti-tearing agent, 40-50 parts of white carbon black, 10-12 parts of a wear-resisting agent and 3-5 parts of rubber lubricating oil.
More preferably, the rubber lubricating oil comprises, by weight, 45 parts of No. 1 standard rubber, 55 parts of synthetic rubber, 2.4 parts of sulfur, 6 parts of an accelerator, 7.0 parts of a vulcanization activator, 7.8 parts of polyethylene glycol, 5.8 parts of an anti-aging agent, 4.5 parts of a homogenized anti-tearing agent, 45 parts of white carbon black, 11 parts of an anti-wear agent and 4 parts of rubber lubricating oil.
Each 55 parts of synthetic rubber consists of 44 parts of solution-polymerized styrene-butadiene rubber and 11 parts of butadiene rubber.
Every 7 parts of vulcanization activator comprises 2.0 parts of stearic acid and 5 parts of nano zinc oxide.
Each 6 parts of accelerator consists of 1.6 parts of accelerator DM, 1.1 parts of accelerator D, as well as 1.1 parts of accelerator TMTD and 2.2 parts of catcher CZ.
Every 5.8 parts of the antioxidant consists of 2.3 parts of antioxidant CD, 2.2 parts of antioxidant KY-405L and 1.3 parts of antioxidant RD.
The polyethylene glycol specification is 4000 molecular weight.
The homogenized tear resistance specification is DS-40.
The anti-wear agent specification is DC-Z-B.
Also comprises 0.4-0.5 part of salicylic acid and 1-3 parts of grass green masterbatch.
A method for preparing rubber for a rubber shoe molding clamp,
(1) manufacturing plasticated rubber, namely putting 40-50 parts of No. 1 standard rubber into an internal mixer, pressing for 3-5 min, then flattening a winding drum to obtain semi-finished rubber with the Weishi plasticity of 0.45-0.52, and standing for more than 24 hours to obtain plasticated rubber;
(2) preparing a master batch, namely putting 50-60 parts of synthetic rubber, 2 parts of stearic acid, 4-5 parts of a homogenizing anti-tearing agent, 7.4-8.2 parts of polyethylene glycol and 40-50 parts of white carbon black into an internal mixer, after 5-6 min of pressure refining, lifting an upper top bolt to turn over the rubber material, after 4-5 min of pressure refining is continued, lifting the upper top bolt of the internal mixer to sweep the powdery material overflowing from the internal mixing chamber back to the internal mixing chamber, then pressure refining for 2-4 min, adding 3-5 parts of rubber softening oil, and discharging after 2-4 min of pressure refining; after the internal mixer discharges materials, immediately putting the discharged materials into an open rubber mixing mill with a roll spacing of 4-5 mm, turning over for 8 times, discharging sheets with a thickness of 4-6 mm, cooling the sheets by adopting normal-temperature water, and standing for more than 24 hours to obtain a master batch, wherein the total amount is 118.3 parts;
and (2) manufacturing the mixed rubber, namely putting the plasticated rubber, the intermediate material (namely 5.5-6.5 parts of accelerator, 5 parts of nano zinc oxide, 5.6-6.0 parts of anti-aging agent, 0.4-0.5 part of salicylic acid, 1-3 parts of grass green master batch and 10-12 parts of wear-resisting agent) and the master batch into an internal mixer for pressure refining for 0.5-1 min, adding 118.3 parts of the master batch, pressure refining for 4-5 min, adding 2.0-2.6 parts of sulfur into the pressure refining for 2-3 min, discharging after pressure refining for 25-30 s, immediately putting the discharged rubber material into a discharge type rubber refining machine with a roll spacing of 4-5 mm for cross refining for 4-6 times, discharging the rubber sheet with a thickness of 4-6 mm, cooling the rubber sheet by using normal temperature water, standing for more than 24 hours to obtain mixed rubber, and inspecting the mixed rubber to obtain a finished product. Wherein the medium materials are accelerator, vulcanization activator, anti-aging agent, wear-resisting agent and salicylic acid. The test indexes of the rubber compound are that the Wei's plasticity of the rubber compound is 0.45-0.55, the Shore hardness is 65-70 degrees, the specific gravity is 1.20 +/-0.02, and the vulcanization starting point at 143 ℃ is 2' 40-3 ' 00.
Uniformly hot-refining the mixed rubber at 40-60 ℃, and cutting into rubber blank sheets in required shapes; then brushing gasoline adhesive cement on the adhesive surface of the rubber stock blank, drying, adhering the rubber stock blank on a core plate of a clamp firmly, and vulcanizing the rubber stock blank in a rubber shoe steam pot under the vulcanization process condition to prepare a rubber shoe molding rubber clamp which is used for clamping and conveying semi-finished rubber shoes in the rubber shoe molding process.
The ingredients are combined with each other, so that the ingredients have positive effects on the product performance, and the method comprises the following steps:
TABLE 1
As shown in table 1, the optimal ratio of the raw rubber to the filling system is as follows: 45 parts of No. 1 standard rubber, 55 parts of synthetic rubber (consisting of 44 parts of butadiene styrene rubber and 11 parts of butadiene rubber), 45 parts of white carbon black, 7.8 parts of polyethylene glycol, 11 parts of wear-resistant agent DC-Z-B, 4 parts of rubber lubricating oil and 4.5 parts of homogenized anti-tearing agent.
TABLE 2
Table 2 shows the following optimum amounts of complexing agents: 2.4 parts of sulfur, 6 parts of accelerator, 7 parts of vulcanization activator, 5.8 parts of anti-aging agent and 0.45 part of salicylic acid.
2) By adopting a novel combined system of 'accelerator DM, accelerator D, accelerator CZ and accelerator TMTD', the rigidity of rubber molecule cross-linking bonds is improved, and excellent wear resistance is provided.
TABLE 3
The optimum amounts of the vulcanization system and the active system are given in table 3: 1.6 parts of accelerator DM, 1.1 parts of accelerator D, 2.2 parts of accelerator CZ, 1.1 parts of accelerator TMTD, 2 parts of nano zinc oxide and 2 parts of stearic acid. The rubber combination property is best under the system condition.
3) The plasticated rubber with the Wei's plasticity of 0.25-0.32 is used, and the high-wear-resistance carbon black and the argil are used as the wear-resistance reinforcing agent, so that the optimal physical and mechanical properties and technological properties are obtained.
TABLE 4
Table 4 shows that the Wei plasticity of the plasticated rubber is controlled to be 0.45-0.52, and the comprehensive physical properties of the rubber are optimal.
4) Relationship between plasticity and rubber performance of rubber compound
TABLE 5
Table 5 shows that the plasticity of the rubber compound is 0.40-0.45, and the physical property and the technological property of the obtained rubber compound are optimal.
5) Age resister and colorant amount test
TABLE 5
6) Table 5 shows that the optimum values for the amounts of anti-aging agent and colorant are: 2.3 parts of age inhibitor CD, 2.2 parts of age inhibitor KY-405L, 1.3 parts of age inhibitor RD and 2 parts of grass green masterbatch, so as to ensure the best color, the longest service time and the best flatting effect.
Due to the adoption of the technical scheme, compared with the prior art, the rubber shoe forming clamp rubber has the advantages that the formula and the preparation method of the rubber shoe forming clamp rubber are improved, the rubber shoe forming clamp rubber with high wet-skid resistance coefficient, good wear resistance and good folding resistance effect is obtained through screening, the wet-skid coefficient reaches 0.75, the rubber Akron abrasion volume is 0.58-0.6 cm3The service life of the product is longer than that of the original product by more than 6 months, the method is simple, and the manufactured product has low cost and good use effect.
Detailed Description
Example 1 of the invention: the rubber shoe forming clamp rubber is prepared from 45 parts of No. 1 standard rubber, 44 parts of solution-polymerized styrene-butadiene rubber, 11 parts of butadiene rubber, 2.4 parts of sulfur, 1.6 parts of accelerator DM, 1.1 parts of accelerator D, 1.1 parts of accelerator TMTD, 2.2 parts of trapping agent CZ, 2.0 parts of stearic acid, 5 parts of nano-zinc oxide, 7.8 parts of polyethylene glycol, 5.8 parts of anti-aging agent, 4.5 parts of homogenized anti-tearing agent, 45 parts of white carbon black, 4 parts of rubber lubricating oil, 11 parts of wear-resisting agent, 0.5 part of salicylic acid and 2 parts of grass green master batch by weight.
A method for preparing rubber for a rubber shoe molding clamp,
the method is characterized in that: (1) manufacturing plasticated rubber, namely putting 40-50 parts of No. 1 standard rubber into an internal mixer, pressing for 3-5 min, then flattening a winding drum to obtain semi-finished rubber with the Weishi plasticity of 0.45-0.52, and standing for more than 24 hours to obtain plasticated rubber; (2) preparing a master batch, namely putting 50-60 parts of synthetic rubber, 2 parts of stearic acid, 4-5 parts of a homogenizing anti-tearing agent, 7.4-8.2 parts of polyethylene glycol and 40-50 parts of white carbon black into an internal mixer, after 5-6 min of pressure refining, lifting an upper top bolt to turn over the rubber material, after 4-5 min of pressure refining is continued, lifting the upper top bolt of the internal mixer to sweep the powdery material overflowing from the internal mixing chamber back to the internal mixing chamber, then pressure refining for 2-4 min, adding 3-5 parts of rubber softening oil, and discharging after 2-4 min of pressure refining; after the internal mixer discharges materials, immediately putting the discharged materials into an open rubber mixing mill with a roll spacing of 4-5 mm, turning over for 8 times, discharging sheets with a thickness of 4-6 mm, cooling the sheets by adopting normal-temperature water, and standing for more than 24 hours to obtain a master batch, wherein the total amount is 118.3 parts; (3) and (2) manufacturing the mixed rubber, namely putting the plasticated rubber, the intermediate material (namely 5.5-6.5 parts of accelerator, 5 parts of nano zinc oxide, 5.6-6.0 parts of anti-aging agent, 0.4-0.5 part of salicylic acid, 1-3 parts of grass green master batch and 10-12 parts of wear-resisting agent) and the master batch into an internal mixer for pressure refining for 0.5-1 min, adding 118.3 parts of the master batch, pressure refining for 4-5 min, adding 2.0-2.6 parts of sulfur into the pressure refining for 2-3 min, discharging after pressure refining for 25-30 s, immediately putting the discharged rubber material into a discharge type rubber refining machine with a roll spacing of 4-5 mm for cross refining for 4-6 times, discharging the rubber sheet with a thickness of 4-6 mm, cooling the rubber sheet by using normal temperature water, standing for more than 24 hours to obtain mixed rubber, and inspecting the mixed rubber to obtain a finished product.
Example 2 of the invention: the rubber shoe forming clamp rubber is prepared from 48 parts by weight of No. 1 standard rubber, 41 parts by weight of solution-polymerized styrene-butadiene rubber, 11 parts by weight of butadiene rubber, 2.3 parts by weight of sulfur, 1.5 parts by weight of accelerator DM, 1.0 part by weight of accelerator D, 1.1 part by weight of accelerator TMTD, 2.2 parts by weight of accelerator CZ, 2.0 parts by weight of stearic acid, 5 parts by weight of nano-zinc oxide, 7.8 parts by weight of polyethylene glycol, 5.8 parts by weight of anti-aging agent, 4.0 parts by weight of homogenized anti-tearing agent, 45 parts by weight of white carbon black, 4 parts by weight of rubber lubricating oil, 10 parts by weight of wear-resisting agent, 0.5 part by weight of salicylic acid and 1.
The preparation method of the rubber shoe molding jig rubber is the same as that of example 1.
Example 3 of the invention: the rubber shoe forming clamp rubber is prepared from, by weight, 42 parts of No. 1 standard rubber, 44 parts of solution-polymerized styrene-butadiene rubber, 14 parts of butadiene rubber, 2.4 parts of sulfur, 1.6 parts of an accelerator DM, 1.1 parts of an accelerator D, 1.1 parts of an accelerator TMTD, 2.2 parts of a trapping agent CZ, 2.0 parts of stearic acid, 5 parts of nano-zinc oxide, 8 parts of polyethylene glycol, 5.8 parts of an anti-aging agent, 4.6 parts of a homogenized anti-tearing agent, 45 parts of white carbon black, 3 parts of rubber lubricating oil, 12 parts of an anti-wear agent, 0.6 part of salicylic acid and 2 parts of grass green master batch.
The rubber shoe molding jig rubber was prepared in the same manner as in example 1.
Claims (10)
1. The utility model provides a rubber shoe shaping jig rubber which characterized in that: the rubber lubricating oil comprises, by weight, 40-50 parts of No. 1 standard rubber, 50-60 parts of synthetic rubber, 2.0-2.6 parts of sulfur, 5.5-6.5 parts of an accelerator, 5 parts of nano zinc oxide, 7.4-8.2 parts of polyethylene glycol, 5.6-6.0 parts of an anti-aging agent, 4-5 parts of a homogenized anti-tearing agent, 40-50 parts of white carbon black, 10-12 parts of a wear-resisting agent and 3-5 parts of rubber lubricating oil.
2. The rubber shoe molding jig rubber according to claim 1, characterized in that: the rubber lubricating oil comprises, by weight, 45 parts of No. 1 standard rubber, 55 parts of synthetic rubber, 2.4 parts of sulfur, 6 parts of an accelerator, 7.0 parts of a vulcanization activator, 7.8 parts of polyethylene glycol, 5.8 parts of an anti-aging agent, 4.5 parts of a homogenized anti-tearing agent, 45 parts of white carbon black, 11 parts of an anti-wear agent and 4 parts of rubber lubricating oil.
3. The rubber shoe molding jig rubber according to claim 1 or 2, characterized in that: each 55 parts of synthetic rubber consists of 44 parts of solution-polymerized styrene-butadiene rubber and 11 parts of butadiene rubber.
4. The rubber shoe molding jig rubber according to claim 1 or 2, characterized in that: every 7 parts of vulcanization activator consists of 2.0 parts of stearic acid and 5 parts of nano zinc oxide, the specification of the polyethylene glycol is 4000 molecular weight, the specification of the homogenized anti-tearing agent is DS-40, and the specification of the wear-resisting agent is DC-Z-B.
5. The rubber shoe molding jig rubber according to claim 1 or 2, characterized in that: each 6 parts of accelerator consists of 1.6 parts of accelerator DM, 1.1 parts of accelerator D, as well as 1.1 parts of accelerator TMTD and 2.2 parts of catcher CZ.
6. The rubber shoe molding jig rubber according to claim 1 or 2, characterized in that: every 5.8 parts of the antioxidant consists of 2.3 parts of antioxidant CD, 2.2 parts of antioxidant KY-405L and 1.3 parts of antioxidant RD.
7. The rubber shoe molding jig rubber according to claim 1 or 2, characterized in that: also comprises 0.4-0.5 part of salicylic acid and 1-3 parts of grass green masterbatch.
8. A preparation method of rubber for a rubber shoe forming clamp is characterized by comprising the following steps: (1) manufacturing plasticated rubber, namely putting 40-50 parts of No. 1 standard rubber into an internal mixer, pressing for 3-5 min, then flattening a winding drum to obtain semi-finished rubber with the Weishi plasticity of 0.45-0.52, and standing for more than 24 hours to obtain plasticated rubber; (2) preparing a master batch, namely putting 50-60 parts of synthetic rubber, 2 parts of stearic acid, 4-5 parts of a homogenizing anti-tearing agent, 7.4-8.2 parts of polyethylene glycol and 40-50 parts of white carbon black into an internal mixer, after 5-6 min of pressure refining, lifting an upper top bolt to turn over the rubber material, after 4-5 min of pressure refining is continued, lifting the upper top bolt of the internal mixer to sweep the powdery material overflowing from the internal mixing chamber back to the internal mixing chamber, then pressure refining for 2-4 min, adding 3-5 parts of rubber softening oil, and discharging after 2-4 min of pressure refining; after the internal mixer discharges materials, immediately putting the discharged materials into an open rubber mixing mill with a roll spacing of 4-5 mm, turning over for 8 times, discharging sheets with a thickness of 4-6 mm, cooling the sheets by adopting normal-temperature water, and standing for more than 24 hours to obtain a master batch, wherein the total amount is 118.3 parts; (3) and (2) manufacturing the rubber compound, namely putting the plasticated rubber, the medium material and the master batch into an internal mixer for pressure refining for 0.5-1 min, adding 118.3 parts of the master batch, pressure refining for 4-5 min, adding 2.0-2.6 parts of sulfur into the internal mixer for pressure refining for 2-3 min, then pressure refining for 25-30 seconds, discharging, immediately putting the discharged rubber material into an open 4-5 mm roller spacing placed rubber refining machine for cross milling for 4-6 times, discharging the rubber material with the thickness of 4-6 mm, cooling the rubber material by using normal temperature water, standing for more than 24 hours to obtain the rubber compound, and inspecting the rubber compound to obtain the finished product of the rubber compound.
9. The method for preparing rubber for the rubber shoe molding jig according to claim 8, characterized in that: the medium materials comprise 5.5-6.5 parts of an accelerator, 5 parts of nano zinc oxide, 5.6-6.0 parts of an anti-aging agent, 0.4-0.5 part of salicylic acid, 1-3 parts of grass green masterbatch and 10-12 parts of a wear-resisting agent.
10. The method for preparing rubber for the rubber shoe molding jig according to claim 8, characterized in that: the inspection indexes of the mixed rubber are that the Wei's plasticity of the mixed rubber is 0.45-0.55, the Shore hardness is 65-70 degrees, the specific gravity is 1.20 +/-0.02, and the vulcanization starting point at 143 ℃ is 2' 40-3 '00'; uniformly hot-refining the mixed rubber at 40-60 ℃, and cutting into rubber blank sheets in required shapes; then brushing gasoline adhesive cement on the adhesive surface of the rubber stock blank, drying, adhering the rubber stock blank on a core plate of a clamp firmly, and vulcanizing the rubber stock blank in a rubber shoe steam pot under the vulcanization process condition to prepare a rubber shoe molding rubber clamp which is used for clamping and conveying semi-finished rubber shoes in the rubber shoe molding process.
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| CN201910926384.2A CN110606999A (en) | 2019-09-27 | 2019-09-27 | Rubber for rubber shoe forming clamp and preparation method thereof |
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| CN201910926384.2A CN110606999A (en) | 2019-09-27 | 2019-09-27 | Rubber for rubber shoe forming clamp and preparation method thereof |
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| JP2002320503A (en) * | 2001-04-25 | 2002-11-05 | Sekaicho Rubber Co Ltd | Anti-slippage shoes sole member |
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| CN102161786A (en) * | 2011-06-01 | 2011-08-24 | 际华三五三七制鞋有限责任公司 | High-mutual viscosity lustered yellowing-resistance bleached sole rubber and preparation method thereof |
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| CN103450518A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Highly wear resistant rubber and preparation method thereof |
| CN103554562A (en) * | 2013-11-05 | 2014-02-05 | 际华三五三七制鞋有限责任公司 | Frosted ruber sole rubber and preparation method thereof, and preparation method of product of frosted ruber sole rubber |
| CN109456515A (en) * | 2018-11-19 | 2019-03-12 | 陶伟珍 | A kind of wearability sole rubber material and preparation method thereof |
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2019
- 2019-09-27 CN CN201910926384.2A patent/CN110606999A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002320503A (en) * | 2001-04-25 | 2002-11-05 | Sekaicho Rubber Co Ltd | Anti-slippage shoes sole member |
| CN101643552A (en) * | 2009-09-21 | 2010-02-10 | 际华三五三七制鞋有限责任公司 | Vulcanized rubber for shoes capable of realizing high effective and fast vulcanization and preparation method and vulcanization process thereof |
| CN102161786A (en) * | 2011-06-01 | 2011-08-24 | 际华三五三七制鞋有限责任公司 | High-mutual viscosity lustered yellowing-resistance bleached sole rubber and preparation method thereof |
| CN102304239A (en) * | 2011-09-07 | 2012-01-04 | 际华三五三七制鞋有限责任公司 | Black bi-vulcanized rubber outsole for mat high-modulus shoe and preparation method thereof |
| CN103450518A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Highly wear resistant rubber and preparation method thereof |
| CN103554562A (en) * | 2013-11-05 | 2014-02-05 | 际华三五三七制鞋有限责任公司 | Frosted ruber sole rubber and preparation method thereof, and preparation method of product of frosted ruber sole rubber |
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