CN109384969A - Endurable rubber soles of top grade and preparation method thereof - Google Patents
Endurable rubber soles of top grade and preparation method thereof Download PDFInfo
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- CN109384969A CN109384969A CN201811289652.6A CN201811289652A CN109384969A CN 109384969 A CN109384969 A CN 109384969A CN 201811289652 A CN201811289652 A CN 201811289652A CN 109384969 A CN109384969 A CN 109384969A
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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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high-grade endurable rubber soles and preparation method thereof.Preparation-obtained high-grade endurable rubber soles directly realize matt effect using its bulk material through the invention, shoe sole print is clear, mold need not make rubber flow rubber flow holes, manufactured shoe sole print not starved, manually investment labour is less, low energy consumption, high-efficient in mixing process.Made sole physical property improves significant compared to general conditions of vulcanization simultaneously, reaches resistance to and wears the service life, conducive to reduce sole because wear the service life it is short due to the environmental pollution that is formed.
Description
Technical field
The present invention relates to a kind of rubber processing, especially a kind of high-grade endurable rubber soles and sole preparation side
Method.
Background technique
In two kinds of appearance development trends of rubber overshoes, belong to working people's by the beautiful type product of representative of high gloss
Preference.With " color is soft, the quiet Fresh and elegant of appearance, gives harmonious quiet style, so that people is felt safe, health is relaxed
Suitable sub-smooth type product ", has the special-effect of stimulation consumer's sense organ vision, and the Major Epidemic for becoming current product color becomes
One of gesture.Sub-smooth type top grade wear well rubber soles because its soft, natural, graceful visual appearance and without stream side glue must, at
For the new lover of high-end consumers.
In general, the Fresh and elegant effect of Yao Shixian rubber overshoes rubber soles component, has following disturbing factor.Mold flower
Line exhaust is insufficient, causes sole starved, poor appearance, in order to ensure decorative pattern not starved, ensures that glue nail decorative pattern is clearly full, is forced
The position of decorative pattern starved is being caused to drill through rubber flow holes, the sole manufactured in this way is followed closely with glue, belongs to the attachment having more, appearance
It is very poor.In addition, the operating pressure due to sole pressing mechanism is limited, it is necessary to make shoes using the relatively high rubber of plasticity
Bottom, this cause again it is bad the result is that: sole is well-pressed, stream side glue is more, also presentation quality is brought to influence.
Need currently exist for it is a kind of be suitable for make rubber overshoes without stream side glue and exhaust nail rubber soles material and optimization processing
Method, to promote rubber overshoes presentation quality.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of high-grade rubber soles and preparation method thereof of wearing well, root
Have the following characteristics that (1) rubber body realizes matte effect and with automatic ventilating function, saving mould according to its obtained product
Have surface and carry out frosted processing, reduces production cost.(2) high well-pressed rubber can be used to realize rubber to the effective of mold cavity
Filling, reaches that shoe sole print is full, appearance is clear, eliminates vulcanizate nail that mold rubber flow holes generate, prevents due to rubber stress
The filling of small generation is not in place to be formed by shoe sole print starved.Reduce labor intensity, improves product quality, it is existing to overcome
There is the deficiency of technology.
The present invention is implemented as follows: high-grade endurable rubber soles, in parts by weight, it includes 35~55 parts of days
Right rubber, 35~45 parts of butadiene-styrene rubber, 10~30 parts of butadiene rubbers, 1.5~2.0 parts of sulphur, 2.5~4.5 parts of vulcanizations promote
Agent, 5-7 parts of nano zine oxides, 2-3 parts of stearic acid, 10-20 parts of rubber softener and 46-50 parts of intermediate super abrasion furnace blacks.
Preferred scheme is that it includes 40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur
Super abrasive charcoal in sulphur, 3.6 parts of vulcanization accelerators, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 15 parts of rubber softener and 48 parts
It is black.
It further include 0.1~0.3 part of antiscorching agent, 0.8~1.2 part of release agent in order to improve effect of the invention, in formula
LTM-A and 2~2.6 part of anti-aging agent.
3.6 parts of above-mentioned vulcanization accelerators are by 0.6 part of altax, 2.5 parts of accelerant CZs and 0.5 part of diphenylguanidine S group
At.
15 parts of above-mentioned rubber softener are made of 5 parts of homogenizing tear-proof agent and 10 parts of naphthenic oils.
The preparation method of the endurable rubber soles of top grade, (1) ingredient: by natural rubber and butadiene-styrene rubber, butadiene rubber
Mixing, obtains A product；Intermediate super abrasion furnace black will be prepared, B product are obtained；Vulcanization accelerator and nano zine oxide, stearic acid are mixed,
Obtain C product；(2) refining is without sulphur rubber compound: A product are put into rubber mixing machine, temperature be 80~125 DEG C, pressure be 0.34~
After being refined 0.5~1 minute under conditions of 0.38Mpa, the rubber softener of B product, C product and half is added, continues 4~5 points of refining
Then clock is added the other half rubber softener and continues refining to uniformly without powder, obtaining being kneaded semi-finished product；Semi-finished product discharge will be kneaded
Supplement is carried out to opening rubber mixing machine to turn refining, and is kept material fully dispersed uniformly, is obtained rubber compound；Rubber compound is made 7~8mm's
Film after then impregnating the film one time with interleaving agent liquid, then with blower is air-dried the moisture on film；(3) manufacture is high
Class wears well rubber boots primer: refining is to smooth on the film investment open mill after air-drying, and sulphur is added, then heat refining is uniform,
Press required thickness tabletting finally to get high-quality sole rubber is arrived；(4) it after obtaining high-grade endurable rubber soles, will obtain
Top grade wear well rubber boots primer, by it at 145~150 DEG C without in rubber flow holes die for shoe-sole, being put in 200 tons of operating pressure
Pressing machine on press heat cure 5~5.5 minutes, sole is taken out into mold, the side Xiu Quliu glue obtains high-grade endurable rubber boots
Bottom.
It is also had the following characteristics that using method rubber soles of the invention
(1) shoe sole print surface is followed closely without outer gummosis, and gained rubber overshoes external form is good-looking, and face shaping is clearly beautiful.
(2) due to being pressed using high tonnage pressing machine, rubber consistency is high, and tensile property and tear resistance are excellent, shoes
Bottom stiffening property is high, and ability of product wearing well improves.
(3) the properties measured value such as hardness, tensile strength, elongation at break, abrasion stability, reproducibility are good, easily
In the service performance for ensuring shoe rubber sole.
Preparation-obtained high-grade endurable rubber soles directly realize matt using its bulk material through the invention
Effect, shoe sole print is clear, and mold need not make rubber flow rubber flow holes, manufactured shoe sole print not starved, people in mixing process
The labour of work investment is less, low energy consumption, high-efficient.Made sole physical property improves significant compared to general conditions of vulcanization simultaneously, reaches
Wear the service life to resistance to, conducive to reduce sole because wear the service life it is short due to the environmental pollution that is formed.
In process of the present invention, the performance of product is tested, formula as below screening test is carried out, to verify the present invention
Technical solution:
Formula test data:
Formula: 40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur, 3.6 parts of vulcanizations promote
Agent, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 15 parts of rubber softener, 48 parts of intermediate super abrasion furnace blacks, 0.2 part of antiscorching agent, 1.0
Part release agent LTM-A, 2.4 parts of anti-aging agents.
Test data screening process:
(1) reinforcing filler quantity research
A basic recipe: 40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur, 3.6 parts of sulphur
Change promotor, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 0.2 part of antiscorching agent, 1.0 parts of release agent LTM-A, 2.4 parts of anti-aging agents.
Intermediate super abrasion furnace black, rubber softener are variable.
B testing program:
Table 1
It is obtained by table 1, test material optimum proportioning are as follows: 48 parts of intermediate super abrasion furnace black, 15 parts of rubber softener.This proportion reaches
To good matt effect, hardness and stiffness, realize that decorative pattern fills full effect, physical property is best, and processing performance is normal.
(2) vulcanizing system comparative test
A basic recipe: 40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur, 6 parts of nanometers
Zinc oxide, 2.5 parts of stearic acid, 15 parts of rubber softener, 48 parts of intermediate super abrasion furnace blacks, 0.2 part of antiscorching agent, 1.0 parts of release agents
LTM-A, 2.4 parts of anti-aging agents.Vulcanization accelerator is variable.
B Experimental Comparison table
Table 2
2 result of table explanation, vulcanizing system and reactive systems optimum amount are as follows: 0.6 part of altax, accelerant CZ 2.5
Part, 0.5 part of diphenylguanidine S.
(3) raw rubber and with test
A basic recipe: 1.8 parts of sulphur, 0.6 part of altax, 2.5 parts of accelerant CZ, 0.5 part, 6 parts of diphenylguanidine S
Nano zine oxide, 2.5 parts of stearic acid, 15 parts of rubber softener, 48 parts of intermediate super abrasion furnace blacks, 0.2 part of antiscorching agent, 1.0 parts of demouldings
Agent LTM-A, 2.4 parts of anti-aging agents；Natural gum and rubber polymer are variable.
B Experimental Comparison
Table 3
3 result of table explanation, natural gum: Butadiene-Styrene Rubber: butadiene rubber=40:40:20 combined effect reaches best water
It is flat, projects performance requirement can be taken into account.
(4) auxiliary material application study:
Table 4
Table 4 show in enclosure material that 0.2 part of antiscorching agent optimum amount, 1.0 parts of release agent LTM-A optimum amount, anti-aging agent are most
2.4 parts of good dosage.
(5) natural gum plasticity comparative test
Table 5
Table 5 shows that natural rubber is not plasticated, and can take into account processing performance, appearance decorative pattern clearly requires, less energy consumption, artificial throwing
Enter less, is not take up place, belongs to optimum condition.
(6) sole conditions of vulcanization is studied
A curing temperature and vulcanization time
Table 6
B sulfide stress influences performance presentation quality
Table 7
It is obtained from table 6 and 7 result of table, optimum cure condition is；The vulcanizing press for the use of operating pressure being 200 tons,
Vulcanize 5.2 minutes under the conditions of 148 DEG C (section is 145-150 DEG C).
Conclusion (of pressure testing):
It is obtained by above-mentioned test, optimum formula and process conditions are as follows:
Optimum formula: 40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur, 3.6 parts of vulcanizations
Promotor, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 15 parts of rubber softener, 48 parts of intermediate super abrasion furnace blacks, 0.2 part of antiscorching agent,
1.0 parts of release agent LTM-A, 2.4 parts of anti-aging agents.
Process control condition: vulcanization starting point 3 ' 20 "-~3 ' 40 ", natural rubber do not need to carry out processing of plasticating.Sill strip processed
Part is that optimum cure condition is；The vulcanizing press for the use of operating pressure being 200 tons, in 148 DEG C of (section is 145-150 DEG C) items
Vulcanize 5.2 minutes under part.
Since gained sole physical property is in optimal level, rubber overshoes are worn the service life and are reached 6 months or more, realize endurable mesh
's.
For the product obtained through the invention directly by rubber soles, rubber body realizes matt effect.Pass through high-tension apparatus
Ensure rubber filling effect, it is full clear to reach decorative pattern, thoroughly eliminates rubber exhaust attachment.Realize the upgrading of sole aesthetics.
Due to not needing that natural rubber is plasticated, this method and process is simple, and production energy consumption is low, the artificial investment of labour
Less, occupied ground is few, reduces production cost, reduces the labor intensity of worker.
Specific embodiment
1:40 parts of natural rubbers of the embodiment of the present invention, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur,
3.6 parts of vulcanization accelerators, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 15 parts of rubber softener, 48 parts of intermediate super abrasion furnace blacks, 0.2
Part antiscorching agent, 1.0 parts of release agent LTM-A, 2.4 parts of anti-aging agents.
The preparation method of the endurable rubber soles of top grade, according to the parts by weight of above-mentioned formula, (1) ingredient: by natural rubber
Glue and butadiene-styrene rubber, butadiene rubber mixing, obtain A product；Intermediate super abrasion furnace black will be prepared, B product are obtained；By vulcanization accelerator and
Nano zine oxide, stearic acid mixing, obtain C product；(2) refining is without sulphur rubber compound: A product being put into rubber mixing machine, are in temperature
80~125 DEG C, pressure be 0.34~0.38Mpa under conditions of refine 0.5~1 minute after, addition B product, C product and half rubber
Softening agent, continues refining 4~5 minutes, the other half rubber softener is then added and continues refining to uniformly without powder, obtaining being kneaded half
Finished product；Mixing semi-finished product discharge is carried out supplement to opening rubber mixing machine to turn refining, keeps material fully dispersed uniformly, is kneaded
Glue；Rubber compound is made to the film of 7~8mm, after then impregnating the film one time with interleaving agent liquid, then with blower by film
On moisture air-dry；(3) the high-grade endurable rubber boots primer of manufacture: on the film investment open mill after air-drying refining to smooth,
And sulphur is added, then heat refining is uniform, press required thickness tabletting finally to get high-quality sole rubber is arrived.
After obtaining high-grade endurable rubber soles, obtained top grade is worn well rubber boots primer, by its 145~
150 DEG C press heat cure 5~5.5 minutes without in rubber flow holes die for shoe-sole, being put on 200 tons of operating pressure of pressing machine, will
Sole takes out mold, and the side Xiu Quliu glue obtains high-grade endurable rubber soles.
The embodiment of the present invention 2: the endurable rubber soles of top grade, it includes 40 parts of natural rubbers, 50 parts of butadiene-styrene rubber, 10
Part butadiene rubber, 1.9 parts of sulphur, 3.6 parts of vulcanization accelerators, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 15 parts of rubber softenings
Agent, 48 parts of intermediate super abrasion furnace blacks.
The preparation method of the endurable rubber soles of top grade, with embodiment 1.
The embodiment of the present invention 3: the endurable rubber soles of top grade, it includes 45 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 15
Part butadiene rubber, 1.8 parts of sulphur, 3.6 parts of vulcanization accelerators, 6 parts of nano zine oxides, 2.5 parts of stearic acid, 14 parts of rubber softenings
Agent, 49 parts of intermediate super abrasion furnace blacks.
The preparation method of the endurable rubber soles of top grade, with embodiment 1.
Claims (6)
1. a kind of high-grade endurable rubber soles, it is characterised in that: in parts by weight, it includes 35~55 parts of natural rubbers
Glue, 35~45 parts of butadiene-styrene rubber, 10~30 parts of butadiene rubbers, 1.5~2.0 parts of sulphur, 2.5~4.5 parts of vulcanization accelerators, 5-
7 parts of nano zine oxides, 2-3 parts of stearic acid, 10-20 parts of rubber softener and 46-50 parts of intermediate super abrasion furnace blacks.
2. high-grade endurable rubber soles according to claim 1, it is characterised in that: in parts by weight, it includes
40 parts of natural rubbers, 40 parts of butadiene-styrene rubber, 20 parts of butadiene rubbers, 1.8 parts of sulphur, 3.6 parts of vulcanization accelerators, 6 parts of nano oxygens
Change zinc, 2.5 parts of stearic acid, 15 parts of rubber softener and 48 parts of intermediate super abrasion furnace blacks.
3. high-grade endurable rubber soles according to claim 1 or 2, it is characterised in that: further include 0.1~0.3 part anti-
Burnt agent, 0.8~1.2 part of release agent LTM-A and 2~2.6 parts of anti-aging agents.
4. high-grade endurable rubber soles according to claim 2, it is characterised in that: 3.6 parts of vulcanization accelerators are by 0.6 part
Altax, 2.5 parts of accelerant CZs and 0.5 part of diphenylguanidine S composition.
5. high-grade endurable rubber soles according to claim 2, it is characterised in that: 15 parts of rubber softener are equal by 5 parts
Change tear-proof agent and 10 parts of naphthenic oil compositions.
6. a kind of preparation method of high-grade endurable rubber soles as described in claim 1, it is characterised in that: (1) ingredient: will
Natural rubber and butadiene-styrene rubber, butadiene rubber mixing, obtain A product；Intermediate super abrasion furnace black will be prepared as B product；Vulcanization is promoted
Into agent and nano zine oxide, stearic acid mixing, C product are obtained；(2) refining is without sulphur rubber compound: A product are put into rubber mixing machine,
After refining 0.5~1 minute under conditions of temperature is 80~125 DEG C, pressure is 0.34~0.38Mpa, B product, C product and half is added
Rubber softener, continue refining 4~5 minutes, the other half rubber softener be then added and continues refining to uniformly without powder, obtaining
It is kneaded semi-finished product；Mixing semi-finished product discharge is carried out supplement to opening rubber mixing machine to turn refining, keeps material fully dispersed uniformly, obtains
Rubber compound；Rubber compound is made to the film of 7~8mm, after then the film is impregnated one time with interleaving agent liquid, then will with blower
Moisture on film air-dries；(3) it manufactures high-grade endurable rubber boots primer: refining on the film investment open mill after air-drying to light
It is sliding, and sulphur is added, then heat refining is uniform, press required thickness tabletting finally to get high-quality sole rubber is arrived；(4) height is being obtained
After quality sole rubber, by it at 145~150 DEG C without the pressing machine in rubber flow holes die for shoe-sole, being put in 200 tons of operating pressure
Upper pressing heat cure 5~5.5 minutes, sole is taken out into mold, the side Xiu Quliu glue obtains high-grade endurable rubber soles.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811289652.6A CN109384969B (en) | 2018-10-31 | 2018-10-31 | High-grade wear-resistant rubber sole and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289652.6A CN109384969B (en) | 2018-10-31 | 2018-10-31 | High-grade wear-resistant rubber sole and preparation method thereof |
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| CN109384969A true CN109384969A (en) | 2019-02-26 |
| CN109384969B CN109384969B (en) | 2021-05-14 |
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ID=65428199
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02295503A (en) * | 1989-05-10 | 1990-12-06 | Yokohama Rubber Co Ltd:The | Golf shoes |
| 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 |
| CN102212199A (en) * | 2011-05-07 | 2011-10-12 | 临安郑氏橡胶制品有限公司 | Method for preparing high-strength aging-resistant vulcanized rubber |
| 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 |
| CN103965524A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Low-temperature-resistant sole material and preparation method thereof |
| CN107200872A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of wear-resisting microcellular foam material |
-
2018
- 2018-10-31 CN CN201811289652.6A patent/CN109384969B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02295503A (en) * | 1989-05-10 | 1990-12-06 | Yokohama Rubber Co Ltd:The | Golf shoes |
| 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 |
| CN102212199A (en) * | 2011-05-07 | 2011-10-12 | 临安郑氏橡胶制品有限公司 | Method for preparing high-strength aging-resistant vulcanized rubber |
| 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 |
| CN103965524A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Low-temperature-resistant sole material and preparation method thereof |
| CN107200872A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of wear-resisting microcellular foam material |
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| Publication number | Publication date |
|---|---|
| CN109384969B (en) | 2021-05-14 |
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