CN103263115B - 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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- CN103263115B CN103263115B CN201310191319.2A CN201310191319A CN103263115B CN 103263115 B CN103263115 B CN 103263115B CN 201310191319 A CN201310191319 A CN 201310191319A CN 103263115 B CN103263115 B CN 103263115B
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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 shoe boots, be specifically related to a kind of dual-density sole and preparation method and antistatic dual-density shoe boots and preparation method.
Background technology
Rubber dual-density shoe boots due to own wt light, wear light, snubber elastomeric is good, the dark welcome by human consumer.But because one deck bipeltate is arranged at the bottom of rubber dual-density shoe boots, the structure of such rubber dual-density shoe boots makes the resistance value of rubber dual-density shoe boots very large.Thus in the ordinary course of things, rubber dual-density shoe boots can not be antistatic because the resistance value of foaming layer rubber is large.About the patent of invention of anlistatig rubber dual-density shoe boots have not been reported.
Summary of the invention
Technical problem to be solved by this invention, is to provide a kind of dual-density sole and preparation method thereof and antistatic dual-density shoe boots and preparation method thereof, and the foaming layer rubber density of obtained rubber dual-density shoe 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 is also provided with conductive nail, foaming layer rubber, wood with and the interior end through, antistatic shoe-pad mixed by rubber dual-density shoe boots, and it becomes footwear resistance values 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 composition of bottom rubber layer, with weight parts, comprising:
Paracril 100 parts, promoting agent 6 ~ 8 parts, 1.6 ~ 2.4 parts, anti-aging agent,
Graphitized carbon black 35 ~ 45 parts, 15 ~ 25 parts, softening agent, tackifier 7 ~ 9 parts,
Vulcanizing agent 1.5 ~ 1.7 parts, promotor 1.8 ~ 2.9 parts;
The raw material composition of foaming layer rubber layer, with weight parts, comprising:
Paracril 100 parts, promoting agent 6 ~ 8 parts, 1.6 ~ 2.4 parts, anti-aging agent,
Carbon black 35 ~ 45 parts, 20 ~ 30 parts, softening agent, tackifier 7 ~ 9 parts,
Vulcanizing agent 2.0 ~ 2.2 parts, promotor 2.0 ~ 3.1 parts, whipping agent 0.10 ~ 0.15 part.
Limit, in described bottom rubber layer raw material as one of the present invention
A) described paracril is the paracril of medium acrylonitrile content;
B) consisting of of the promoting agent described in: 4 ~ 5 parts, zinc oxide, stearic acid 2 ~ 3 parts;
C) anti-aging agent described in is: 0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 0.8 ~ 1.2 part;
D) promotor described in is: thiazole accelerator 1.0 ~ 1.5 parts, sulfenamide type accelerators 0.5 ~ 0.8 part, thiuram type accelerator 0.3 ~ 0.6 part.
As the further restriction to above-mentioned restriction, described graphitized carbon black is Shawinigan black;
Described heterocyclic anti-aging agent is 2-mercaptobenzimidazole; Described amines antioxidants is anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulphenamide; Described thiuram type accelerator is tetramethyl-thiuram disulfide;
Described softening agent is dioctyl phthalate (DOP); Described tackifying resin is the solid grand resin of horse;
Described vulcanizing agent is the SULPHUR POWDER of more than fineness 200 order.
As the detailed statement to foregoing of the present invention, particular content is as follows:
Use the paracril N230S of medium acrylonitrile content in the present invention, adopt at the bottom of the obtained glue of the paracril of medium acrylonitrile content and there is good electroconductibility and oil-proofness;
Use anti-aging agent 2-mercaptobenzimidazole (antioxidant MB) in the present invention, good protective effect can be played to the thermo-oxidative ageing, Weather etc. of rubber soles; Use anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine (antioxidant 4010NA), to the ozone-resistant aging resistance, the effect of being very helpful of flex cracking resistance performance that improve rubber soles; Antioxidant MB and 4010NA with the use of, to preventing rubber thermal ageing, oxygen aging, photoaging, dynamic fatigue and resisting that the catalysis of the poisonous metal such as copper, manganese is aging efficient synergy.
In the present invention, the graphitized carbon black of use is Shawinigan black.This is the electroconductibility in order to increase cross-linked rubber, improves into the static resistance of footwear.The addition of Shawinigan black is 35-45 part, because the calendering process of Shawinigan black is bad, exceed this amount, the processibility of rubber unvulcanizate can serious deterioration.On the contrary, if use level is lower than 35-45 part, then the electroconductibility at the bottom of glue can not reach requirement.
The use of accelerator dibenzothiazyl disulfide (altax), can improve rubber vulcanization speed and state of vulcanization in the present invention, and because thiazole accelerator plays sulphur comparatively early, vulcanization rate is fast, and state of vulcanization is high, so vulcanizating glue physical performance is good.
Use promotor sulphenamide (i.e. accelerant CZ) and tetramethyl-thiuram disulfide (i.e. Vulcanization accelerator TMTD) as secondary accelerator in the present invention.The use of these two kinds of promotor, plays activation for altax, can improve vulcanization rate and the state of vulcanization of sizing material further, improve the physicals of cross-linked rubber.
In the present invention, the altax of 1-1.5 weight part, can ensure that cross-linked rubber has suitable state of vulcanization.If exceed this number, the vulcanization rate of sizing material can be too fast, unfavorable to the safety in production of sizing material, also increases the danger of cross-linked rubber bloom; If lower than this number, the state of vulcanization of cross-linked rubber can be caused not high, and rubber unvulcanizate vulcanization rate is partially slow, be not suitable for using on rubber dual-density shoe boots production line, the physicals of its cross-linked rubber also can decline, and specifically, the possibility becoming wear-resisting, the folding quality of footwear not to reach requirement strengthens.
Other two kinds of accelerant CZs and TMTD in the present invention, belong to secondary accelerator, use level is less, and major function plays the effect to primary accelerator activation, and object improves the state of vulcanization of cross-linked rubber further, improves the physicals of cross-linked rubber.In the present invention, the use level of accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide (i.e. accelerant CZ) is 0.5-0.8 part, because the guarantor that accelerant CZ is a kind of rear acting type enters agent, as a kind of secondary accelerator, primary accelerator DM can be activated, to improve the effect of primary accelerator DM.As secondary accelerator, use level is that the half of primary accelerator is comparatively suitable, so determine that the suitable use level of accelerant CZ is 0.5-0.8 part.
In the present invention, the use level of accelerant disulfide tetra methylthiuram (being Vulcanization accelerator TMTD) is 0.3-0.6 part.Because Vulcanization accelerator TMTD is the promotor that a kind of activity is stronger, be used alone, its vulcanization rate is fast, and state of vulcanization is high.As secondary accelerator, its use level is unsuitable large, and in the present invention, the use level of Vulcanization accelerator TMTD is lower than the use level of accelerant CZ, is 0.3-0.6 part.Mainly control the vulcanization rate of rubber unvulcanizate.If the use level of Vulcanization accelerator TMTD is lower than this, then do not have the activation to primary accelerator DM, if higher than this use level, the vulcanization rate of rubber unvulcanizate can be made again too fast, be not suitable as primer and use on rubber dual density production line.
In the present invention, the use of the solid grand resin of horse of tackifier, mainly increases the autohension of sizing material, improves the explained hereafter performance of rubber unvulcanizate, and then improve the qualification rate of finished product.
In the present invention, the use level of plasticizer DOP is 15-25 part, and the effect of softening agent mainly controls the hardness of sizing material, improves the operating procedure performance of sizing material, is convenient to processing.Because the hardness at the bottom of rubber dual-density shoe boots glue is generally ShoreA about 55 degree, so in the present invention, use level 15-25 part of plasticizer DOP is proper.If exceed this amount, after footwear last pressure terminates, one-tenth footwear hardness can be on the low side, nonconforming.On the contrary, if plasticizer loading is lower than 15-25 part, can cause rubber compounding difficulty, the dispersion of other compounding ingredient is bad, and cross-linked rubber hardness is higher, becomes the hardness at the bottom of footwear glue also nonconforming.
In the present invention, the use of vulcanizing agent, rubber unvulcanizate can be made chemical reaction can to occur after being heated, vulcanization crosslinking, and rubber is transformed into build macromole from linear macromolecule, and then becomes the cross-linked rubber having stable chemical state.The parts by weight of vulcanizing agent are 1.5-1.7, if higher than this number, have following two disadvantages:
A). cross-linked rubber state of vulcanization can be made higher, and cross-linked rubber hardness is nonconforming;
B). the vulcanization rate of rubber unvulcanizate can be made fast, and sulfuration is too short for inductive phase, and sizing material does not have enough safety in production, and rubber dual-density shoe boots production line cannot normally be produced;
If but lower than this number, have following two disadvantages:
A). vulcanization rate can be caused excessively slow, normally can not produce on rubber dual-density shoe boots production line;
B). cross-linked rubber state of vulcanization can be made too low, and vulcanizating glue physical performance does not reach requirement, and product shoes is nonconforming.
Limit, in described foaming layer rubber layer raw material as another kind of the present invention
A) described paracril is the paracril of low acrylonitrile content, N240S;
B) consisting of of the promoting agent described in: 4 ~ 5 parts, zinc oxide, stearic acid 2 ~ 3 parts;
C) anti-aging agent described in is: 0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 0.8 ~ 1.2 part;
D) promotor described in is: thiazole accelerator 1.0 ~ 1.5 parts, sulfenamide type accelerators 0.5 ~ 0.8 part, thiuram type accelerator 0.5 ~ 0.8 part.
As the further restriction of above-mentioned restriction, described carbon black is high abrasion furnace carbon black N330;
Described heterocyclic anti-aging agent chemical name is 2-mercaptobenzimidazole; Described amines antioxidants is anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulphenamide; Described thiuram type accelerator is tetramethyl-thiuram disulfide;
Described softening agent is dioctyl phthalate (DOP); Described tackifying resin is the solid grand resin of horse;
Described vulcanizing agent is the SULPHUR POWDER of more than fineness 200 order; Described whipping agent is two benzol sulfohydrazide ethers.
State in detail as to foregoing of the present invention, particular content is as follows:
Use the paracril of low acrylonitrile content in the present invention, model is N240S, mainly because in rubber dual-density shoe boots, foaming layer rubber layer will with bottom rubber layer covulcanization, namely both in conjunction with problem, owing to employing conductive nail in the present invention, so no longer consider the electroconductibility of rubber in foaming layer rubber layer, relative to the paracril of medium acrylonitrile content, the vulcanization rate of the paracril of low acrylonitrile content will obviously be accelerated, the good manufacturability of sizing material, be adapted at using in foaming layer rubber layer, and they all belong to a class rubber together, so, as long as control the vulcanization rate of sizing material well, good covulcanization should be had between the two.
Use anti-aging agent 2-mercaptobenzimidazole (i.e. antioxidant MB) in the present invention, good protective effect can be played to the thermo-oxidative ageing, Weather etc. of rubber soles; Use anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine (i.e. antioxidant 4010NA), to the ozone-resistant aging resistance, the effect of being very helpful of flex cracking resistance performance that improve rubber soles; Antioxidant MB and 4010NA with the use of, to preventing rubber thermal ageing, oxygen aging, photoaging, dynamic fatigue and resisting that the catalysis of the poisonous metal such as copper, manganese is aging efficient synergy.
In the present invention, the carbon black used in foamed glue is high abrasion furnace carbon black N330, this is because in the present invention, the rear heel of footwear boots have employed metallic conduction nail by the short circuit of foaming layer rubber, and foaming rubber layer no longer needs to consider electroconductibility.Only require to a certain degree to carbon black reinforcing.
The use of accelerator dibenzothiazyl disulfide (altax), can improve rubber vulcanization speed and state of vulcanization in the present invention, and because thiazole accelerator plays sulphur early, vulcanization rate is fast, and state of vulcanization is high, so vulcanizating glue physical performance is good.
Use promotor sulphenamide (accelerant CZ) and tetramethyl-thiuram disulfide (Vulcanization accelerator TMTD) in the present invention.The use of these two kinds of promotor, plays activation to primary accelerator DM.Vulcanization rate and the state of vulcanization of sizing material can be improved further, improve the physicals of cross-linked rubber.
In the present invention, the altax of 1-1.5 parts by weight, can ensure that cross-linked rubber has suitable state of vulcanization.If exceed this number, the vulcanization rate of sizing material can be too fast, unfavorable to the safety in production of sizing material, also increases the danger of cross-linked rubber bloom; If lower than this number, the state of vulcanization of cross-linked rubber can be caused not high, vulcanization rate is partially slow, and the possibility of owing sulphur strengthens, the physicals of cross-linked rubber declines, and can have influence on the bondability of foamed glue and upper of a shoe.
Other two kinds of accelerant CZs and TMTD in the present invention, belong to secondary accelerator, use level is less, and major function plays the effect to primary accelerator activation, and object improves the state of vulcanization of cross-linked rubber further, improves the physicals of cross-linked rubber.
In the present invention, the use level of accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide (accelerant CZ) is 0.5-0.8 part, because the guarantor that accelerant CZ is a kind of rear acting type enters agent, as a kind of secondary accelerator, primary accelerator DM can be activated, to improve the effect of primary accelerator DM.As secondary accelerator, use level is the half best results of altax, so determine that the suitable use level of accelerant CZ is 0.5-0.8 part.
In the present invention, the use level of accelerant disulfide tetra methylthiuram (Vulcanization accelerator TMTD) is 0.5-0.8 part.Because Vulcanization accelerator TMTD is the promotor that a kind of activity is stronger, if be used alone, its vulcanization rate is very fast, and state of vulcanization is higher.As secondary accelerator, its use level is unsuitable excessive, in the present invention, in foamed glue, the use level of Vulcanization accelerator TMTD is larger than the use level of Vulcanization accelerator TMTD in primer, reason is on rubber dual-density shoe boots production line, the curing time of foaming layer rubber is shorter than the curing time of bottom rubber, and thus, the vulcanization rate of foamed glue must be faster than the vulcanization rate of primer.If the use level of Vulcanization accelerator TMTD is lower than this, the vulcanization rate of rubber unvulcanizate can be made again partially slow, be not suitable for using on rubber dual density production line.
In the present invention, the effect of plasticizer DOP mainly reduces the hardness of sizing material, improves the operating procedure performance of sizing material.Because the basic hardness of rubber dual-density shoe boots rubber pange glue is generally about ShoreA40 degree, so in the present invention, use level 20-30 part of plasticizer DOP is proper.If exceed this amount, rubber unvulcanizate can too soft, and one is unfavorable for that workman refines glue, and two come after footwear last pressure terminates, and one-tenth 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.
In the present invention, in foaming rubber layer, the use level of vulcanizing agent is 2.0-2.2 part, larger than the use level of bottom rubber layer.Mainly in order to improve the vulcanization rate of sizing material, be applicable to the actual requirement on rubber dual-density shoe boots production line.
Present invention also offers the preparation method of above-mentioned dual-density sole, wherein, the preparation method of bottom rubber layer carries out according to following steps order:
(1) weighing of rubber compounding material prepares
According to recipe requirements, various material is carried out precise, for subsequent use;
(2) sizing material banburying
The raw materials such as above-mentioned ready paracril, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(3) rubber compounding
Fall behind under sizing material, bag roller, adds vulcanizing agent, promotor, after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(4) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, after qualified, carry out next step;
(5) adhesive tape manufacture
The above-mentioned rubber unvulcanizate be up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter sizing material to be manufactured the thick adhesive tape of the wide 1cm of 8cm, for rubber dual-density shoe boots production line.
The preparation method of foaming layer rubber layer carries out according to following steps order:
(1) weighing of rubber compounding material prepares
According to recipe requirements, various material is carried out precise, for subsequent use;
(2) sizing material banburying
The raw materials such as above-mentioned ready paracril, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(3) rubber compounding
Fall behind under sizing material, bag roller, adds vulcanizing agent, promotor, whipping agent, after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(4) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, after qualified, carry out next step;
(5) adhesive tape manufacture
The above-mentioned rubber unvulcanizate be up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter sizing material to be manufactured the thick adhesive tape of the wide 1cm of 8cm, for rubber dual-density shoe boots production line.
Present invention also offers a kind of antistatic dual-density shoe boots, it comprises upper of a shoe and sole, and sole comprises bottom rubber layer, the foaming layer rubber layer of above-mentioned preparation, also comprises in spring heel portion and through foamed glue, wood with the conductive nail at, the interior end.
Described conductive nail is bar-shaped, diameter 3mm, length 15mm, two ends head is rounded, material is common carbon steel, and it runs through and the wood being fixed on the rear portion of rubber dual-density shoe boots is followed, and penetrates the foaming layer rubber of footwear boots, contact with the bottom rubber phase of rubber dual-density shoe boots, the order from top to bottom of the sole heel that conductive nail runs through is inner sole, wood is with, foaming layer rubber.Like this, footwear boots are under wearing effect, and human body can pass through shoe-pad, along conductive nail, is connected with primer, because primer electroconductibility is better, so the resistance value of whole shoes is 10
5-10
9between ohm, thus realize the anlistatig object of footwear boots.
Present invention also offers the preparation method of above-mentioned antistatic dual-density shoe boots, it carries out according to following steps order:
(1) help to cut out under sheet: material, standard, pattern carry out various material and tailor according to the rules;
(2) seam side: side sheet good for above-mentioned download is made by regulation, becomes side;
(3) end processed: stretch tight above-mentioned one-tenth side shoe last or hat block, the end processed;
(4) conductive nail is installed: at wood with middle part, apart from wood front portion 3cm, at wood with middle part, is about 2.75cm place apart from edge, first beats the hole of diameter 3mm, and pass the interior end, and then metallic conduction is bound into, metallic conduction is followed closely equal with inner bottom surface;
(5) check: after the assay was approved, send mould pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual-density shoe boots production line, adjust various parameter, notice that the metallic conduction nail at counter place is not tear-away, lose, during overshoes upper of a shoe will be noted to strike to pound putting in place on iron pin.After every preparation work puts in place, sizing material is injected mould, start mold pressing.After mold pressing terminates, take out into footwear, inspection.Wait is dispatched from the factory.
Owing to have employed above-mentioned technical scheme, compared with prior art, acquired technical progress is in the present invention:
The sole of dual-density shoe boots of the present invention adopts paracril and graphitized carbon black material, the rubber soles of obtained dual density is made to have obvious oil-proofness and electroconductibility, compared with antistatic polyurethane class sole, its hydrolytic resistance, winter hardiness is all relatively good, the footwear boots antistatic life-span is long, to avoid in prior art in polyurethanes sole in order to antistatic and add static inhibitor wherein, static inhibitor used is mostly quaternary ammonium salt static inhibitor, this static inhibitor is after footwear boots wear several years, static resistance can be lost at leisure, and the not hydrolysis of polyurethanes sole, winter hardiness is bad.Use static inhibitor in polyurethanes sole after, the hardness of corresponding one-tenth footwear can decline, and folding resistance declines, and the demould time of sole can be affected aborning, reduce the production efficiency in actual production, obtained sole is easily pierced through by pricking object because of softer, affects the quality of footwear.And instant invention overcomes above-mentioned technical problem.
The foaming layer rubber layer density of the antistatic dual-density shoe obtained by the present invention is 0.7-0.8 g/cm
3between, bottom rubber layer density is 1.1-1.2 g/cm
3also conductive nail is provided with in dual-density sole, foaming layer rubber layer, wood with and the interior end through, from electrotechnical angle, to be equivalent to conducting metal nail the foaming layer rubber layer of sole, wood with, short circuit of the interior end, so just significantly can be lowered into the resistance value of footwear, so just anti-static function can be possessed with the dual-density shoe boots that this method is made.The resistance value of the one-tenth footwear of obtained antistatic dual-density shoe is 10
5-10
9between ohm, meet the national standard anti-static shoes technical requirements of antistatic shoes boots.
The present invention is applicable to the preparation of antistatic rubber dual-density shoe boots, is further applied to military antistatic shoes boots.
The present invention is described in further detail below in conjunction with specific embodiment.
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 conductive nail at, the end, and wherein the raw material composition of bottom rubber layer is with weight parts, comprising:
Paracril 100 parts, 5 parts, zinc oxide, stearic acid 3 parts;
2 ~ mercaptobenzimidazole 0.8 part, N-sec.-propyl N '-diphenyl-para-phenylene diamine 0.8 part;
Shawinigan black 35 parts, dioctyl phthalate (DOP) 15 parts, the admittedly grand resin of horse 7 parts,
SULPHUR POWDER 1.5 parts, dibenzothiazyl disulfide 1.0 parts,
N-cyclohexyl-2-[4-morpholinodithio sulphenamide 0.5 part, tetramethyl-thiuram disulfide 0.3 part.
The raw material composition of foaming layer rubber layer, with weight parts, comprising:
Paracril 100 parts, 5 parts, zinc oxide, stearic acid 3 parts;
2 ~ mercaptobenzimidazole 0.8 part, N-sec.-propyl N`-diphenyl-para-phenylene diamine 0.8 part;
High abrasion furnace carbon black N330 35 parts, dioctyl phthalate (DOP) 20 parts, the admittedly grand resin of horse 7 parts,
SULPHUR POWDER 1.5 parts, dibenzothiazyl disulfide 1.0 parts,
N-cyclohexyl-2-[4-morpholinodithio sulphenamide 0.5 part, tetramethyl-thiuram disulfide 0.5 part,
Two 0.10 part, benzol sulfohydrazide ethers.
Prepare the method for above-mentioned dual-density sole, wherein, bottom rubber layer is similar to the preparation method of foaming layer rubber layer, and concrete preparation method carries out according to following steps order:
(1) weighing of rubber compounding material prepares
According to recipe requirements, various material is carried out precise, for subsequent use;
(2) sizing material banburying
The raw materials such as above-mentioned ready paracril, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(3) rubber compounding
Fall behind under sizing material, bag roller, adds vulcanizing agent, promotor (foaming layer rubber adds whipping agent at this moment), after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(4) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, after qualified, carry out next step;
(5) adhesive tape manufacture
The above-mentioned rubber unvulcanizate be up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter sizing material to be manufactured the thick adhesive tape of the wide 1cm of 8cm, for rubber dual-density shoe boots production line.
The preparation method of the antistatic dual-density shoe boots that the present embodiment provides, it carries out according to following steps order:
(1) help to cut out under sheet: material, standard, pattern carry out various material and tailor according to the rules;
(2) seam side: side sheet good for above-mentioned download is made by regulation, becomes side;
(3) end processed: above-mentioned one-tenth side is stretched tight shoe last or hat block the end processed, make according to the rules by dual-density sole;
(4) conductive nail is installed: at wood with middle part, apart from wood front portion 3cm, at wood with middle part, is about 2.75cm place apart from edge, first beats the hole of diameter 3mm, and pass the interior end, and then metallic conduction is bound into, metallic conduction is followed closely equal with inner bottom surface;
(5) check: after the assay was approved, send mould pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual-density shoe boots production line, adjust various parameter, notice that the metallic conduction nail at counter place is not tear-away, lose, during overshoes upper of a shoe will be noted to strike to pound putting in place on iron pin.After every preparation work puts in place, sizing material is injected mould, start mold pressing.After mold pressing terminates, take out into footwear, inspection, the resistance value of obtained antistatic dual-density shoe is 10
6ohm.
embodiment 2-5
Embodiment 2-5 is respectively a kind of antistatic dual-density shoe boots, the kind of each raw material composition implemented and the preparation method of antistatic dual-density shoe and the identical of embodiment 1, and difference is only the difference of parts by weight used, specifically as shown in Table 1 and Table 2:
embodiment 6-7
Embodiment 6-7 is respectively a kind of antistatic rubber dual-density shoe boots, the kind of the raw material composition of each enforcement and the preparation method of antistatic dual-density shoe and the identical of embodiment 1, difference is only the difference of raw material composition parts by weight used, specifically as shown in Table 3 and Table 4:
From the data in table 3 and table 4, owing to employing Shawinigan black 55 parts in bottom rubber layer in embodiment 6, sizing material processibility serious deterioration, rubber dual-density shoe boots production line cannot normally be produced.
Executing in example 7, the use level due to Shawinigan black is 50 parts, and final one-tenth footwear resistance value is 10
3ohm, becomes a kind of conductive shoes, instead of antistatic shoes.
Claims (5)
1. a dual-density sole, comprises bottom rubber layer and foaming layer rubber layer, it is characterized in that:
1. the raw material composition of bottom rubber layer is with weight parts, comprising:
Paracril 100 parts, promoting agent 6 ~ 8 parts, 1.6 ~ 2.4 parts, anti-aging agent,
Graphitized carbon black 35 ~ 45 parts, 15 ~ 25 parts, softening agent, tackifier 7 ~ 9 parts,
Vulcanizing agent 1.5 ~ 1.7 parts, promotor 1.8 ~ 2.9 parts;
2. the raw material composition of foaming layer rubber layer is with weight parts, comprising:
Paracril 100 parts, promoting agent 6 ~ 8 parts, 1.6 ~ 2.4 parts, anti-aging agent,
Carbon black 35 ~ 45 parts, 20 ~ 30 parts, softening agent, tackifier 7 ~ 9 parts,
Vulcanizing agent 2.0 ~ 2.2 parts, promotor 2.0 ~ 3.1 parts, whipping agent 0.10 ~ 0.15 part;
In described bottom rubber layer raw material:
A) described paracril is the paracril of medium acrylonitrile content;
B) consisting of of the promoting agent described in: 4 ~ 5 parts, zinc oxide, stearic acid 2 ~ 3 parts;
C) anti-aging agent described in is: 0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 0.8 ~ 1.2 part;
D) promotor described in is: thiazole accelerator 1.0 ~ 1.5 parts, sulfenamide type accelerators 0.5 ~ 0.8 part,
Thiuram type accelerator 0.3 ~ 0.6 part;
E) graphitized carbon black described in is Shawinigan black;
F) softening agent described in is dioctyl phthalate (DOP); Described tackifier are the solid grand resin of horse;
In described foaming layer rubber layer raw material:
A) described paracril is the paracril of low levels vinyl cyanide;
B) consisting of of the promoting agent described in: 4 ~ 5 parts, zinc oxide, stearic acid 2 ~ 3 parts;
C) anti-aging agent described in is: 0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 0.8 ~ 1.2 part;
D) promotor described in is: thiazole accelerator 1.0 ~ 1.5 parts, sulfenamide type accelerators 0.5 ~ 0.8 part,
Thiuram type accelerator 0.5 ~ 0.8 part;
E) carbon black described in is high abrasion furnace carbon black N330;
F) softening agent described in is dioctyl phthalate (DOP); Described tackifier are the solid grand resin of horse;
The preparation method of bottom rubber layer carries out according to following steps order:
(1) weighing of rubber compounding material prepares
According to recipe requirements, various material is carried out precise, for subsequent use;
(2) sizing material banburying
The raw materials such as above-mentioned paracril, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(3) rubber compounding
Fall behind under sizing material, bag roller, adds powder, and powder comprises vulcanizing agent and promotor, after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(4) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, qualified laggard
Go next step;
(5) adhesive tape manufacture
Above-mentioned rubber unvulcanizate is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter sizing material to be manufactured the thick adhesive tape of the wide 1cm of 8cm, for rubber dual-density shoe boots production line;
The preparation method of foaming layer rubber layer carries out according to following steps order:
(1) weighing of rubber compounding material prepares
According to recipe requirements, various material is carried out precise, for subsequent use;
(2) sizing material banburying
The raw materials such as above-mentioned paracril, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(3) rubber compounding
Fall behind under sizing material, bag roller, adds powder, and powder comprises vulcanizing agent, promotor and whipping agent, after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(4) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, after qualified, carry out next step;
(5) adhesive tape manufacture
Above-mentioned rubber unvulcanizate is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter sizing material to be manufactured the thick adhesive tape of the wide 1cm of 8cm, for rubber dual-density shoe boots production line.
2., according to the dual-density sole described in claim 1, it is characterized in that:
Described heterocyclic anti-aging agent is 2-mercaptobenzimidazole; Described amines antioxidants is anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-[4-morpholinodithio sulphenamide; Described thiuram type accelerator is tetramethyl-thiuram disulfide;
Described vulcanizing agent is the SULPHUR POWDER of more than fineness 200 order.
3., according to the dual-density sole described in claim 1, it is characterized in that:
Described heterocyclic anti-aging agent chemical name is 2-mercaptobenzimidazole; Described amines antioxidants is that anti-aging agent N-is different
Propyl group N '-diphenyl-para-phenylene diamine;
Described thiazole accelerator is dibenzothiazyl disulfide; Described sulfenamide type accelerators is N-cyclohexyl-2-benzene
And thiazolesulfenamide; Described thiuram type accelerator is tetramethyl-thiuram disulfide;
Described vulcanizing agent is the SULPHUR POWDER of more than fineness 200 order; Described whipping agent is two benzol sulfohydrazide ethers.
4. antistatic dual-density shoe boots, it is characterized in that it comprises upper of a shoe and sole, sole comprises bottom rubber layer, the foaming layer rubber layer of the dual-density sole according to any one of claim 1-3, also comprise be positioned at spring heel portion and through foaming layer rubber layer and wood with and the conductive nail at the end.
5. a preparation method for antistatic dual-density shoe boots as claimed in claim 4, is characterized in that it carries out according to following steps order:
(1) help to cut out under sheet: material, standard, pattern carry out various material and tailor according to the rules;
(2) seam side: above-mentioned side sheet is made by regulation, obtains into side;
(3) end processed: stretch tight above-mentioned one-tenth side shoe last or hat block, the end processed;
(4) conductive nail is installed: the medium position of following at wood, apart from wood front portion 3cm place, is about 2.75cm place apart from edge, beats the hole of diameter 3mm, and pass the interior end, and then metallic conduction is bound into, one end that metallic conduction is followed closely is equal with inner bottom surface;
(5) check: after the assay was approved, send mould pressing production line;
(6) upper of a shoe, adhesive tape are transported to rubber dual-density shoe boots production line, adjust various parameter, check the installation feelings of conductive nail
Condition, and sizing material is injected mould, start mold pressing, after mold pressing terminates, take out into footwear, inspection.
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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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| 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 |
| CN104473379A (en) * | 2014-11-06 | 2015-04-01 | 际华三五一五皮革皮鞋有限公司 | Dual density outsole shoemaking technology |
| CN105411103B (en) * | 2015-11-25 | 2019-06-14 | 际华三五一五皮革皮鞋有限公司 | Bottom upper of a shoe forming process in a kind of half |
| CN106317506B (en) * | 2016-08-24 | 2018-07-27 | 际华三五一三实业有限公司 | A kind of anti-skidding and oil resistant dual-density rubber sole |
| 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 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614188A1 (en) * | 1986-04-26 | 1987-10-29 | Basf Ag | Two-layer shoe sole having an outsole of polyurethane-polyurea elastomers, and a process for the production thereof |
| CN2126664Y (en) * | 1992-06-12 | 1993-02-03 | 胡德文 | Antistatic-electricity shoes |
| EP1281506A1 (en) * | 2001-08-02 | 2003-02-05 | Ipsa | Process for the production by moulding of a double density sole for footwear and in particular for safety shoes or sport shoes |
| CN100480030C (en) * | 2006-04-13 | 2009-04-22 | 天津雪豹鞋业有限公司 | Method of manufacturing injection-forming safety shoes with air vent system |
| CN101255243B (en) * | 2008-04-02 | 2010-04-14 | 际华三五一四制革制鞋有限公司 | Double-density shoe leather fast curing rubber size suitable for injection technique and production method thereof |
| CN101768292B (en) * | 2008-12-26 | 2011-06-15 | 际华三五一五皮革皮鞋有限公司 | Dual-density rubber material production formula and process thereof |
| CN101768297B (en) * | 2008-12-26 | 2011-11-09 | 际华三五一五皮革皮鞋有限公司 | Production formula of flame retardant dual density glue and production technique |
| CN102485778B (en) * | 2010-12-06 | 2014-05-07 | 际华三五一五皮革皮鞋有限公司 | Internal foaming rubber of dual density Goodyear outsole and preparation method thereof |
| CN102504362B (en) * | 2011-11-30 | 2014-05-21 | 际华三五一四制革制鞋有限公司 | Sizing material for rubber shoe sole and preparation method thereof |
| CN102718992B (en) * | 2012-06-06 | 2013-06-05 | 际华三五三九制鞋有限公司 | Oil-proof antistatic mould-pressing outsole rubber compound and preparation method thereof |
| CN102964640B (en) * | 2012-11-09 | 2014-12-31 | 际华三五一四制革制鞋有限公司 | Special rubber welt for rubber double-density shoes and preparation method thereof |
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