CN103263115A - Double-density sole, preparation method of double-density sole, antistatic double-density shoe and preparation method of antistatic double-density shoe - Google Patents
Double-density sole, preparation method of double-density sole, antistatic double-density shoe and preparation method of antistatic double-density shoe Download PDFInfo
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Abstract
The invention discloses a double-density sole and a preparation method of the double-density sole, and further discloses an antistatic double-density shoe and a preparation method of the antistatic double-density shoe. Due to the fact that butadiene-acrylonitrile rubber and conductive black materials are adopted by the double-density sole of the double-density shoe, the rubber sole of the manufactured rubber double-density shoe has obvious oil resistivity and electrical conductivity, compared with a polyurethane sole, the rubber sole is good in hydrolysis resistance and cold tolerance, and the double-density sole is long in antistatic service life. The density of a manufactured foaming rubber layer is within the range of 0.7g/cm<3> to 0.8g/cm<3>. The sole of the double-density shoe is further provided with conductive nails which penetrate through a bottom rubber layer, the foaming rubber layer, a wooden heel and an insole, the resistance value of a finished shoe of the double-density shoe is within the range of 105 ohms to 109 ohms, and the double-density shoe meets China national standards for antistatic shoes. The double-density sole, the preparation method of the double-density sole, the antistatic double-density shoe and the preparation method of the antistatic double-density shoe are applicable to preparation of the antistatic rubber shoes, and are further applied to military antistatic shoes.
Description
Technical field
The invention belongs to shoe-making field, relate to a kind of rubber dual density footwear boots, be specifically related to a kind of dual density sole and preparation method and antistatic dual density footwear boots and preparation method.
Background technology
Rubber dual density footwear boots are because own wt is light, wears lightly, cushion good springiness, are subjected to consumer's welcome deeply.But because one deck bipeltate is arranged at the bottom of rubber dual density footwear boots, the structure of such rubber dual density footwear boots makes that the resistance value of rubber dual density footwear boots is very big.Thereby in the ordinary course of things, rubber dual density footwear boots can not be antistatic because the resistance value of foaming layer rubber is big.The patent of invention of relevant anlistatig rubber dual density footwear boots yet there are no report.
Summary of the invention
Technical problem to be solved by this invention provides a kind of dual density sole and preparation method thereof and antistatic dual density footwear boots and preparation method thereof, and the foaming layer rubber density of obtained rubber dual density footwear boots is at 0.7-0.8g/cm
3Between, the density 1.1-1.2g/cm of bottom rubber
3Between.The heel of rubber dual density sole also is provided with the conduction nail, and foaming layer rubber, wood are followed and the perforation of the interior end, and rubber dual density footwear boots are mixed antistatic shoe-pad, and it becomes the footwear resistance value 10
5-10
9Between ohm, meet the national standard requirement of antistatic shoes boots.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of dual density sole comprises bottom rubber layer and foaming layer rubber layer.
The raw material of bottom rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 6～8 parts of activating agents, 1.6～2.4 parts in age resistor,
35～45 parts of conductive blacks, 15～25 parts in plasticizer, 7～9 parts of tackifier,
1.5～1.7 parts of vulcanizing agents, 1.8～2.9 parts of promoter;
The raw material of foaming layer rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 6～8 parts of activating agents, 1.6～2.4 parts in age resistor,
35～45 parts of carbon blacks, 20～30 parts in plasticizer, 7～9 parts of tackifier,
2.0～2.2 parts of vulcanizing agents, 2.0～3.1 parts of promoter, 0.10～0.15 part of blowing agent.
As a kind of restriction of the present invention, in the described bottom rubber layer raw material
A) described acrylonitrile-butadiene rubber is the acrylonitrile-butadiene rubber of medium acrylonitrile content;
B) consisting of of described activating agent: 4～5 parts in zinc oxide, 2～3 parts of stearic acid;
C) described age resistor is: 0.8～1.2 part in heterocyclic age resistor, 0.8～1.2 part of amines antioxidants;
D) described promoter is: 1.0～1.5 parts of thiazole accelerators, 0.5～0.8 part of sulfenamide type accelerators, 0.3～0.6 part of thuriam acceserator.
As the further restriction to above-mentioned restriction, described conductive black is acetylene carbon black;
Described heterocyclic age resistor is 2-mercaptobenzimidazole; Described amines antioxidants is age resistor N-isopropyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulfenamide; Described thuriam acceserator is tetramethylthiuram disulfide;
Described plasticizer is dioctyl phthalate; Described tackifying resin is the grand resin of solid horse;
Described vulcanizing agent is the above Cosans of fineness 200 orders.
As the set forth in detail to foregoing of the present invention, particular content is as follows:
Use the acrylonitrile-butadiene rubber N230S of medium acrylonitrile content in the present invention, have electric conductivity and oil resistivity preferably at the bottom of the glue that adopts the acrylonitrile-butadiene rubber of medium acrylonitrile content to make;
Use age resistor 2-mercaptobenzimidazole (antioxidant MB) in the present invention, can play protective action preferably to the thermo-oxidative ageing of rubber soles, Weather etc.; Use age resistor N-isopropyl N '-diphenyl-para-phenylene diamine (antioxidant 4010NA), to improving anti-ozone aging performance, the anti-flex crack performance effect of being very helpful of rubber soles; Antioxidant MB and 4010NA are used, to preventing rubber heat ageing, oxygen aging, light aging, dynamic fatigue and resisting that poisonous metal catalysis such as copper, manganese are aging an efficient synergy.
In the present invention, the conductive black that uses is acetylene carbon black.This is in order to increase the electric conductivity of vulcanizate, to improve into the antistatic behaviour of footwear.The addition of acetylene carbon black is 35-45 part, because the calendering process of acetylene carbon black is bad, surpasses this amount, and the processability of elastomeric compound can serious deterioration.On the contrary, if use level is lower than 35-45 part, then the electric conductivity at the bottom of the glue can not reach requirement.
The use of accelerator dibenzothiazyl disulfide (altax) can improve rubber vulcanization speed and state of cure (vulcanization) in the present invention, because thiazole accelerator plays sulphur early, curingprocess rate is fast, and the state of cure (vulcanization) height is so vulcanizating glue physical performance is good.
Use promoter sulfenamide (being accelerant CZ) and tetramethylthiuram disulfide (being TM monex TD) as kicker in the present invention.The use of these two kinds of promoter is played activation for altax, can further improve curingprocess rate and the state of cure (vulcanization) of sizing material, improves the physical property of vulcanizate.
Among the present invention, the altax of 1-1.5 weight portion can guarantee that vulcanizate has suitable state of cure (vulcanization).If surpass this umber, the curingprocess rate of sizing material can be too fast, and is unfavorable to the safety in production of sizing material, also strengthened the danger of vulcanizate bloom; If be lower than this umber, can cause the state of cure (vulcanization) of vulcanizate not high, the elastomeric compound curingprocess rate is slow partially, be not suitable for using at rubber dual density footwear boots production line, the physical property of its vulcanizate also can descend, and specifically, the possibility that wear-resisting, the folding quality of one-tenth footwear do not reach requirement strengthens.
Other two kinds of accelerant CZs and TMTD belong to kicker in the present invention, and use level is less, and major function is the effect of playing the primary accelerator activation, and purpose is further to improve the state of cure (vulcanization) of vulcanizate, improves the physical property of vulcanizate.In the present invention, the use level of accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide (being accelerant CZ) is 0.5-0.8 part, advances agent because accelerant CZ is a kind of guarantor of aftereffect type, as a kind of kicker, can activate primary accelerator DM, to improve the effectiveness of primary accelerator DM.As kicker, use level is that half of primary accelerator is comparatively suitable, so determine that the suitable use level of accelerant CZ is 0.5-0.8 part.
Among the present invention, the use level of accelerant disulfide tetra methylthiuram (being TM monex TD) is 0.3-0.6 part.Because TM monex TD is the stronger promoter of a kind of activity, to use separately, its curingprocess rate is fast, the state of cure (vulcanization) height.As kicker, its use level is unsuitable big, and in the present invention, the use level of TM monex TD is lower than the use level of accelerant CZ, is 0.3-0.6 part.It mainly is the curingprocess rate of control elastomeric compound.If the use level of TM monex TD is lower than this, then do not have the activation to primary accelerator DM, if be higher than this use level, can make the curingprocess rate of elastomeric compound too fast again, be not suitable as primer and use at rubber dual density production line.
Among the present invention, the use of the grand resin of the solid horse of tackifier mainly is the tack that increases sizing material, improves the explained hereafter performance of elastomeric compound, and then improves the qualification rate of finished product.
Among the present invention, the use level of plasticizer DOP is 15-25 part, and the effect of plasticizer mainly is the hardness of control sizing material, improves the operating procedure performance of sizing material, is convenient to processing.Because the hardness at the bottom of the rubber dual density footwear boots glue is generally about ShoreA 55 degree, so in the present invention, use level 15-25 part of plasticizer DOP is proper.After if this amount of surpassing, footwear last are pressed and finished, become the meeting of footwear hardness on the low side, nonconforming.On the contrary, if plasticizer loading is lower than 15-25 part, can cause the mixing difficulty of sizing material, other compounding ingredient disperses bad, and vulcanizate hardness is higher, and the hardness at the bottom of the one-tenth footwear glue is also nonconforming.
Among the present invention, the use of vulcanizing agent can be so that chemical reaction can take place in elastomeric compound after being heated, vulcanization crosslinking, and rubber is transformed into the big molecule of build from linear macromolecule, and then becomes the vulcanizate that stable chemical state is arranged.The parts by weight of vulcanizing agent are 1.5-1.7, if be higher than this umber, have following two disadvantages:
A). can make the vulcanizate state of cure (vulcanization) higher, vulcanizate hardness is nonconforming;
B). can make the curingprocess rate of elastomeric compound fast, sulfuration is too short induction period, and sizing material does not have enough safety in production, cannot ordinary production on rubber dual density footwear boots production line;
If but were lower than this umber, would have following two disadvantages:
A). can cause curingprocess rate slow excessively, can not be on rubber dual density footwear boots production line ordinary production;
B). can make the vulcanizate state of cure (vulcanization) low excessively, vulcanizating glue physical performance does not reach requirement, and product shoes is nonconforming.
As another kind of restriction the of the present invention, in the described foaming layer rubber layer raw material
A) described acrylonitrile-butadiene rubber is the acrylonitrile-butadiene rubber of low acrylonitrile content, N240S;
B) consisting of of described activating agent: 4～5 parts in zinc oxide, 2～3 parts of stearic acid;
C) described age resistor is: 0.8～1.2 part in heterocyclic age resistor, 0.8～1.2 part of amines antioxidants;
D) described promoter is: 1.0～1.5 parts of thiazole accelerators, 0.5～0.8 part of sulfenamide type accelerators, 0.5～0.8 part of thuriam acceserator.
As the further restriction of above-mentioned restriction, described carbon black is high wear-resistant carbon black N330;
Described heterocyclic age resistor chemical name is 2-mercaptobenzimidazole; Described amines antioxidants is age resistor N-isopropyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulfenamide; Described thuriam acceserator is tetramethylthiuram disulfide;
Described plasticizer is dioctyl phthalate; Described tackifying resin is the grand resin of solid horse;
Described vulcanizing agent is the above Cosans of fineness 200 orders; Described blowing agent is two benzene sulfonyl hydrazide ethers.
As to foregoing set forth in detail of the present invention, particular content is as follows:
Use the acrylonitrile-butadiene rubber of low acrylonitrile content in the present invention, model is N240S, mainly be because in rubber dual density footwear boots, the foaming layer rubber layer will with bottom rubber layer co-vulcanization, both in conjunction with problem just, owing to used the conduction nail in the present invention, so no longer consider the electric conductivity of rubber in the foaming layer rubber layer, with respect to the acrylonitrile-butadiene rubber of medium acrylonitrile content, the curingprocess rate of the acrylonitrile-butadiene rubber of low acrylonitrile content will obviously be accelerated, the good manufacturability of sizing material, be adapted at using in the foaming layer rubber layer, and they all belong to a class rubber together, so, as long as control the curingprocess rate of sizing material well, good co-vulcanization should be arranged between the two.
Use age resistor 2-mercaptobenzimidazole (being antioxidant MB) in the present invention, can play protective action preferably to the thermo-oxidative ageing of rubber soles, Weather etc.; Use age resistor N-isopropyl N '-diphenyl-para-phenylene diamine (being antioxidant 4010NA), to improving anti-ozone aging performance, the anti-flex crack performance effect of being very helpful of rubber soles; Antioxidant MB and 4010NA are used, to preventing rubber heat ageing, oxygen aging, light aging, dynamic fatigue and resisting that poisonous metal catalysis such as copper, manganese are aging an efficient synergy.
In the present invention, the carbon black that uses in the foamed glue is high wear-resistant carbon black N330, and this is because in the present invention, and the rear heel of footwear boots has adopted the metallic conduction nail with the short circuit of foaming layer rubber, and foaming rubber layer no longer needs to consider electric conductivity.Carbon black is only required that reinforcement to a certain degree gets final product.
The use of accelerator dibenzothiazyl disulfide (altax) can improve rubber vulcanization speed and state of cure (vulcanization) in the present invention, because thiazole accelerator plays sulphur early, curingprocess rate is fast, and the state of cure (vulcanization) height is so vulcanizating glue physical performance is good.
Use promoter sulfenamide (accelerant CZ) and tetramethylthiuram disulfide (TM monex TD) in the present invention.The use of these two kinds of promoter, DM plays activation to primary accelerator.Can further improve curingprocess rate and the state of cure (vulcanization) of sizing material, improve the physical property of vulcanizate.
Among the present invention, the altax of 1-1.5 parts by weight can guarantee that vulcanizate has suitable state of cure (vulcanization).If surpass this umber, the curingprocess rate of sizing material can be too fast, and is unfavorable to the safety in production of sizing material, also strengthened the danger of vulcanizate bloom; If be lower than this umber, can cause the state of cure (vulcanization) of vulcanizate not high, curingprocess rate is slow partially, and the possibility of owing sulphur strengthens, the physical property of vulcanizate descends, and can have influence on the bondability of foamed glue and upper of a shoe.
Other two kinds of accelerant CZs and TMTD belong to kicker in the present invention, and use level is less, and major function is the effect of playing the primary accelerator activation, and purpose is further to improve the state of cure (vulcanization) of vulcanizate, improves the physical property of vulcanizate.
In the present invention, the use level of accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide (accelerant CZ) is 0.5-0.8 part, advances agent because accelerant CZ is a kind of guarantor of aftereffect type, as a kind of kicker, can activate primary accelerator DM, to improve the effectiveness of primary accelerator DM.As kicker, use level is half best results of altax, so determine that the suitable use level of accelerant CZ is 0.5-0.8 part.
Among the present invention, the use level of accelerant disulfide tetra methylthiuram (TM monex TD) is 0.5-0.8 part.Because TM monex TD is the stronger promoter of a kind of activity, if use separately, its curingprocess rate is very fast, and state of cure (vulcanization) is higher.As kicker, its use level is unsuitable excessive, in the present invention, the use level of TM monex TD is bigger than the use level of TM monex TD in the primer in the foamed glue, reason is on rubber dual density footwear boots production line, the cure time of foaming layer rubber is shorter than the cure time of bottom rubber, thereby the curingprocess rate of foamed glue must be faster than the curingprocess rate of primer.If the use level of TM monex TD is lower than this, can make the curingprocess rate of elastomeric compound slow partially again, be not suitable for using at rubber dual density production line.
Among the present invention, the effect of plasticizer DOP mainly is the hardness that reduces sizing material, improves the operating procedure performance of sizing material.Because the basic hardness of rubber dual density footwear boots rubber pange glue is generally about the ShoreA40 degree, so in the present invention, use level 20-30 part of plasticizer DOP is proper.If surpass this amount, elastomeric compound can be too soft, and one is unfavorable for that the workman refines glue, two come the footwear last to press finish after, become the footwear hardness can be on the low side, nonconforming.On the contrary, if plasticizer loading is lower than 20-30 part, become the hardness of footwear foaming layer rubber also nonconforming.
Among the present invention, the use level of vulcanizing agent is 2.0-2.2 part in the foaming rubber layer, and is bigger than the use level of bottom rubber layer.Mainly be in order to improve the curingprocess rate of sizing material, to be fit to the actual requirement on the rubber dual density footwear boots production line.
The present invention also provides above-mentioned dual density preparation of soles method, and wherein, the preparation method of bottom rubber layer carries out according to the following steps order:
(1) weighing of rubber compounding ingredient is prepared
According to the prescription requirement, various materials are carried out accurate weighing, standby;
(2) sizing material banburying
Raw materials such as above-mentioned ready acrylonitrile-butadiene rubber, activating agent, age resistor, carbon black, tackifier, plasticizer are dropped into banbury carry out banburying, when the sizing material temperature reaches 120 ℃, binder removal;
(3) sizing material is mixing
Fall behind under the sizing material, the bag roller adds vulcanizing agent, promoter, treats that above-mentioned powder sneaks into after the sizing material, and sizing material is played five triangle bags powder is uniformly dispersed in sizing material, slice then, cooling makes elastomeric compound, and is standby;
(4) check of elastomeric compound
Above-mentioned elastomeric compound was left standstill 24 hours, therefrom extract sample, carry out the check of vulcanization characteristics, physical property, carry out next step after qualified;
(5) adhesive tape manufacturing
The above-mentioned elastomeric compound that is up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, use cutter that sizing material is manufactured the thick adhesive tape of the wide 1cm of 8cm, use for rubber dual density footwear boots production line.
The preparation method of foaming layer rubber layer carries out according to the following steps order:
(1) weighing of rubber compounding ingredient is prepared
According to the prescription requirement, various materials are carried out accurate weighing, standby;
(2) sizing material banburying
Raw materials such as above-mentioned ready acrylonitrile-butadiene rubber, activating agent, age resistor, carbon black, tackifier, plasticizer are dropped into banbury carry out banburying, when the sizing material temperature reaches 120 ℃, binder removal;
(3) sizing material is mixing
Fall behind under the sizing material, the bag roller adds vulcanizing agent, promoter, blowing agent, treats that above-mentioned powder sneaks into after the sizing material, and sizing material is played five triangle bags powder is uniformly dispersed in sizing material, slice then, cooling makes elastomeric compound, and is standby;
(4) check of elastomeric compound
Above-mentioned elastomeric compound was left standstill 24 hours, therefrom extract sample, carry out the check of vulcanization characteristics, physical property, carry out next step after qualified;
(5) adhesive tape manufacturing
The above-mentioned elastomeric compound that is up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, use cutter that sizing material is manufactured the thick adhesive tape of the wide 1cm of 8cm, use for rubber dual density footwear boots production line.
The present invention also provides a kind of antistatic dual density footwear boots, and it comprises upper of a shoe and sole, and sole comprises bottom rubber layer, the foaming layer rubber layer of above-mentioned preparation, also comprise spring heel portion and through foamed glue, wood with the nail of the conduction at, the interior end.
Described conduction nail is bar-shaped, diameter 3mm, length 15mm, the two ends head is rounded, material is common carbon steel, and it runs through and the wood that is fixed in the rear portion of rubber dual density footwear boots is followed, and penetrates the foaming layer rubber of footwear boots, contact with the bottom rubber phase of rubber dual density footwear boots, conduction is followed closely the order from top to bottom of the sole heel that runs through for the end, wood in the footwear are followed, foaming layer rubber.Like this, the footwear boots are being worn under the state, and human body can pass through shoe-pad, along the conduction nail, are connected with primer, because primer electric conductivity is better, so the resistance value of whole shoes is 10
5-10
9Between ohm, thereby realize the anlistatig purpose of footwear boots.
The present invention also provides the preparation method of above-mentioned antistatic dual density footwear boots, and it carries out according to the following steps order:
(1) group cuts out under the sheet: material, standard, pattern carry out various materials and tailor according to the rules;
(2) seam group: group's sheet that above-mentioned download is good is made in accordance with regulations, becomes group;
(3) end processed: above-mentioned one-tenth is helped to stretch tight shoe last or hat block, the end processed;
(4) the conduction nail is installed: at wood with the middle part, apart from wood front the 3cm of portion, at wood with the middle part, about 2.75cm place apart from the edge, the hole of diameter 3mm is beaten by elder generation, and passes at the interior end, and then with metallic conduction bind into, metallic conduction is followed closely equal with inner bottom surface;
(5) check: after the assay was approved, send the mold pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual density footwear boots production line, adjust various parameters, notice that the metallic conduction nail at counter place is not tear-away, lose, will note during overshoes on the iron pin upper of a shoe struck to pound putting in place.After every preparation puts in place, sizing material is injected mould, the beginning mold pressing.Mold pressing is taken out into footwear after finishing, check.Wait is dispatched from the factory.
Owing to adopted above-mentioned technical scheme, the present invention compared with prior art, obtained technological progress is:
The sole of dual density footwear boots of the present invention adopts acrylonitrile-butadiene rubber and conductive black material, make the rubber soles of prepared dual density have tangible oil resistivity and electric conductivity, compare with antistatic polyurethane class sole, its hydrolytic resistance, cold resistance is all relatively good, the antistatic life-span of footwear boots is long, avoided in the prior art in the polyurethanes sole for antistatic and add antistatic additive therein, used antistatic additive mostly is the quaternary ammonium salt antistatic additive, this antistatic additive is after the footwear boots wear several years, can lose antistatic behaviour at leisure, and the not hydrolysis of polyurethanes sole, cold resistance is bad.Use antistatic additive in the polyurethanes sole after, become the hardness of footwear to descend accordingly, folding resistance descends, and can influence the demould time of sole aborning, reduce the production efficiency in the actual production, prepared sole influences the quality of footwear because softer and pierced through by pricking object easily.And the present invention has overcome above-mentioned technical problem.
The foaming layer rubber layer density of the prepared antistatic dual density footwear of the present invention is 0.7-0.8 g/cm
3Between, bottom rubber layer density is 1.1-1.2 g/cm
3Also be provided with the conduction nail in the dual density sole, foaming layer rubber layer, wood are followed and the perforation of the interior end, from electrotechnical angle, be equivalent to conducting metal nail the foaming layer rubber layer of sole, wood follow, the short circuit of the interior end, the dual density footwear boots made from the method so just can significantly be lowered into the resistance value of footwear, so just can possess anti-static function.The resistance value of the one-tenth footwear of prepared antistatic dual density footwear is 10
5-10
9Between ohm, meet the national standard anti-static shoes specification requirement of antistatic shoes boots.
The present invention is applicable to the preparation of antistatic rubber dual density footwear boots, further is applied to military antistatic shoes boots.
The present invention is described in further detail below in conjunction with specific embodiment.
The specific embodiment
Embodiment 1
A kind of dual density sole, it comprises upper of a shoe and sole, sole comprises bottom rubber layer, foaming layer rubber layer and is positioned at spring heel portion and runs through foaming layer rubber layer, wood with the conduction nail at, the end that wherein the raw material of bottom rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 5 parts in zinc oxide, 3 parts of stearic acid;
0.8 part of 2～mercaptobenzimidazole, 0.8 part of N-isopropyl N '-diphenyl-para-phenylene diamine;
35 parts of acetylene carbon blacks, 15 parts of dioctyl phthalates, 7 parts of the grand resins of solid horse,
1.5 parts of Cosans, 1.0 parts of dibenzothiazyl disulfides,
0.5 part of N-cyclohexyl-2-[4-morpholinodithio sulfenamide, 0.3 part of tetramethylthiuram disulfide.
The raw material of foaming layer rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 5 parts in zinc oxide, 3 parts of stearic acid;
0.8 part of 2～mercaptobenzimidazole, 0.8 part of N-isopropyl N`-diphenyl-para-phenylene diamine;
35 parts of high wear-resistant carbon black N330,20 parts of dioctyl phthalates, 7 parts of the grand resins of solid horse,
1.5 parts of Cosans, 1.0 parts of dibenzothiazyl disulfides,
0.5 part of N-cyclohexyl-2-[4-morpholinodithio sulfenamide, 0.5 part of tetramethylthiuram disulfide,
0.10 part in two benzene sulfonyl hydrazide ethers.
The method for preparing above-mentioned dual density sole, wherein, the bottom rubber layer is similar to the preparation method of foaming layer rubber layer, and concrete preparation method carries out according to the following steps order:
(1) weighing of rubber compounding ingredient is prepared
According to the prescription requirement, various materials are carried out accurate weighing, standby;
(2) sizing material banburying
Raw materials such as above-mentioned ready acrylonitrile-butadiene rubber, activating agent, age resistor, carbon black, tackifier, plasticizer are dropped into banbury carry out banburying, when the sizing material temperature reaches 120 ℃, binder removal;
(3) sizing material is mixing
Fall behind under the sizing material, the bag roller adds vulcanizing agent, promoter (foaming layer rubber adds blowing agent at this moment), treat that above-mentioned powder sneaks into after the sizing material, sizing material is played five triangle bags powder is uniformly dispersed in sizing material, then slice, cooling makes elastomeric compound, and is standby;
(4) check of elastomeric compound
Above-mentioned elastomeric compound was left standstill 24 hours, therefrom extract sample, carry out the check of vulcanization characteristics, physical property, carry out next step after qualified;
(5) adhesive tape manufacturing
The above-mentioned elastomeric compound that is up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, use cutter that sizing material is manufactured the thick adhesive tape of the wide 1cm of 8cm, use for rubber dual density footwear boots production line.
The preparation method of the antistatic dual density footwear boots that present embodiment provides, it carries out according to the following steps order:
(1) group cuts out under the sheet: material, standard, pattern carry out various materials and tailor according to the rules;
(2) seam group: group's sheet that above-mentioned download is good is made in accordance with regulations, becomes group;
(3) end processed: above-mentioned one-tenth is helped to stretch tight at shoe last or hat block and the end processed, be about to the dual density sole and make according to the rules;
(4) the conduction nail is installed: at wood with the middle part, apart from wood front the 3cm of portion, at wood with the middle part, about 2.75cm place apart from the edge, the hole of diameter 3mm is beaten by elder generation, and passes at the interior end, and then with metallic conduction bind into, metallic conduction is followed closely equal with inner bottom surface;
(5) check: after the assay was approved, send the mold pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual density footwear boots production line, adjust various parameters, notice that the metallic conduction nail at counter place is not tear-away, lose, will note during overshoes on the iron pin upper of a shoe struck to pound putting in place.After every preparation puts in place, sizing material is injected mould, the beginning mold pressing.Mold pressing is taken out into footwear after finishing, check, and the resistance value of prepared antistatic dual density footwear is 10
6Ohm.
Embodiment 2-5
Embodiment 2-5 is respectively a kind of antistatic dual density footwear boots, and the kind that each raw material of implementing is formed and the preparation method of antistatic dual density footwear are identical with embodiment's 1, and difference only is the difference of used parts by weight, specifically as shown in Table 1 and Table 2:
Embodiment 6-7
Embodiment 6-7 is respectively a kind of antistatic rubber dual density footwear boots, the kind that each raw material of implementing is formed and the preparation method of antistatic dual density footwear are identical with embodiment's 1, difference only is the difference of used raw material composition parts by weight, specifically shown in table 3 and table 4:
By the data in table 3 and the table 4 as can be known, owing to used 55 parts of acetylene carbon blacks in the bottom rubber layer, the serious deterioration of sizing material processability can't ordinary production on rubber dual density footwear boots production line among the embodiment 6.
In executing example 7, because the use level of acetylene carbon black is 50 parts, finally becoming the footwear resistance value is 10
3Ohm becomes a kind of conductive shoes, rather than antistatic shoes.
Claims (9)
1. a dual density sole comprises bottom rubber layer and foaming layer rubber layer,
It is characterized in that:
1. the raw material of bottom rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 6～8 parts of activating agents, 1.6～2.4 parts in age resistor,
35～45 parts of conductive blacks, 15～25 parts in plasticizer, 7～9 parts of tackifier,
1.5～1.7 parts of vulcanizing agents, 1.8～2.9 parts of promoter;
2. the raw material of foaming layer rubber layer is formed in parts by weight, comprising:
100 parts of acrylonitrile-butadiene rubbers, 6～8 parts of activating agents, 1.6～2.4 parts in age resistor,
35～45 parts of carbon blacks, 20～30 parts in plasticizer, 7～9 parts of tackifier,
2.0～2.2 parts of vulcanizing agents, 2.0～3.1 parts of promoter, 0.10～0.15 part of blowing agent.
2. dual density sole according to claim 1,
It is characterized in thatIn the described bottom rubber layer raw material
:
A) described acrylonitrile-butadiene rubber is the acrylonitrile-butadiene rubber of medium acrylonitrile content;
B) consisting of of described activating agent: 4～5 parts in zinc oxide, 2～3 parts of stearic acid;
C) described age resistor is: 0.8～1.2 part in heterocyclic age resistor, 0.8～1.2 part of amines antioxidants;
D) described promoter is: 1.0～1.5 parts of thiazole accelerators, 0.5～0.8 part of sulfenamide type accelerators, 0.3～0.6 part of thuriam acceserator;
E) described conductive black is acetylene carbon black;
F) described plasticizer is dioctyl phthalate; Described tackifying resin is the grand resin of solid horse.
3. dual density sole according to claim 2,
It is characterized in that:
Described heterocyclic age resistor is 2-mercaptobenzimidazole; Described amines antioxidants is age resistor N-isopropyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulfenamide; Described thuriam acceserator is tetramethylthiuram disulfide;
Described vulcanizing agent is the above Cosans of fineness 200 orders.
4. dual density sole according to claim 1,
It is characterized in thatIn the described foaming layer rubber layer raw material
:
A) described acrylonitrile-butadiene rubber is the acrylonitrile-butadiene rubber of low content acrylonitrile;
B) consisting of of described activating agent: 4～5 parts in zinc oxide, 2～3 parts of stearic acid;
C) described age resistor is: 0.8～1.2 part in heterocyclic age resistor, 0.8～1.2 part of amines antioxidants;
D) described promoter is: 1.0～1.5 parts of thiazole accelerators, 0.5～0.8 part of sulfenamide type accelerators, 0.5～0.8 part of thuriam acceserator;
E) described carbon black is high wear-resistant carbon black N330;
F) described plasticizer is dioctyl phthalate; Described tackifying resin is the grand resin of solid horse.
5. dual density sole according to claim 4,
It is characterized in that:
Described heterocyclic age resistor chemical name is 2-mercaptobenzimidazole; Described amines antioxidants is age resistor N-isopropyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulfenamide; Described thuriam acceserator is tetramethylthiuram disulfide;
Described vulcanizing agent is the above Cosans of fineness 200 orders; Described blowing agent is two benzene sulfonyl hydrazide ethers.
6. one kind as each described dual density preparation of soles method among the claim 1-5,
It is characterized in thatThe preparation method of bottom rubber layer carries out according to the following steps order:
(1) weighing of rubber compounding ingredient is prepared
According to the prescription requirement, various materials are carried out accurate weighing, standby;
(2) sizing material banburying
Raw materials such as above-mentioned ready acrylonitrile-butadiene rubber, activating agent, age resistor, carbon black, tackifier, plasticizer are dropped into banbury carry out banburying, when the sizing material temperature reaches 120 ℃, binder removal;
(3) sizing material is mixing
Fall behind under the sizing material, the bag roller adds vulcanizing agent, promoter, treats that above-mentioned powder sneaks into after the sizing material, and sizing material is played five triangle bags powder is uniformly dispersed in sizing material, slice then, cooling makes elastomeric compound, and is standby;
(4) check of elastomeric compound
Above-mentioned elastomeric compound was left standstill 24 hours, therefrom extract sample, carry out the check of vulcanization characteristics, physical property, carry out next step after qualified;
(5) adhesive tape manufacturing
The above-mentioned elastomeric compound that is up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, use cutter that sizing material is manufactured the thick adhesive tape of the wide 1cm of 8cm, use for rubber dual density footwear boots production line.
7. one kind as each described dual density preparation of soles method among the claim 1-5,
It is characterized in thatThe preparation method of foaming layer rubber layer carries out according to the following steps order:
(1) weighing of rubber compounding ingredient is prepared
According to the prescription requirement, various materials are carried out accurate weighing, standby;
(2) sizing material banburying
Raw materials such as above-mentioned ready acrylonitrile-butadiene rubber, activating agent, age resistor, carbon black, tackifier, plasticizer are dropped into banbury carry out banburying, when the sizing material temperature reaches 120 ℃, binder removal;
(3) sizing material is mixing
Fall behind under the sizing material, the bag roller adds vulcanizing agent, promoter, blowing agent, treats that above-mentioned powder sneaks into after the sizing material, and sizing material is played five triangle bags powder is uniformly dispersed in sizing material, slice then, cooling makes elastomeric compound, and is standby;
(4) check of elastomeric compound
Above-mentioned elastomeric compound was left standstill 24 hours, therefrom extract sample, carry out the check of vulcanization characteristics, physical property, carry out next step after qualified;
(5) adhesive tape manufacturing
The above-mentioned elastomeric compound that is up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, use cutter that sizing material is manufactured the thick adhesive tape of the wide 1cm of 8cm, use for rubber dual density footwear boots production line.
8. antistatic dual density footwear boots,
It is characterized in thatIt comprises upper of a shoe and sole, and sole comprises bottom rubber layer, the foaming layer rubber layer of each described dual density sole among the claim 1-5, also comprises being positioned at spring heel portion and following the conduction nail that reaches the end through foaming layer rubber layer and wood.
9. the preparation method of antistatic dual density footwear boots as claimed in claim 8,
It is characterized in thatIt carries out according to the following steps order:
(1) group cuts out under the sheet: material, standard, pattern carry out various materials and tailor according to the rules;
(2) seam group: group's sheet that above-mentioned download is good is made in accordance with regulations, becomes group;
(3) end processed: above-mentioned one-tenth is helped to stretch tight shoe last or hat block, the end processed;
(4) the conduction nail is installed: at the medium position that wood is followed, apart from portion 3cm place, wood front, the hole of diameter 3mm is beaten at about 2.75cm place apart from the edge, and passes at the interior end, and then with metallic conduction bind into, the end that metallic conduction is followed closely is equal with inner bottom surface;
(5) check: after the assay was approved, send the mold pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual density footwear boots production line, adjust various parameters, check the installation situation of conduction nail, and sizing material is injected mould, the beginning mold pressing, mold pressing is taken out into footwear after finishing, check.
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| CN201310191319.2A CN103263115B (en) | 2013-05-22 | 2013-05-22 | Double-density sole, preparation method of double-density sole, antistatic double-density shoe and preparation method of antistatic double-density shoe |
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| CN103483643A (en) * | 2013-10-11 | 2014-01-01 | 昆山纯柏精密五金有限公司 | Rubber composition for firefighting shoes |
| CN103589009A (en) * | 2013-10-24 | 2014-02-19 | 安徽工贸职业技术学院 | Electroconductive rubber sole glue stock |
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| CN105411103A (en) * | 2015-11-25 | 2016-03-23 | 际华三五一五皮革皮鞋有限公司 | Novel half-insole and shoe-upper forming technology |
| CN106317506A (en) * | 2016-08-24 | 2017-01-11 | 际华三五三实业有限公司 | Anti-skid and oil-resistant rubber soles with dual density |
| CN109575374A (en) * | 2018-12-17 | 2019-04-05 | 际华三五三实业有限公司 | A kind of dual-density sole |
| CN111471227A (en) * | 2020-04-24 | 2020-07-31 | 广东百卓鞋业有限公司 | Anti-electric shock double-density primer and preparation method thereof |
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