Summary of the invention
Technical problem to be solved by this invention is: provide a kind of loss of gloss type height surely to stretch footwear with at the bottom of black two sulphur and the preparation method, product resulting according to it realized complete loss of gloss by rubber body, production method is simple, low production cost, labour intensity is low, resulting good product quality is to overcome the deficiencies in the prior art.
At the bottom of the present invention is achieved in that loss of gloss type height is stretched footwear use black two sulphur surely, calculate by weight, it comprises 50~65 parts of natural rubbers, 10~15 parts of styrene-butadiene rubber(SBR), 25~35 parts of cis-butadiene cements, 1.9~2.1 parts of sulphur, 1.2~2.0 parts of vulcanization accelerators, 6~10 parts of vulcanization levellers, 1.2~1.5 parts of anti-aging agent, 15~25 parts of Rubber Softener and 50~60 parts of high wear-resistant carbon blacks.
Preferred scheme is, calculate by weight, it comprises 60 parts of natural rubbers, 10 parts of styrene-butadiene rubber(SBR), 30 parts of cis-1,4-polybutadiene rubbers, 2.0 parts of sulphur, 1.5 parts of vulcanization accelerators, 8.5 parts of vulcanization levellers, 1.4 parts of anti-aging agent, 20 parts of Rubber Softener and 55 parts of high wear-resistant carbon blacks.
Also comprise 0.1~0.4 part of Whitfield's ointment and 1.0~1.5 parts of releasing agent 935P.
Every 1.5 parts of vulcanization accelerators are comprised of 0.5 part of altax and 1.0 parts of accelerant CZs.
Every 8.5 parts of vulcanization levellers are comprised of 0.5 part of light magnesium oxide, 3 parts of stearic acid and 5 parts of nano zine oxides.
Every 20 parts of Rubber Softener are comprised of 3 parts of solid coumarones and 17 parts of machinery oil.
loss of gloss type height is stretched the preparation method at the bottom of footwear are used black two sulphur surely, and natural rubber is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber, dropped into successively styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, solid coumarone, light magnesium oxide, 1 part of stearic acid and 27 parts of high wear-resistant carbon blacks in Banbury mixer mixing 8 minutes jointly, add machinery oil, after refining glue load gos up, when pressing again refining to load to descend, discharge enters in opening rubber mixing machine, and after turning refining under 5~6mm roll spacing 8~9 minutes slice, get pre-dispersed carbon black rubber master batch, with broken-(down)rubber, pre-dispersed carbon black rubber master batch and middle material drop into and press refining 1 minute in Banbury mixer, add 28 parts of carbon blacks, continuing refining pressed 7 minutes, the cleaning Banbury mixer rim charge that will overflow adds banburying chamber, add simultaneously 7 parts of machinery oil, press again refining 2 minutes after continuing to press refining to go up to load, discharge enters opening rubber mixing machine, sizing material enters after mill in drop-down logical 8 roads of 4~5mm roll spacing, add sulphur, until sulphur eat powder complete after, operating on lower machine left and right intersects 8 roads that turn refining, adopt normal-temperature water to carry out two-sided cooling 30S after slice, upper separant, again material air is chilled to room temperature, namely get mixed sheet, after mixed sheet is deposited 3~4 days, the film of getting respectively same quantity from five parts of mixed sheets adds in opening rubber mixing machine, with film refine soft, refining is smooth, more lower sheet to enter refiner smooth with sizing material surface refining, scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain, two sulphur bottom die patterned surfaces are carried out the sandblast scale removal, with the mould after sandblast 150~170 ℃ of lower preheatings 15~20 minutes, load weighted two sulphur primer sheets are added to be preheating in satisfactory mould again, mould is pushed in vulcanizer, it is 20MPa that matched moulds is pressurized to operating pressure, the matched moulds time kept 1 second, unclamp exhaust handle, make the filler mould drop to the end, so repeat 3 times, matched moulds is pressurized to operating pressure 20MPa again, maintenance work pressure and homo(io)thermism sulfuration 4~8min, curing cycle unclamps mould after finishing, to take out from mould at the bottom of glue, namely obtain finished product at the bottom of two sulphur.
Described middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent.
Adopt method of the present invention to produce product, the performance of product tested, carry out following formulation screening test, thereby verify technical scheme of the present invention:
The formula test data:
Formula: 60 parts of natural rubbers, 10 parts of styrene-butadiene rubber(SBR), 30 parts of cis-1,4-polybutadiene rubbers, 2.0 parts of sulphur, 0.5 part of altax, 1.0 parts of accelerant CZs, 0.5 part of light magnesium oxide, 3 parts of stearic acid and 5 parts of nano zine oxides, 3 parts of solid coumarones, 17 parts of machinery oil, 55 parts of high wear-resistant carbon blacks.
The testing data screening process:
(1) reinforcing filler quantity research
The A basic recipe: it is variable that 60 parts of natural rubbers, 10 parts, styrene-butadiene rubber(SBR), 30 parts of cis-butadiene cements, 2 parts, sulphur, 1.5 parts of vulcanization accelerators, 8.5 parts of vulcanization levellers, solid coumarone, machinery oil, high abrasion are deceived.
The B testing program:
Table 1
Drawn by table 1, the best proportioning of test materials is: 55 parts of high wear-resistant carbon blacks, 3 parts of solid coumarones, 17 parts, machinery oil.This proportioning reaches the loss of gloss effect, and physicals is best, and processing performance is normal.
(2) vulcanization system simultaneous test
The A basic recipe: 60 parts of natural rubbers, 10 parts, styrene-butadiene rubber(SBR), 30 parts of cis-butadiene cements, 2 parts, sulphur, 3 parts of solid coumarones, 17 parts, machinery oil, black 55 parts of high abrasion, vulcanization accelerator, promoting agent are variable.
B Experimental Comparison table
Table 2
Annotate: anti-aging agent is by anti-aging agent CD1.5 part.
Table 2 presentation of results, vulcanization system and reactive systems optimum amount are: 0.5 part of altax, 1.0 parts of accelerant CZs, 5 parts of nano zine oxides, 3 parts of stearic acid, 0.4 part of light magnesium oxide.
(3) rubber is also with test
A basic recipe: 2.0 parts, sulphur, 0.5 part of altax, 1.0 parts of accelerant CZs, 5 parts of nano zine oxides, 3 parts of stearic acid, 0.4 part of light magnesium oxide, anti-aging agent CD1.0 part, 1.3 parts of antioxidant 4010NAs, 55 parts of carbon blacks, 17 parts, machinery oil, 3 parts of solid coumarones; Natural gum and synthetical glue are variable.
The B Experimental Comparison
Table 3
Table 3 presentation of results, the combined effect of natural gum: styrene-butadiene rubber(SBR): cis-butadiene cement=60:10:30 reaches best level, can take into account projects performance requriements.
(4) natural gum plasticity number simultaneous test
Table 4
Table 4 shows, when natural rubber was prepared as broken-(down)rubber, its plasticity number was at 0.40~0.50 o'clock, can take into account processing performance, loss of gloss specification of quality, belonged to top condition.
(5) vulcanisation operation mode and loss of gloss effect test
Table 5
For preventing that vulcanized rubber from producing the glue dirt and causing patterned surface shinny, require with the mould sandblast once every day.To guarantee loss of gloss effect and level.
Conclusion (of pressure testing):
Draw by above-mentioned test, optimum formula and processing condition are as follows:
Optimum formula: 60 parts of natural rubbers, 10 parts of styrene-butadiene rubber(SBR), 30 parts of cis-1,4-polybutadiene rubbers, 2.0 parts of sulphur, 0.5 part of altax, 1.0 parts of accelerant CZs, 0.5 part of light magnesium oxide, 3 parts of stearic acid and 5 parts of nano zine oxides, 3 parts of solid coumarones, 17 parts of machinery oil, 55 parts of high wear-resistant carbon blacks.
Process control condition: sulfuration starting point 2 ' 50 "~3 ' 20 ", the broken-(down)rubber plasticity number 0.40~0.50 of natural rubber.
Vulcanizing the end processed operation scheme is: after adding the sole film in the mould in the vulcanizing press, matched moulds is pressurized to operating pressure 20MPa, the matched moulds time was kept 1 second, unclamp exhaust handle, make the filler mould drop to the end, repeat operation 3 times, matched moulds is pressurized to operating pressure 20MPa again, maintenance work pressure and homo(io)thermism sulfuration 3-8min, and curing cycle finishes, rapping takes out rubber from mould.The exhaust number of times that requires simultaneously to add is no more than 1 time, and must at the sulfuration matched moulds in earlier stage, complete continuously.
The product that obtains by the present invention is directly generated by the rubber components original position, and rubber body realizes the loss of gloss effect.
From optical angle, loss of gloss claims again loss of gloss, refers to after the gloss paint film forming that tarnish or paint film are glossy at that time after doing, the gloss phenomenon of fading in a short time, and its reason is that article surface is too coarse.
Corresponding with loss of gloss, to be product weaken the part of light in delustring, and the product surface glossiness is less than 16% the delustring that is.The body delustring of product comes from the optical heterogeneity of body, and this and material property have substantial connection, and wherein the factor of most critical is refractive index difference between inner each microcell of goods.When light enters goods inside through product surface, the optical heterogeneity of goods inside makes light that repeatedly refraction occur, and refraction each time all can be followed scattering and cause light intensity loss, increases this volume scattering, the light that appears thus goods on incident direction will weaken greatly, thereby form delustring.Black rubber does not produce the light transmission phenomenon, in order to reach body loss of gloss purpose, must guarantee that the light reflecting angle that shines on rubber surface is little, require rubber article to light, good diffuse-reflectance performance to be arranged, product surface has extremely strong scattering process to light, could realize the loss of gloss effect.
According to above-mentioned experimental data, directly utilize its bulk material and surface treatment to realize the loss of gloss effect by the preparation-obtained loss of gloss type of the present invention sole, after this bulk material adopts matte surface to process, by suitable working method, guarantee that sandblast forms splendid surfaceness, keep the surperficial loss of gloss of realizing for a long time vulcanized rubber.Technique of the present invention is simple, do not need rubber overshoes spray extinction surface face oil has been reduced production cost, only need to carry out a small amount of simple frosted at die surface and process, greatly reduced workman's labour intensity, and sole surface loss of gloss effect can not change because of use.
Embodiment
embodiments of the invention 1: at the bottom of loss of gloss type height is stretched footwear use black two sulphur surely, calculate by weight, it comprises 60 parts of natural rubbers, 10 parts of styrene-butadiene rubber(SBR), 30 parts of cis-1,4-polybutadiene rubbers, 2.0 part sulphur, 1.5 part vulcanization accelerator (every 1.5 parts of vulcanization accelerators are comprised of 0.5 part of altax and 1.0 parts of accelerant CZs), 8.5 (every 8.5 parts of vulcanization levellers are by 0.5 part of light magnesium oxide for a part vulcanization leveller, 3 parts of stearic acid and 5 parts of nano zine oxides form), 20 parts of Rubber Softener (every 20 parts of Rubber Softener are comprised of 3 parts of solid coumarones and 17 parts of machinery oil), 55 parts of high wear-resistant carbon blacks, 0.3 part Whitfield's ointment, 1.2 part releasing agent 935P and 1.4 parts of anti-aging agent.
Loss of gloss type height is stretched the preparation method at the bottom of footwear are used black two sulphur surely, and natural rubber is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into successively styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, solid coumarone, light magnesium oxide, 1 part of stearic acid and 27 parts of high wear-resistant carbon blacks in Banbury mixer mixing 8 minutes jointly, add machinery oil, after refining glue load gos up, press again refining to stop when load descends, then discharge enters in opening rubber mixing machine, and after turning refining under the 5mm roll spacing 8 minutes slice, get pre-dispersed carbon black rubber master batch; Broken-(down)rubber, pre-dispersed carbon black rubber master batch and middle material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) are dropped into and press refining 1 minute in Banbury mixer, add 28 parts of carbon blacks, continuing refining pressed 7 minutes, the cleaning Banbury mixer rim charge that will overflow adds banburying chamber, add simultaneously 7 parts of machinery oil, press refining 2 minutes after continuing to press refining to go up to load, discharge enters opening rubber mixing machine again.Sizing material enters after mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, until sulphur eat powder complete after, operating on lower machine left and right intersects 8 roads that turn refining, and adopts normal-temperature water to carry out two-sided cooling 30s, upper separant after slice, again material air is chilled to room temperature, namely gets mixed sheet; After mixed sheet is deposited 3 days, the film of getting respectively same quantity from five parts of mixed sheets adds in opening rubber mixing machine, with film refine soft, refining is smooth, more lower sheet to enter refiner smooth with sizing material surface refining, scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die patterned surfaces are carried out the sandblast scale removal, with the mould after sandblast 160 ℃ of lower preheatings 18 minutes; Load weighted two sulphur primer sheets are added to be preheating in satisfactory mould again, mould is pushed in vulcanizer, it is 20MPa that matched moulds is pressurized to operating pressure, the matched moulds time kept 1 second, unclamp exhaust handle, make the filler mould drop to the end, after so repeating aforesaid operations 3 times, matched moulds is pressurized to operating pressure 20MPa again, maintenance work pressure and homo(io)thermism sulfuration 5min, curing cycle unclamps mould after finishing, to take out from mould at the bottom of glue, namely obtain finished product at the bottom of two sulphur.
embodiments of the invention 2: at the bottom of loss of gloss type height is stretched footwear use black two sulphur surely, calculate by weight, it comprises 50 parts of natural rubbers, 15 parts of styrene-butadiene rubber(SBR), 35 parts of cis-1,4-polybutadiene rubbers, 1.9 part sulphur, 1.2 part vulcanization accelerator (every 1.5 parts of vulcanization accelerators are comprised of 0.5 part of altax and 1.0 parts of accelerant CZs), (every 8.5 parts of vulcanization levellers are by 0.5 part of light magnesium oxide for 7 parts of vulcanization levellers, 3 parts of stearic acid and 5 parts of nano zine oxides form), 15 parts of Rubber Softener (every 20 parts of Rubber Softener are comprised of 3 parts of solid coumarones and 17 parts of machinery oil), 50 parts of high wear-resistant carbon blacks, 0.1 part Whitfield's ointment, 1 part of releasing agent 935P and 1.2 parts of anti-aging agent.
Loss of gloss type height is stretched the preparation method at the bottom of footwear are used black two sulphur surely, and natural rubber is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into successively styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, solid coumarone, light magnesium oxide, 1 part of stearic acid and 27 parts of high wear-resistant carbon blacks in Banbury mixer mixing 8 minutes jointly, add machinery oil, after refining glue load gos up, press again refining to stop when load descends, then discharge enters in opening rubber mixing machine, and after turning refining under the 5mm roll spacing 8 minutes slice, get pre-dispersed carbon black rubber master batch; Broken-(down)rubber, pre-dispersed carbon black rubber master batch and middle material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) are dropped into and press refining 1 minute in Banbury mixer, add 28 parts of carbon blacks, continuing refining pressed 7 minutes, the cleaning Banbury mixer rim charge that will overflow adds banburying chamber, add simultaneously 7 parts of machinery oil, press refining 2 minutes after continuing to press refining to go up to load, discharge enters opening rubber mixing machine again.Sizing material enters after mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, until sulphur eat powder complete after, operating on lower machine left and right intersects 8 roads that turn refining, and adopts normal-temperature water to carry out two-sided cooling 30S, upper separant after slice, again material air is chilled to room temperature, namely gets mixed sheet; After mixed sheet is deposited 3 days, the film of getting respectively same quantity from five parts of mixed sheets adds in opening rubber mixing machine, with film refine soft, refining is smooth, more lower sheet to enter refiner smooth with sizing material surface refining, scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die patterned surfaces are carried out the sandblast scale removal, with the mould after sandblast 170 ℃ of lower preheatings 15 minutes; Load weighted two sulphur primer sheets are added to be preheating in satisfactory mould again, mould is pushed in vulcanizer, it is 20MPa that matched moulds is pressurized to operating pressure, the matched moulds time kept 1 second, unclamp exhaust handle, make the filler mould drop to the end, after repeating aforesaid operations 3 times, matched moulds is pressurized to operating pressure 20MPa again, maintenance work pressure and homo(io)thermism sulfuration 4min, curing cycle unclamps mould after finishing, to take out from mould at the bottom of glue, namely obtain finished product at the bottom of two sulphur.
embodiments of the invention 3: at the bottom of loss of gloss type height is stretched footwear use black two sulphur surely, calculate by weight, it comprises 65 parts of natural rubbers, 15 parts of styrene-butadiene rubber(SBR), 20 parts of cis-1,4-polybutadiene rubbers, 2.2 part sulphur, 2 parts of vulcanization accelerators (every 1.5 parts of vulcanization accelerators are comprised of 0.5 part of altax and 1.0 parts of accelerant CZs), (every 8.5 parts of vulcanization levellers are by 0.5 part of light magnesium oxide for 10 parts of vulcanization levellers, 3 parts of stearic acid and 5 parts of nano zine oxides form), 25 parts of Rubber Softener (every 20 parts of Rubber Softener are comprised of 3 parts of solid coumarones and 17 parts of machinery oil), 60 parts of high wear-resistant carbon blacks, 0.4 part Whitfield's ointment, 1.5 part releasing agent 935P and 1.5 parts of anti-aging agent.
Loss of gloss type height is stretched the preparation method at the bottom of footwear are used black two sulphur surely, and natural rubber is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into successively styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, solid coumarone, light magnesium oxide, 1 part of stearic acid and 27 parts of high wear-resistant carbon blacks in Banbury mixer mixing 8 minutes jointly, add machinery oil, after refining glue load gos up, press again refining to stop when load descends, then discharge enters in opening rubber mixing machine, and after turning refining under the 5mm roll spacing 8 minutes slice, get pre-dispersed carbon black rubber master batch; Broken-(down)rubber, pre-dispersed carbon black rubber master batch and middle material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) are dropped into and press refining 1 minute in Banbury mixer, add 28 parts of carbon blacks, continuing refining pressed 7 minutes, the cleaning Banbury mixer rim charge that will overflow adds banburying chamber, add simultaneously 7 parts of machinery oil, press refining 2 minutes after continuing to press refining to go up to load, discharge enters opening rubber mixing machine again.Sizing material enters after mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, until sulphur eat powder complete after, operating on lower machine left and right intersects 8 roads that turn refining, and adopts normal-temperature water to carry out two-sided cooling 30S, upper separant after slice, again material air is chilled to room temperature, namely gets mixed sheet; After mixed sheet is deposited 4 days, the film of getting respectively same quantity from five parts of mixed sheets adds in opening rubber mixing machine, with film refine soft, refining is smooth, more lower sheet to enter refiner smooth with sizing material surface refining, scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die patterned surfaces are carried out the sandblast scale removal, with the mould after sandblast 150 ℃ of lower preheatings 20 minutes; Load weighted two sulphur primer sheets are added to be preheating in satisfactory mould again, mould is pushed in vulcanizer, it is 20MPa that matched moulds is pressurized to operating pressure, the matched moulds time kept 1 second, unclamp exhaust handle, make the filler mould drop to the end, after repeating aforesaid operations 3 times, matched moulds is pressurized to operating pressure 20MPa again, maintenance work pressure and homo(io)thermism sulfuration 8min, curing cycle unclamps mould after finishing, to take out from mould at the bottom of glue, namely obtain finished product at the bottom of two sulphur.