CN114752120A - Rubber for controlling resistance of anti-static rubber shoes and preparation method and application thereof - Google Patents

Rubber for controlling resistance of anti-static rubber shoes and preparation method and application thereof Download PDF

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CN114752120A
CN114752120A CN202210551658.6A CN202210551658A CN114752120A CN 114752120 A CN114752120 A CN 114752120A CN 202210551658 A CN202210551658 A CN 202210551658A CN 114752120 A CN114752120 A CN 114752120A
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rubber
parts
resistance
static
compound
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张世林
晋齐怀
侯文霞
毛昌虎
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Jihua 3537 Co ltd
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Jihua 3537 Co ltd
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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
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a rubber for controlling the resistance of an antistatic rubber shoe, and a preparation method and application thereof, wherein the rubber comprises, by weight, 20-25 parts of butadiene rubber, 75-80 parts of standard rubber, 2-2.4 parts of sulfur, 5.5-6 parts of a vulcanization accelerator, 7-7.5 parts of nano zinc oxide, 12-14 parts of stearic acid, 65-70 parts of pottery clay, 0.4-0.6 part of salicylic acid, 30-35 parts of medium-wear-resistant carbon black, 15-18 parts of precipitated white carbon black, 2-3 parts of solid coumarone, 8-12 parts of a rubber softener, 3-5 parts of tackifying resin and 1-2 parts of an anti-aging agent. The invention selects the hard rubber insole as the rubber for controlling the resistance of the anti-static rubber shoe, and screens and optimizes the rubber material of the hard rubber insole and the preparation method, so that the rubber material of the hard rubber insole obtained by production has the characteristic of stable resistance value, and the preparation method is simple and has wide material sources.

Description

Rubber for controlling resistance of anti-static rubber shoes and preparation method and application thereof
Technical Field
The invention relates to the field of rubber processing, in particular to rubber for controlling resistance of an anti-static rubber shoe, and a preparation method and application thereof.
Background
The rubber hard midsole sizing material of the rubber shoe is mainly used for the dithio rubber shoe, and has the functions of filling a groove formed by enclosing of sponge and a shoe upper of the dithio shoe and bonding the rubber shoe outsole and the sponge midsole into a whole under vulcanization conditions. The anti-static hard midsole is an important component of the anti-static performance of the rubber shoe, and the resistance domain value of the anti-static hard midsole plays an important role in controlling the resistance value of the anti-static rubber shoe.
Generally, the resistance value of the anti-static rubber shoe is formed by adding the resistance values of the rubber shoe outsole, the anti-static hard midsole and the anti-static sponge. Therefore, to realize the antistatic performance of the rubber shoe, four methods can be adopted:
the method comprises the steps that a rubber sole is used as a core control component of a rubber shoe resistor, and the method has two defects, on one hand, enough carbon black is needed for reinforcement when the comprehensive performance of the sole is optimal, so that the resistance of the sole is extremely lower than 5-power ohm of 10, and the anti-static function cannot be well realized; on the other hand, if the large-sole resistance is between 5-9 ohms of 10, the amount of carbon black in the rubber must be reduced, so that the wear resistance and tensile property of the sole are greatly reduced, and the service performance of the rubber shoe cannot be ensured. Therefore, in order to ensure the comprehensive performance of the antistatic rubber shoes, the outsole cannot be used as a core component for controlling the resistance of the rubber shoes.
In the second method, the sponge is used as a core control component of the rubber shoe resistor, and the method has the defects of influencing the production yield and the quality of the component. Because the foaming capacity and the cell size of the sponge can cause the resistance of the part to fluctuate, and the wearing quality of the product can be influenced. When the resistance value is in the antistatic requirement range, an overproof state of resistance increase can be formed along with fluctuation of rubber foaming, a sponge bottom which is high in resistance and unqualified is generated, and the rejection rate is increased. If the resistance is qualified by reducing the foaming rate of the sponge rubber, the rubber material has poor foaming effect and poor wearing quality. Therefore, to achieve high quality and production efficiency of the anti-static rubber shoe sponge, the sponge cannot be used as a core control component of the rubber shoe resistor.
In the third method, the rubber sole, the rubber hard midsole and the sponge are adopted to jointly control the resistance of the anti-static rubber shoe, so that the defects of the first method and the second method and the comprehensive difficulty of the rubber hard midsole exist. The method has the advantages of higher control difficulty, complex process, low qualification rate and high cost.
And in the fourth method, the rubber hard midsole is used as a core control component of the anti-static rubber shoe resistor. The method has low requirements on the quality of the sizing material, and only one path of resistance for stably controlling the sizing material exists. The balance of the sizing resistance is the work focus.
As a key part for controlling the resistance of high-grade anti-static disulfide shoes, the rubber formula is not optimized sufficiently, the process rationality is poor, the resistance of the rubber shoes is fluctuated frequently, and the product percent of pass is influenced, so that the component proportion and the manufacturing process of the rubber hard insole material become the key for influencing the resistance of the rubber shoes.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the rubber for controlling the resistance of the anti-static rubber shoes and the preparation method and the application thereof are provided, the rubber has the characteristics of simple manufacture, low cost and stable resistance value, the production efficiency and the product quality of the anti-static rubber shoes and the sponge are improved, and the defects of the prior art are overcome.
The invention is realized by the following steps: the rubber for controlling the resistance of the anti-static rubber shoes comprises, by weight, 20-25 parts of butadiene rubber, 75-80 parts of standard rubber, 2-2.4 parts of sulfur, 5.5-6 parts of vulcanization accelerator, 7-7.5 parts of nano zinc oxide, 12-14 parts of stearic acid, 65-70 parts of pottery clay, 0.4-0.6 part of salicylic acid, 30-35 parts of medium-wear-resistant carbon black, 15-18 parts of precipitated white carbon black, 2-3 parts of solid coumarone, 8-12 parts of rubber softener, 3-5 parts of tackifying resin and 1-2 parts of anti-aging agent.
More preferably, the rubber composition comprises, by weight, 22 parts of butadiene rubber, 78 parts of standard rubber, 2.2 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.2 parts of nano zinc oxide, 13 parts of stearic acid, 68 parts of clay, 0.5 part of salicylic acid, 32 parts of medium-wear-resistant carbon black, 17 parts of precipitated white carbon black, 2.5 parts of solid coumarone, 10.5 parts of rubber softener, 4 parts of tackifying resin and 1.5 parts of anti-aging agent.
The standard rubber is 2# standard rubber, and the type of the butadiene rubber is BR 9000.
The rubber softener is dibutyl phthalate, the specification type of tackifying resin is odorless tackifying resin DT100, and the type of anti-aging agent is KY-405L
The vulcanization accelerator is composed of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS in every 5.8 parts of vulcanization accelerator.
The preparation method of the rubber for controlling the resistance of the anti-static rubber shoes comprises the following steps of taking the components according to the weight percentage,
(1) preparing carbon black master batch: plasticating 20-25 parts of standard rubber on a rubber mixing mill at the temperature of not higher than 50 ℃ until the Weibull plasticity is 0.55-0.60 to obtain plasticated rubber; adding plasticated rubber into internal mixing, adding 1 part of stearic acid, solid coumarone and butadiene rubber, adding medium super wear-resistant carbon black after refining for 1 minute, refining for 4 minutes, adding 5-7 rubber softener, after loading the internal mixer, refining for 3 minutes, after loading a rubber refining machine, refining for 1 minute to enable the rubber softener to be completely contained in the rubber, discharging to an open rubber refining machine, uniformly stirring the rubber at a roller spacing of 5-6 mm, discharging, naturally cooling to room temperature, taking carbon black masterbatch, and standing for 24 hours for later use;
(2) preparing antistatic hard mid-sole compound rubber: adding the rest of standard rubber, the carbon black master batch prepared in the step (1), an anti-aging agent and tackifying resin into an internal mixer for milling for 2 minutes, adding 50-60 parts of argil and the rest of rubber softener, milling for 5 minutes, uniformly kneading all the materials, discharging the materials into an open rubber mill, turning the materials until the surface of the rubber materials is smooth, discharging the materials at a roller spacing of 8-10mm, cooling the discharged rubber sheets with room temperature water, air-drying the cooled rubber sheets to room temperature, and collecting the sheets to obtain the antistatic hard middle base compounded rubber for later use;
(3) preparing a first-stage rubber compound: adding the antistatic hard middle sole compound rubber into an internal mixer, and adding the compound rubber medium material of the ingredients, wherein the medium material comprises: the vulcanization accelerator, the nano zinc oxide, the rest stearic acid and the rest salicylic acid are pressed for one minute, the precipitated white carbon black is added, the pressing is carried out for 3 minutes, the rest argil is added, the pressing is carried out for more than 3 minutes, all the edge overflow powder is swept in, the refining is carried out for 1 to 2 minutes, the discharging is carried out to an open rubber mixer, the sulfur is added after the temperature of the rubber material is reduced for three times, the stirring is uniform, the rubber material is placed at the position of 6 to 8mmm, the water cooling and the air drying are carried out, and the rubber is placed for one day at the room temperature, so that a section of rubber compound is obtained;
(4) preparing a second-stage rubber compound: putting a section of rubber compound into an internal mixer, internally mixing for 4.5 minutes at the temperature of 60-110 ℃, discharging materials to an XK-450 open rubber mixing mill to mill the surface of the rubber compound till the surface of the rubber compound is smooth, discharging the rubber compound at the roller distance of 6-8mm, performing water cooling and air drying, and performing quick detection on the rubber compound to ensure that the vulcanization starting point of the rubber compound is 3 min to 10 sec to 3 min to 40 sec, the plasticity is 0.45-0.53, and the flat vulcanized rubber resistance of the rubber compound is under the condition of 0.45MPaX5 min: 0.5-9M omega to obtain two-stage rubber compound, namely the rubber for controlling the resistance of the anti-static rubber shoes.
The application of the rubber for controlling the resistance of the anti-static rubber shoes comprises the steps of softening the rubber on an open rubber mixing mill for controlling the resistance of the anti-static rubber shoes, extruding a scribing sheet into a rubber mixing extruder to remove bubbles, pressing the rubber sheet into a rubber sheet with the thickness of 1.0-1.2 mm through a rubber calender, cooling and shaping the rubber sheet at room temperature for 15 minutes, and punching the rubber sheet into a required shape by using a cantilever punching machine to obtain a semi-finished rubber sheet for controlling the resistance of the anti-static rubber shoes; and (3) sticking the rubber semi-finished product film for controlling the resistance of the anti-static rubber shoe in a groove formed by enclosing the secondary vulcanized sponge rubber surface and the upper vamp and then bonding the rubber semi-finished product film with the anti-static rubber sole.
To further verify the effect of the present invention, the following experiment was performed:
first, preparation of carbon black masterbatch and process effect
1, formulation test
TABLE 1 parts of the formula
Figure BDA0003650224820000041
According to the refining effect of the rubber material and the resistance measurement result, the optimal material ratio of the carbon black master batch is as follows: the carbon black master batch comprises the following components in percentage by weight: 22 parts of butadiene rubber, 22 parts of 2# standard rubber, 1 part of stearic acid, 32 parts of medium and super wear-resistant carbon black, 2.5 parts of solid coumarone and 6.5 parts of rubber softener, wherein the total parts are as follows: 86 parts of the raw materials.
2. Carbon black masterbatch process test:
TABLE 2 carbon Black masterbatch Process rubber mixing procedure
Figure BDA0003650224820000042
Figure BDA0003650224820000051
The optimum carbon black masterbatch process mixing procedure, obtained from table 2, was: plasticating 22 parts of standard rubber on a rubber mixing mill at the temperature of not higher than 50 ℃ until the Weibull plasticity is 0.55-0.60 to obtain plasticated rubber; adding plasticated rubber into internal mixing, adding 1 part of stearic acid, 2.5 parts of solid coumarone and 22 parts of butadiene rubber, adding 32 parts of medium-super wear-resistant carbon black after refining for 1 minute, adding 6.5 parts of rubber softener after refining for 4 minutes, after loading the internal mixer, refining for 3 minutes, after loading a rubber refining machine, refining for 1 minute to enable the rubber softener to be completely contained in the rubber, discharging to an open rubber refining machine, uniformly stirring the rubber material at a roller distance of 5-6 mm, discharging, and naturally cooling to room temperature
Second, preparation of antistatic hard mid-sole compound rubber
1. Influence of anti-static hard insole compound mixing ratio on rubber quality
TABLE 3 anti-static hard middle sole compound mixing ratio test
Figure BDA0003650224820000052
Figure BDA0003650224820000061
According to the test results in table 3, the optimal mixture ratio of the antistatic hard mid-sole compound rubber is as follows: 56 parts of standard rubber, 86 parts of carbon black masterbatch, 1.5 parts of anti-aging agent, 4 parts of tackifying resin, 56 parts of argil and 4 parts of rubber softener. 207.0 portions in total.
2. Anti-static hard middle sole compound rubber manufacturing process test
TABLE 4 COMPARATIVE TABLE FOR MANUFACTURING TECHNOLOGY OF ANTI-STATIC ELECTROSTATIC HARD MEDIUM BASE SYNTHETIC RUBBER
Figure BDA0003650224820000062
The optimal process procedure of the anti-static hard mid-sole compound rubber is as follows from table 4: adding carbon black masterbatch, No. 1 standard rubber and intermediate materials (stearic acid, an anti-aging agent and the like), refining for 3 minutes, turning, adding argil (30 kilograms) and a rubber softener, refining for about 2 minutes, lifting load, refining for 3 minutes, lifting load and stabilizing, and discharging after the lifting load is stabilized (the total time is 9-10 minutes). After the sizing material enters the flat machine, the sizing material is stamped by starting the sizing material overturning device for 6 minutes (8-9 times), and then the sheet can be discharged, and the surface of the discharged sizing material is basically flat.
Thirdly, preparing anti-static hard midsole first-stage rubber compound
1. Anti-static hard insole section rubber compound proportioning test
TABLE 5 anti-static hard insole one-stage compound mix proportion test table (part)
Figure BDA0003650224820000071
The test of Table 5 shows that the optimal mixing ratio of the anti-static hard insole section rubber compound is as follows: 207.0 parts of antistatic hard middle sole compound rubber, 2.2 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.2 parts of nano zinc oxide, 13 parts of stearic acid, 0.5 part of salicylic acid, 17 parts of white carbon black, 12 parts of pottery clay and 6 parts of rubber softener. The resistance of the rubber shoe is ensured to be 10 kilohms, the requirement of the anti-static rubber shoe is met, and the resistance performance of the product is ensured to be stable.
2. Procedure test of anti-static hard midsole rubber compound
TABLE 6 procedure test of anti-static hard midsole rubber compound
Figure BDA0003650224820000081
The test in table 6 shows that the optimal procedure of the anti-static hard midsole rubber compound is as follows: the method comprises the steps of static-free hard middle sole combined rubber, middle materials and argil, press refining for 1 minute, adding white carbon black, press refining for 3 minutes, lifting top bolt sweeping powder, press refining for 1.5 minutes again, sweeping powder for 1.5 minutes, discharging, pulling through a flat machine, reducing the temperature, adding sulfur, and discharging the slice after the sulfur is completely consumed and the slice is turned over for more than 6 times.
Four, anti-static hard insole two-stage mixing test
TABLE 7 antistatic hard midsole two-stage mixing test
Test protocol Content providing method and apparatus Resistance stability
1 Two-stage mixing Is stable and uniform
2 Mixing in one stage Unstable and uneven
Thirdly, the combined system of the accelerant has influence on the resistance of the antistatic hard insole
TABLE 4 Effect of accelerator combination system on the resistance of antistatic hard midsole
Figure BDA0003650224820000091
As can be seen from table 4, the optimum ratio of the accelerator is: every 5.8 parts of vulcanization accelerator consists of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS.
Due to the adoption of the technical scheme, compared with the prior art, the rubber material of the rubber hard insole and the preparation method are screened and optimized, so that the rubber material of the rubber hard insole obtained by production has the characteristic of stable resistance value, and the preparation method is simple and has wide material sources. The invention is simple and easy to implement, low in cost and good in using effect of the product.
Detailed Description
Example 1 of the invention: the rubber for controlling the resistance of the antistatic rubber shoes comprises, by weight, 22 parts of butadiene rubber, 78 parts of standard rubber, 2.2 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.2 parts of nano zinc oxide, 13 parts of stearic acid, 68 parts of pottery clay, 0.5 part of salicylic acid, 32 parts of medium-wear-resistant carbon black, 17 parts of precipitated white carbon black, 2.5 parts of solid coumarone, 10.5 parts of rubber softener, 4 parts of tackifying resin and 1.5 parts of anti-aging agent.
The vulcanization accelerator is composed of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS in every 5.8 parts of vulcanization accelerator.
The preparation method of the rubber for controlling the resistance of the antistatic rubber shoes comprises the following steps of 1) preparing carbon black master batch by taking the following components in parts by weight:
(1) the carbon black master batch comprises the following components in percentage by weight: 22 parts of butadiene rubber, 22 parts of 2# standard rubber, 1 part of stearic acid, 32 parts of medium and super wear-resistant carbon black, 2.5 parts of solid coumarone and 6.5 parts of rubber softener, wherein the total parts are as follows: 86 parts of the raw materials. The construction is enlarged by 2.5 times during rubber mixing.
(2) Preparing carbon black master batch: a was carried out using a 160 liter internal mixer. B, a manufacturing process: plasticating 22 parts of standard rubber on a rubber mixing mill at the temperature of not higher than 50 ℃ until the Weibull plasticity is 0.55-0.60 to obtain plasticated rubber; adding plasticated rubber into internal mixing, adding 1 part of stearic acid, 2.5 parts of solid coumarone and 22 parts of butadiene rubber, adding 32 parts of medium-super wear-resistant carbon black after refining for 1 minute, adding 6.5 parts of rubber softener after refining for 4 minutes, after loading the internal mixer, refining for 3 minutes, after loading a rubber refining machine, refining for 1 minute to enable the rubber softener to be completely contained in the rubber, discharging to an open rubber refining machine, uniformly turning the rubber material at a roller distance of 5-6 mm, discharging, naturally cooling to room temperature, weighing 86 parts of carbon black masterbatch, and standing for 24 hours for later use;
(3) preparing antistatic hard mid-sole compound rubber: adding 56 parts of standard rubber and 86 parts of carbon black master batch prepared in the step (2), 1.5 parts of anti-aging agent and 4 parts of tackifying resin (DT100) into an internal mixer for milling for 2 minutes, then adding 56 parts of argil and 4 parts of rubber softener, milling for 5 minutes, kneading all the materials uniformly, discharging the materials into an open rubber mill, turning until the surface of the rubber material is smooth, discharging the rubber sheet at a roller distance of 8-10mm, cooling the discharged rubber sheet by room temperature water, air-drying to room temperature, collecting and weighing 207.0 parts of the rubber sheet, and obtaining the antistatic hard middle sole compounded rubber for later use.
(4) Preparing a first-stage rubber compound: 207.0 parts of antistatic hard middle sole compound rubber is put into an internal mixer, 26.5 parts of the compounded compound rubber medium material (the medium material comprises 5.8 parts of vulcanization accelerator, 7.2 parts of nano zinc oxide, 13 parts of stearic acid and 0.5 part of salicylic acid) is added, one part of the mixed rubber medium material is pressed for one minute, 17 parts of precipitated silica is added, the mixture is pressed for 3 minutes, 12 parts of argil is added, the mixture is pressed for more than 3 minutes, all the overflowed powder is swept in, the mixture is further refined for 1 to 2 minutes, the mixture is discharged to an open rubber refining machine (XK-450 type), 2.2 parts of sulfur is added after the temperature of the rubber material is reduced for three times, the mixture is uniformly turned, the mixture is cut into pieces with the size of 6 to 8mmm, and the pieces are cooled by water and dried in the air, and the mixture is kept at room temperature for one day. Obtain a whole part of the rubber compound.
(5) Preparing a second-stage rubber compound: and (3) putting the whole section of rubber compound into an internal mixer, carrying out internal mixing for 4.5 minutes at the temperature of 60-110 ℃, discharging materials to an XK-450 open rubber mixing mill, mixing the surface of the rubber material until the surface of the rubber material is smooth, discharging the rubber material at a roller distance of 6-8mm, carrying out water cooling and air drying, and carrying out rapid detection on the rubber material. The vulcanization starting point of the mixed rubber is 3 min 10 s-3 min 40 s, the plasticity is 0.45-0.53, and the flat vulcanized rubber resistance of the mixed rubber is under the condition of 0.45MPaX5 min: 0.5-9M omega to obtain two-stage rubber compound, namely the rubber for controlling the resistance of the anti-static rubber shoes.
The application of the rubber for controlling the resistance of the anti-static rubber shoes is characterized in that: softening the rubber open rubber mixing mill for controlling the resistance of the anti-static rubber shoes, cutting the rubber into a rubber mixing extruder to extrude and remove air bubbles, pressing the rubber into a rubber sheet with the thickness of 1.0-1.2 mm through a rubber calender, cooling and shaping the rubber sheet at room temperature for 15 minutes, and then punching the rubber sheet into a required shape by using a cantilever punching machine to obtain a semi-finished rubber sheet for controlling the resistance of the anti-static rubber shoes; and (3) sticking the rubber semi-finished product rubber sheet for controlling the resistance of the anti-static rubber shoe in a groove formed by enclosing the secondary vulcanized sponge rubber surface and the upper vamp and then bonding the rubber semi-finished product rubber sheet with the anti-static rubber sole.
Example 2 of the invention: the rubber for controlling the resistance of the antistatic rubber shoes comprises, by weight, 22 parts of butadiene rubber, 78 parts of standard rubber, 2.3 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.5 parts of nano zinc oxide, 13 parts of stearic acid, 70 parts of argil, 0.5 part of salicylic acid, 32 parts of medium-wear-resistant carbon black, 17 parts of precipitated white carbon black, 2.5 parts of solid coumarone, 8 parts of rubber softener, 4 parts of tackifying resin and 1.5 parts of anti-aging agent. The vulcanization accelerator is composed of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS in every 5.8 parts of vulcanization accelerator.
The preparation method and the application are as in claim 1.
Example 3 of the invention: the rubber for controlling the resistance of the antistatic rubber shoes comprises, by weight, 22 parts of butadiene rubber, 78 parts of standard rubber, 2.0 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.0 parts of nano zinc oxide, 13 parts of stearic acid, 66 parts of pottery clay, 0.5 part of salicylic acid, 32 parts of medium-ultra wear-resistant carbon black, 17 parts of precipitated white carbon black, 3 parts of solid coumarone, 10.5 parts of rubber softener, 5 parts of tackifying resin and 1.5 parts of anti-aging agent. Every 5.8 parts of vulcanization accelerator consists of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS.
The preparation method and the application are as in claim 1.

Claims (7)

1. The utility model provides a rubber of control antistatic rubber shoes resistance which characterized in that: the rubber comprises, by mass, 20-25 parts of butadiene rubber, 75-80 parts of standard rubber, 2-2.4 parts of sulfur, 5.5-6 parts of vulcanization accelerator, 7-7.5 parts of nano zinc oxide, 12-14 parts of stearic acid, 65-70 parts of pottery clay, 0.4-0.6 part of salicylic acid, 30-35 parts of medium-super wear-resistant carbon black, 15-18 parts of precipitated white carbon black, 2-3 parts of solid coumarone, 8-12 parts of rubber softener, 3-5 parts of tackifying resin and 1-2 parts of anti-aging agent.
2. The rubber for controlling the resistance of the anti-static rubber shoes as claimed in claim 1, wherein: the rubber comprises, by mass, 22 parts of butadiene rubber, 78 parts of standard rubber, 2.2 parts of sulfur, 5.8 parts of vulcanization accelerator, 7.2 parts of nano zinc oxide, 13 parts of stearic acid, 68 parts of argil, 0.5 part of salicylic acid, 32 parts of medium and super wear-resistant carbon black, 17 parts of precipitated white carbon black, 2.5 parts of solid coumarone, 10.5 parts of rubber softener, 4 parts of tackifying resin and 1.5 parts of anti-aging agent.
3. The rubber for controlling the resistance of the anti-static rubber shoes according to the claim 1 or 2, characterized in that: the standard rubber is 2# standard rubber, and the type of the butadiene rubber is BR 9000.
4. The rubber for controlling the resistance of the anti-static rubber shoes according to claim 1 or 2, characterized in that: the rubber softener is dibutyl phthalate, the specification type of the tackifying resin is odorless tackifying resin DT100, and the type of the anti-aging agent is KY-405L.
5. The rubber for controlling the resistance of the anti-static rubber shoes according to claim 1 or 2, characterized in that: the vulcanization accelerator is composed of 0.8 part of accelerator M, 2.2 parts of accelerator DM, 1.0 part of accelerator CZ and 1.8 parts of accelerator DS in every 5.8 parts of vulcanization accelerator.
6. The method for preparing the rubber for controlling the resistance of the anti-static rubber shoes according to claim 1, which is characterized in that: taking the components according to the weight fraction,
(1) preparing carbon black master batch: plasticating 20-25 parts of standard rubber on a rubber mixing mill at the temperature of not higher than 50 ℃ until the Weibull plasticity is 0.55-0.60 to obtain plasticated rubber; adding plasticated rubber into internal mixing, adding 1 part of stearic acid, solid coumarone and butadiene rubber, adding medium super wear-resistant carbon black after refining for 1 minute, refining for 4 minutes, adding 5-7 rubber softener, after loading the internal mixer, refining for 3 minutes, after loading a rubber refining machine, refining for 1 minute to enable the rubber softener to be completely contained in the rubber, discharging to an open rubber refining machine, uniformly stirring the rubber at a roller spacing of 5-6 mm, discharging, naturally cooling to room temperature, taking carbon black masterbatch, and standing for 24 hours for later use;
(2) preparing antistatic hard mid-sole compound rubber: adding the rest of standard rubber, the carbon black master batch prepared in the step (1), an anti-aging agent and tackifying resin into an internal mixer for milling for 2 minutes, adding 50-60 parts of argil and the rest of rubber softener, milling for 5 minutes, uniformly kneading all the materials, discharging the materials into an open rubber mill, turning the materials until the surface of the rubber materials is smooth, discharging the materials at a roller spacing of 8-10mm, cooling the discharged rubber sheets with room temperature water, air-drying the cooled rubber sheets to room temperature, and collecting the sheets to obtain the antistatic hard middle base compounded rubber for later use;
(3) preparing a first-stage rubber compound: adding the antistatic hard middle sole compound rubber into an internal mixer, and adding the compound rubber medium material of the ingredients, wherein the medium material comprises: the vulcanization accelerator, the nano zinc oxide, the rest stearic acid and the rest salicylic acid are pressed for one minute, the precipitated white carbon black is added, the pressing is carried out for 3 minutes, the rest argil is added, the pressing is carried out for more than 3 minutes, all the edge overflow powder is swept in, the refining is carried out for 1 to 2 minutes, the discharging is carried out to an open rubber mixer, the sulfur is added after the temperature of the rubber material is reduced for three times, the stirring is uniform, the rubber material is placed at the position of 6 to 8mmm, the water cooling and the air drying are carried out, and the rubber is placed for one day at the room temperature, so that a section of rubber compound is obtained;
(4) preparing a second-stage rubber compound: putting a section of rubber compound into an internal mixer, internally mixing for 4.5 minutes at the temperature of 60-110 ℃, discharging materials to an XK-450 open rubber mixing mill to mill the surface of the rubber compound till the surface of the rubber compound is smooth, discharging the rubber compound at the roller distance of 6-8mm, performing water cooling and air drying, and performing quick detection on the rubber compound to ensure that the vulcanization starting point of the rubber compound is 3 min to 10 sec to 3 min to 40 sec, the plasticity is 0.45-0.53, and the flat vulcanized rubber resistance of the rubber compound is under the condition of 0.45MPaX5 min: 0.5-9M omega to obtain two-stage rubber compound, namely the rubber for controlling the resistance of the anti-static rubber shoes.
7. Use of the rubber for controlling the resistance of an antistatic rubber shoe according to claim 1, wherein: softening the rubber open type rubber mixing machine for controlling the resistance of the anti-static rubber shoes, scribing, entering a rubber mixing extruder to extrude and remove bubbles, pressing the rubber mixing extruder into a rubber sheet with the thickness of 1.0-1.2 mm through a rubber calender, cooling and shaping the rubber sheet at room temperature for 15 minutes, and then punching the rubber sheet into a required shape by using a cantilever punching machine to obtain a semi-finished rubber sheet for controlling the resistance of the anti-static rubber shoes; and (3) sticking the rubber semi-finished product film for controlling the resistance of the anti-static rubber shoe in a groove formed by enclosing the secondary vulcanized sponge rubber surface and the upper vamp and then bonding the rubber semi-finished product film with the anti-static rubber sole.
CN202210551658.6A 2022-05-18 2022-05-18 Rubber for controlling resistance of anti-static rubber shoes and preparation method and application thereof Pending CN114752120A (en)

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CN102924764A (en) * 2012-11-22 2013-02-13 际华三五一七橡胶制品有限公司 Military shoe outsole rubber material and processing method of military shoe outsole sizing material
CN103275361A (en) * 2013-06-18 2013-09-04 际华三五三七制鞋有限责任公司 Wear-resistant and anti-static sole rubber, as well as preparation method and application 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
CN103665451A (en) * 2013-11-05 2014-03-26 际华三五三七制鞋有限责任公司 Molded rubber outsole without exhaust hole and preparation method of molded rubber outsole
CN103849013A (en) * 2014-01-23 2014-06-11 怡维怡橡胶研究院有限公司 Low-heat highly-wearable rubber composition and production method thereof
CN109608696A (en) * 2018-11-16 2019-04-12 青岛科技大学 A kind of compound sulphur and its preparation and application
CN112390985A (en) * 2020-11-14 2021-02-23 际华三五一七橡胶制品有限公司 Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur
CN113861523A (en) * 2021-10-28 2021-12-31 际华三五三七有限责任公司 High-tensile odorless black sole rubber and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102924764A (en) * 2012-11-22 2013-02-13 际华三五一七橡胶制品有限公司 Military shoe outsole rubber material and processing method of military shoe outsole sizing material
CN103275361A (en) * 2013-06-18 2013-09-04 际华三五三七制鞋有限责任公司 Wear-resistant and anti-static sole rubber, as well as preparation method and application 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
CN103665451A (en) * 2013-11-05 2014-03-26 际华三五三七制鞋有限责任公司 Molded rubber outsole without exhaust hole and preparation method of molded rubber outsole
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CN112390985A (en) * 2020-11-14 2021-02-23 际华三五一七橡胶制品有限公司 Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur
CN113861523A (en) * 2021-10-28 2021-12-31 际华三五三七有限责任公司 High-tensile odorless black sole rubber and preparation method and application thereof

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