Summary of the invention
Technical problem to be solved by this invention is: provide a kind of loss of gloss type height stretch surely footwear with black two sulphur at the bottom of and the preparation method; Realize complete loss of gloss according to its resulting product by rubber body; Working method is simple; Low production cost; Labour intensity is low; Resulting good product quality is to overcome the deficiency of prior art.
The present invention be achieved in that loss of gloss type height stretch surely footwear with black two sulphur at the bottom of; Calculate by weight, it comprises 50~65 parts of tree elastomers, 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 tree elastomers, 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.
Per 1.5 parts of vulcanization accelerators are made up of 0.5 part of altax and 1.0 parts of accelerant CZs.
Per 8.5 parts of vulcanization levellers are made up of 0.5 part of light magnesium oxide, 3 parts of stearic acid and 5 parts of nano zine oxides.
Per 20 parts of Rubber Softener are made up of 3 parts of solid coumarones and 17 parts of machinery oil.
Loss of gloss type height is stretched the preparation method of footwear at the bottom of with black two sulphur surely, and tree elastomer is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into 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 successively in Banbury mixer mixing 8 minutes jointly; Add machinery oil; After refining glue load gos up; When pressing refining to load to descend again; Discharge gets in the opening rubber mixing machine; And after turning refining under 5~6mm roll spacing 8~9 minutes slice, 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 the 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 7 parts of machinery oil simultaneously; Continue to press refining 2 minutes again after pressure is refined the load rise; Discharge gets into opening rubber mixing machine, in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur after the sizing material entering mill; After treating that sulphur is eaten powder and finished; Intersect 8 roads that turn refining about the machine of operating on down, adopt normal-temperature water to carry out two-sided cooling 30S, last separant after the slice; Again that material is air-cooled to room temperature, promptly get mixed sheet; After mixed sheet deposited 3~4 days; The film of from five parts of mixed sheets, getting same quantity respectively adds in the opening rubber mixing machine, with film refine soft, refining is smooth, descend sheet to get into refiner again and refine the sizing material surface smooth; Scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die decorative pattern faces are carried out the sandblast scale removal, with the mould after the sandblast 150~170 ℃ of following preheatings 15~20 minutes; Load weighted two sulphur primer sheets adding has been preheating in the satisfactory mould again, mould is pushed in the 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; Keep operating pressure and homo(io)thermism sulfuration 4~8min, curing cycle unclamps mould after finishing; To from mould, take out at the bottom of the glue, promptly obtain finished product at the bottom of two sulphur.
Material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent in described.
Adopt method of the present invention to produce product, performance of products tested, carry out following formulation screening test, thereby verify technical scheme of the present invention:
The formula test data:
Prescription: 60 parts of tree elastomers, 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 tree elastomers, 10 parts in styrene-butadiene rubber(SBR), 30 parts of cis-butadiene cements, 2 parts in 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 in 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 tree elastomers, 10 parts in styrene-butadiene rubber(SBR), 30 parts of cis-butadiene cements, 2 parts in sulphur, 3 parts of solid coumarones, 17 parts in machinery oil, black 55 parts of high abrasion, vulcanization accelerator, promoting agent are variable.
B tests contrast 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 in 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 in machinery oil, 3 parts of solid coumarones; Natural gum and synthetical glue are variable.
B tests contrast
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 that when tree elastomer 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 the decorative pattern face shinny, require with the mould sandblast once every day.To guarantee loss of gloss effect and level.
Conclusion (of pressure testing):
Draw through above-mentioned test, optimum formula and processing condition are following:
Optimum formula: 60 parts of tree elastomers, 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 tree elastomer.
Sulfuration system end operation scheme is: after adding the sole film in the mould in 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; So repetitive operation is 3 times; Matched moulds is pressurized to operating pressure 20MPa again, keeps operating 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 accomplish continuously at the sulfuration matched moulds in earlier stage.
The product that obtains through 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 is claimed loss of gloss again, is meant after the gloss paint film forming that tarnish or paint film were 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 a refractive index difference between inner each microcell of goods.When light sees through product surface entering goods inside; The inner optical heterogeneity of goods makes light that repeatedly refraction take place, and refraction each time all can be followed scattering and cause light intensity loss, increases this volume scattering; The light that on incident direction, appears goods thus 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 reflective angle of light that shines on the rubber surface is little, require rubber article that light is had good diffuse-reflectance performance; 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 through the prepared loss of gloss type sole that obtains of the present invention; After this bulk material adopts matte surface to handle; Through suitable working method; Guarantee that sandblast forms splendid surfaceness, keep the surperficial loss of gloss of realizing vulcanized rubber for a long time.Technology of the present invention is simple; Need not reduce production cost, only need carry out a spot of simple frosted and handle at die surface to rubber overshoes spray extinction surface face oil; Significantly reduced working strength of workers, and sole surface loss of gloss effect can not change because of use.
Embodiment
Embodiments of the invention 1: loss of gloss type height stretch surely footwear with black two sulphur at the bottom of; Calculate by weight, it comprises 60 parts of tree elastomers; 10 parts of styrene-butadiene rubber(SBR); 30 parts of cis-1,4-polybutadiene rubbers; 2.0 part sulphur; 1.5 part vulcanization accelerator (per 1.5 parts of vulcanization accelerators are made up of 0.5 part of altax and 1.0 parts of accelerant CZs); 8.5 (per 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 are formed); 20 parts of Rubber Softener (per 20 parts of Rubber Softener are made up 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 of footwear at the bottom of with black two sulphur surely, and tree elastomer is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into 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 successively in Banbury mixer mixing 8 minutes jointly; Add machinery oil; After refining glue load gos up; Press refining when load descends, to stop again; Discharge gets in the opening rubber mixing machine then; And after turning refining under the 5mm roll spacing 8 minutes slice, pre-dispersed carbon black rubber master batch; With broken-(down)rubber, pre-dispersed carbon black rubber master batch and in material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) drop into and press refining 1 minute in the 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 7 parts of machinery oil simultaneously; Continue to press refining 2 minutes again, discharge entering opening rubber mixing machine after pressure is refined the load rise.Sizing material gets into after the mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, treat that sulphur is eaten powder and finished after; Intersect 8 roads that turn refining about the machine of operating on down, adopt normal-temperature water to carry out two-sided cooling 30s, last separant after the slice; Again that material is air-cooled to room temperature, promptly get mixed sheet; After mixed sheet deposited 3 days; The film of from five parts of mixed sheets, getting same quantity respectively adds in the opening rubber mixing machine, with film refine soft, refining is smooth, descend sheet to get into refiner again and refine the sizing material surface smooth; Scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die decorative pattern faces are carried out the sandblast scale removal, with the mould after the sandblast 160 ℃ of following preheatings 18 minutes; Load weighted two sulphur primer sheets adding has been preheating in the satisfactory mould again, mould is pushed in the 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 aforesaid operations 3 times after; Matched moulds is pressurized to operating pressure 20MPa again; Keep operating pressure and homo(io)thermism sulfuration 5min, curing cycle unclamps mould after finishing; To from mould, take out at the bottom of the glue, promptly obtain finished product at the bottom of two sulphur.
Embodiments of the invention 2: loss of gloss type height stretch surely footwear with black two sulphur at the bottom of; Calculate by weight, it comprises 50 parts of tree elastomers; 15 parts of styrene-butadiene rubber(SBR); 35 parts of cis-1,4-polybutadiene rubbers; 1.9 part sulphur; 1.2 part vulcanization accelerator (per 1.5 parts of vulcanization accelerators are made up of 0.5 part of altax and 1.0 parts of accelerant CZs); (per 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 are formed); 15 parts of Rubber Softener (per 20 parts of Rubber Softener are made up 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 of footwear at the bottom of with black two sulphur surely, and tree elastomer is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into 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 successively in Banbury mixer mixing 8 minutes jointly; Add machinery oil; After refining glue load gos up; Press refining when load descends, to stop again; Discharge gets in the opening rubber mixing machine then; And after turning refining under the 5mm roll spacing 8 minutes slice, pre-dispersed carbon black rubber master batch; With broken-(down)rubber, pre-dispersed carbon black rubber master batch and in material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) drop into and press refining 1 minute in the 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 7 parts of machinery oil simultaneously; Continue to press refining 2 minutes again, discharge entering opening rubber mixing machine after pressure is refined the load rise.Sizing material gets into after the mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, treat that sulphur is eaten powder and finished after; Intersect 8 roads that turn refining about the machine of operating on down, adopt normal-temperature water to carry out two-sided cooling 30S, last separant after the slice; Again that material is air-cooled to room temperature, promptly get mixed sheet; After mixed sheet deposited 3 days; The film of from five parts of mixed sheets, getting same quantity respectively adds in the opening rubber mixing machine, with film refine soft, refining is smooth, descend sheet to get into refiner again and refine the sizing material surface smooth; Scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die decorative pattern faces are carried out the sandblast scale removal, with the mould after the sandblast 170 ℃ of following preheatings 15 minutes; Load weighted two sulphur primer sheets adding has been preheating in the satisfactory mould again, mould is pushed in the 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, repeat aforesaid operations 3 times after; Matched moulds is pressurized to operating pressure 20MPa again; Keep operating pressure and homo(io)thermism sulfuration 4min, curing cycle unclamps mould after finishing; To from mould, take out at the bottom of the glue, promptly obtain finished product at the bottom of two sulphur.
Embodiments of the invention 3: loss of gloss type height stretch surely footwear with black two sulphur at the bottom of; Calculate by weight, it comprises 65 parts of tree elastomers; 15 parts of styrene-butadiene rubber(SBR); 20 parts of cis-1,4-polybutadiene rubbers; 2.2 part sulphur; 2 parts of vulcanization accelerators (per 1.5 parts of vulcanization accelerators are made up of 0.5 part of altax and 1.0 parts of accelerant CZs); (per 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 are formed); 25 parts of Rubber Softener (per 20 parts of Rubber Softener are made up 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 of footwear at the bottom of with black two sulphur surely, and tree elastomer is refined, and makes its Wei Shi plasticity number reach 0.40~0.50, makes broken-(down)rubber; Dropped into 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 successively in Banbury mixer mixing 8 minutes jointly; Add machinery oil; After refining glue load gos up; Press refining when load descends, to stop again; Discharge gets in the opening rubber mixing machine then; And after turning refining under the 5mm roll spacing 8 minutes slice, pre-dispersed carbon black rubber master batch; With broken-(down)rubber, pre-dispersed carbon black rubber master batch and in material (middle material comprises promotor, anti-aging agent, scorch retarder, zinc oxide and 2 parts of stearic acid and releasing agent) drop into and press refining 1 minute in the 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 7 parts of machinery oil simultaneously; Continue to press refining 2 minutes again, discharge entering opening rubber mixing machine after pressure is refined the load rise.Sizing material gets into after the mill in drop-down logical 8 roads of 4~5mm roll spacing, adds sulphur, treat that sulphur is eaten powder and finished after; Intersect 8 roads that turn refining about the machine of operating on down, adopt normal-temperature water to carry out two-sided cooling 30S, last separant after the slice; Again that material is air-cooled to room temperature, promptly get mixed sheet; After mixed sheet deposited 4 days; The film of from five parts of mixed sheets, getting same quantity respectively adds in the opening rubber mixing machine, with film refine soft, refining is smooth, descend sheet to get into refiner again and refine the sizing material surface smooth; Scribing calendering water-cooled, the die-cut two sulphur primer sheets that obtain; Two sulphur bottom die decorative pattern faces are carried out the sandblast scale removal, with the mould after the sandblast 150 ℃ of following preheatings 20 minutes; Load weighted two sulphur primer sheets adding has been preheating in the satisfactory mould again, mould is pushed in the 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, repeat aforesaid operations 3 times after; Matched moulds is pressurized to operating pressure 20MPa again; Keep operating pressure and homo(io)thermism sulfuration 8min, curing cycle unclamps mould after finishing; To from mould, take out at the bottom of the glue, promptly obtain finished product at the bottom of two sulphur.