CN101735495A - Formula of sole of high oil resistant rubber sneakers and manufacturing method of soles - Google Patents
Formula of sole of high oil resistant rubber sneakers and manufacturing method of soles Download PDFInfo
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Abstract
The invention relates to a formula of soles of high oil resistant rubber sneakers, which is characterized in that the raw materials of oil resistant rubber outsoles are divided into two parts, wherein according to a formula, the first part comprises the following raw materials in percentage by mass: 40.1 to 46.8 percent of nitrile rubber, 8.4 to 11.7 percent of butadiene rubber (BR9000), 5.0 and 8.4 percent of natural rubber, 2.7 to 3.3 percent of butadiene styrene rubber (SBR), 26.8 to 33.5 percent of white smoke, 5.0 to 6.7 percent of operating oil (DOP), 0.4 percent of stearic acid, 3.3 percent of zinc oxide, 0.7 percent of antioxidant (BHT), 0.4 percent of antifoggant (1956), 2.7 percent of white smoke active agent (PEG4000), 1 percent of white smoke active agent (AT-55), 2 percent of wear-resisting agent (Si-69), 0.7 percent of colophony (P-90) and 0.8 percent of antiozonant (Cm-4); and the second part is added on the basis of one kilogram of the first part, which comprises 13 grams of insoluble sulfur (IS-75), 12grams of accelerator (No.1), 3 grams of accelerator (TRA) and 1 gram of accelerator (NS-80). The invention provides the rubber soles with wear resistance, slip limit, shock absorption and long oil resistant service life and a preparation method thereof.
Description
Technical field
The present invention relates to a kind of special athletic shoe sole, especially relate to a kind of prescription and manufacturing process flow thereof of oil resisting rubber sole.
Background technology
China is maximum footwear production and export State of the whole world, according to " 2008 sports goods market report " data of sports goods association issue, singly is that the sport footwear retail sales breaks through 17,000,000,000 dollars.Along with the development of social work's diversification, all trades and professions are more and more diversified to the functional requirement of footwear, and the sole oil resistant is exactly one of wherein very important needs.In the environment of lipid is arranged, as oil field, refinery, kitchen, market etc., when athletic shoe sole and wet ground or the ground that is attached with oil stain contact, water, oil will be attached to sole surface and form moisture film, oil film, make the unexpected danger that takes place of slipping happen occasionally.Like this, the quality of oil-proofness is one of important factor that directly influences footwear work-ing life, also is safety, is comfortablely ensured a key factor, because greasy environment is arranged, lipid can directly corrode our sole, makes that sole is slowly dissolved, loss.So just shortened the work-ing life of footwear greatly; Grease infiltrates in the footwear simultaneously, makes the comfort level of shoes, and security reduces greatly.
In addition, more and more tighter to the requirement of sole function in the world after China's entry into the World Trade Organization, limit the outlet of Chinese footwear so greatly.In order to increase shoes work-ing life, prevent the generation of the accident of falling down, increasing human consumer and importor, focusing onto increases on sole oil resistant and the non-skid property, like this, research and development high oil-resistant rubber sole can further improve the use value of shoes, guarantee human consumer's interests and security, more help improving the quality of China's footwear footwear, make China in the competition of international overall situation quality awareness in 21 worlds and quality, establish oneself in an unassailable position, continue to keep China footwear outlet the world's strongest nation status.The rubber soles material is by natural rubber and multiple auxiliary agent synthetic high molecular polymer, closely bound up with physics, the chemical property of the material of sole own, therefore must select and synthesize the sole chemical materials of high oil resistance, just can produce real grease-proof footwear material.Traditional rubber soles is mainly synthetic with natural rubber and partial synthesis Rubber processing, though can reach the big base of rubber wear-resisting, anti-slip effect originally, does not almost have grease-proof performance.CN1262076 has invented a kind of neoprene oil resistant boots, but its mainly to be main component with the chloroprene rubber improve oil-proofness, and chloroprene rubber is not suitable for athletic shoe sole, this patent is not tested its oil-proofness in addition.CN101250290 discloses a kind of high temperature resistant, fire-retardant, oil resisting rubber sizing material and production method thereof, and nitrile rubber sizing material improves that sole is high temperature resistant though its adopts, flame retardant properties and oil resistance, and it does not test oil resistance yet.CN2233178 invents a kind of oil resistant leather shoes, but leather shoes and sports shoes have very large difference at composition and function.CN1772802 provides a kind of formed material of anti-slip oil resistant sole, but it mainly adopts polyvinyl chloride to improve the wear-resisting and oil resistance of sole, and polyvinyl chloride generally is not used in the manufacturing of athletic shoe sole because it does not have folding resistance.CN201019058 has invented a kind of oil resistant on-slip sole, but it is not to realize by changing production formula, but realizes oil resistant by the moulding that changes sole.
Although above-mentioned patent documentation has been done suitable research to the oil resistant effect of some material for sole of shoe, all be not suitable for the sports shoes bottom material, make that it can only be as the reference of on-slip campaign shoe sole production.And up to the present, yet there are no about the relevant patent in sports shoes bottom material on-slip aspect.
Summary of the invention
The objective of the invention is at the existing difficult problem that does not almost have oil resistance of existing rubber sneaker sole, a kind of both wear-resisting, on-slip, shock-absorbing are provided; And longer rubber soles of oil resistant life-span is filled a prescription and preparation method thereof.
To achieve these goals, solution of the present invention is:
A kind of high oil resistant rubber sneakers formula of soles, the raw material at the big end of oil resisting rubber is formed and is divided into two portions, first part by the prescription of mass ratio is: paracril 40.1-46.8%, cis-1,4-polybutadiene rubber (BR9000) 8.4-11.7%, natural rubber 5.0-8.4%, styrene-butadiene rubber(SBR) (SBR) 2.7-3.3%, white cigarette 26.8-33.5%, process oil (DOP) 5.0-6.7%, stearic acid 0.4%, zinc oxide 3.3%, anti-aging agent (BHT) 0.7%, antifogging agent (1956) 0.4%, white smoke active agent (PEG4000) 2.7%, white smoke active agent (AT-55) 1%, anti-wear agent (Si-69) 2%, rosin (P-90) 0.7%, antiozonidate (Cm-4) 0.8%; Second section is the add-on on the first part basis, it is every kilogram of insoluble sulfur (IS-75) 13g/ first part, every kilogram of promotor (1#) 12g/ first part, every kilogram of promotor (TRA) 3g/ first part, every kilogram of promotor (NS-80) 1g/ first part.
Above-mentioned high oil resistant rubber sneakers manufacture method of sole may further comprise the steps:
1) pound material
1. according to the prescription mass percent accurately weigh, N-41, BR9000, SBR1502, after SVR-3L and P-90 weigh together;
2. JS-160, ST, ZnO, BHT, 1956, PEG4000, AT-55 puts together after the Si-69 pound is good, adds the DOP consumption by formulation weight at last.
2) banburying
Rubber major ingredient class and tackifier class raw material are mixed, put into the Banbury mixer banburying, open banburying and mix, after 1 minute, add 1/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, again lump, when treating that temperature reaches 100 ℃, about 3 minutes, add 2/3 remaining precipitated hydrated silica and anti-wear agent and all auxiliary agents, when temperature continues to be elevated to 130 ℃, after 7 minutes, blanking.
3) open refining
Open refining, sizing material is with the sheet material discharging, the roller spacing of opening refining has just begun to be 3mm, after to thin its roller spacing again be 1.0mm (1-2 time), during discharging 5mm, the main purpose of opening refining is that rubber, Synergist S-421 95 are mixed is more even, and another purpose is to make sizing material with the sheet discharging, is convenient to further processing treatment.Supercooled water, behind antiseized groove, section was left standstill 24 hours.
4) dosing
To leave standstill material after 24 hours, in mill, carry out dosing, earlier sheet material is played the triangle bag three times in mill, above running roller, leave spacer gel, simultaneously sulphur, vulcanization accelerator and coloring agent are added on the spacer gel, then smash glue, mix, open the refining play and be changed to triangle bag and the clot method of beating, after mixing, discharging is describedly beaten the first time and the roll spacing of triangle bag for the second time is 1.0mm, and the thickness of discharging is 3.0mm or the standard thickness set according to the footwear type.
5) survey vulcanization curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey vulcanization curve, record time of scorch and sulfurizing time, curing time according to record time of scorch and sulfurizing time adjusting oil press, above material is cut into the sole shape with the die of rubber soles puts into the moulding of rubber boots mould oil pressure, will check oil pressure platform temperature (160 ℃) when adding sulphur earlier, pressure (150MPA) whether reaches standard and whether curing time (sulfurizing time) is set correct.Sulphur to be added finishes, and presses setting-up time (270 seconds), opens mould and takes out sole.Promptly get the sole sample.
The present invention compared with the big end of traditional rubber, and is not only wear-resisting, on-slip is good, anti-and oil resistant preferably arranged, shock-absorbing effect can be used for the sports shoes of special occasions, as surfing, drift about, also can invent distinctive oil-proofness thereby embody this with among the footware that the lipid severe environment are arranged.
Description of drawings
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Embodiment
The present invention is further described below in conjunction with embodiment.
The raw material at the big end of oil resisting rubber of the present invention is formed and is divided into two portions, first part by the prescription of mass ratio for by mass percentage prescription is: paracril 40.1-46.8%, cis-1,4-polybutadiene rubber (BR9000) 8.4-11.7%, natural rubber 5.0-8.4%; styrene-butadiene rubber(SBR) (SBR) 2.7-3.3%; white cigarette 26.8-33.5%, process oil (DOP) 5.0-6.7%, stearic acid 0.4%; zinc oxide 3.3%; anti-aging agent (BHT) 0.7%, antifogging agent (1956) 0.4%, white smoke active agent (PEG4000) 2.7%; white smoke active agent (AT-55) 1%; anti-wear agent (Si-69) 2%, rosin (P-90) 0.7%, antiozonidate (Cm-4) 0.8%.Second section is the add-on on the first part basis, it is every kilogram of insoluble sulfur (IS-75) 13g/ first part, every kilogram of promotor (1#) 12g/ first part, every kilogram of promotor (TRA) 3g/ first part, every kilogram of promotor (NS-80) 1g/ first part.
The preparation method at the big end of oil resisting rubber of the present invention may further comprise the steps:
1) pound material
1. according to the prescription mass percent accurately weigh, N-41, BR9000, SBR1502, after SVR-3L and P-90 weigh together.
2. JS-160, ST, ZNO, BHT, 1956, PEG4000, AT-55, the Si-69 pound is put together well, adds the DOP consumption by formulation weight at last.
2) banburying
Rubber major ingredient class and tackifier class raw material are mixed, put into the Banbury mixer banburying, open banburying and mix, after 1 minute, add 1/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, again lump, when treating that temperature reaches 100 ℃, about 3 minutes, add 2/3 remaining precipitated hydrated silica and anti-wear agent and all auxiliary agents, when temperature continues to be elevated to 130 ℃, after 7 minutes, blanking.
3) open refining
Open refining, sizing material is with the sheet material discharging, the roller spacing of opening refining has just begun to be 3mm, after to thin its roll spacing again be 1.0mm (1-2 time), during discharging 5mm, the main purpose of opening refining is that rubber, Synergist S-421 95 are mixed is more even, and another purpose is to make sizing material with the sheet discharging, is convenient to further processing treatment.Supercooled water, behind antiseized groove, section was left standstill 24 hours.
4) dosing
To leave standstill material after 24 hours, in mill, add sulphur, earlier sheet material is played the triangle bag three times in mill, above running roller, leave spacer gel, simultaneously sulphur, vulcanization accelerator and coloring agent are added on the spacer gel, then smash glue, mix, open the refining play and be changed to triangle bag and the clot method of beating, after mixing, discharging is describedly beaten the first time and the roll spacing of triangle bag for the second time is 1.0mm, and the thickness of discharging is 3.0mm or the standard thickness set according to the footwear type.
5) survey vulcanization curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey vulcanization curve, record time of scorch and sulfurizing time, curing time according to record time of scorch and sulfurizing time adjusting oil press, above material is cut into the sole shape with the die of rubber soles puts into the moulding of rubber boots mould oil pressure, will check temperature (160 ℃) when adding sulphur earlier, pressure (150MPA) whether reaches standard and whether curing time (sulfurizing time) is set correct.Sulphur to be added finishes, and presses setting-up time (270 seconds), opens mould and takes out sole.Promptly get the sole sample.
The product that prescription of the present invention and technology are made can carry out the test of rerum natura: the rubber soles finished product made after lining, laboratory (23 ℃) is placed 24 hours, can be carried out the test of rerum naturas such as (DIN) is wear-resisting, hardness, write down test values such as wear-resisting and hardness number.And oil resistant experiment: rubber oil resistant test ASTM USS test oil.Before the sample testing tester thermostatic oil bath is heated to 50 ± 1 ℃, behind temperature-stable, the sample that weighs up weight is put into oil groove to be soaked 72 hours, take out sample and remove the grease of remained on surface, weigh up the weight of test again, the weight of test deducts the weight difference before the test, divided by the weight before the test, is the oil resistant value of this material.
Concrete, the formula range at the big end of oil resisting rubber of the present invention sees the following form
Make sample (enforcement sample) by following prescription, and measure DIN mill, dry type, wet type on-slip coefficient in inspection center, hardness, proportion is torn, tension, unit elongation and oil resistant value (annotate: listed sample implements to be not only the later stage prescription in that this material of research and development is done to test).
For result of study can better be described, the ratio that changes fourth rubber, natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber respectively makes it not meet or exceed optimized proportion scope (seeing Table 4), comparative example 1 is that paracril, natural rubber ratio be not in the optimized proportion scope, comparative example 2 is that paracril, styrene-butadiene rubber(SBR) is not in the optimized proportion scope, comparative example 3 is that butadiene-acrylonitrile rubber, natural rubber have surpassed the optimized proportion scope, and comparative example 4 is that paracril, natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber are all less than in the optimized proportion scope.Make sample (comparative example) according to the following table prescription, and the physical index of testing by the requirement of surveying embodiment in inspection center, its result does a comparison at other in next table.
Each embodiment and comparative example physical property measurement result:
Above physical property measurement result, the whole object of embodiment is better than comparative example, and particularly oil resistant effect embodiment is greatly improved than comparative example.
Conclusion
By the big end of oil resisting rubber of our company's invention, its oil resistant degree can reach European Union's standard (50 ℃, 72 hours≤12%), and this material is wear-resisting simultaneously, on-slip, and shock-absorbing also is better than the big end of traditional rubber.If this material is designed in the sports shoes, this sports shoes almost can still keep its comfort level, weather resistance in any environment.
Claims (2)
1. high oil resistant rubber sneakers formula of soles, it is characterized in that: the raw material at the big end of oil resisting rubber is formed and is divided into two portions, first part by the prescription of mass ratio is: paracril 40.1-46.8%, cis-1,4-polybutadiene rubber (BR9000) 8.4-11.7%, natural rubber 5.0-8.4%, styrene-butadiene rubber(SBR) (SBR) 2.7-3.3%, white cigarette 26.8-33.5%, process oil (DOP) 5.0-6.7%, stearic acid 0.4%, zinc oxide 3.3%, anti-aging agent (BHT) 0.7%, antifogging agent (1956) 0.4%, white smoke active agent (PEG4000) 2.7%, white smoke active agent (AT-55) 1%, anti-wear agent (Si-69) 2%, rosin (P-90) 0.7%, antiozonidate (Cm-4) 0.8%; Second section is the add-on on the first part basis, it is every kilogram of insoluble sulfur (IS-75) 13g/ first part, every kilogram of promotor (1#) 12g/ first part, every kilogram of promotor (TRA) 3g/ first part, every kilogram of promotor (NS-80) 1g/ first part.
2. according to right 1 described a kind of high oil resistant rubber sneakers manufacture method of sole, it is characterized in that: may further comprise the steps:
1) pound material
1. according to the prescription mass percent accurately weigh, N-41, BR9000, SBR1502, after SVR-3L and P-90 weigh together;
2. JS-160, ST, ZnO, BHT, 1956, PEG4000, AT-55, the Si-69 pound is put together well, adds the DOP consumption by formulation weight at last.
2) banburying
Rubber major ingredient class and tackifier class raw material are mixed, put into the Banbury mixer banburying, open banburying and mix, after 1 minute, add 1/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, again lump, when treating that temperature reaches 100 ℃, about 3 minutes, add 2/3 remaining precipitated hydrated silica and anti-wear agent and all auxiliary agents, when temperature continues to be elevated to 130 ℃, after 7 minutes, blanking.
3) open refining
Open refining, sizing material is with the sheet material discharging, the roller spacing of opening refining has just begun to be 3mm, after to thin its roll spacing again be 1.0mm (1-2 time), during discharging 5mm, the main purpose of opening refining is that rubber, Synergist S-421 95 are mixed is more even, and another purpose is to make sizing material with the sheet discharging, is convenient to further processing treatment.Supercooled water, behind antiseized groove, section was left standstill 24 hours.
4) dosing
To leave standstill material after 24 hours, in mill, carry out dosing, earlier with sheet material after playing three triangle bags in the mill, above running roller, leave spacer gel, simultaneously sulphur, vulcanization accelerator and coloring agent are added on the spacer gel, then smash glue, mix, open the refining play and be changed to triangle bag and the clot method of beating, after mixing, discharging is describedly beaten the first time and the roll spacing of triangle bag for the second time is 1.0mm, and the thickness of discharging is 3.0mm or the standard thickness set according to the footwear type.
5) survey vulcanization curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey vulcanization curve, record time of scorch and sulfurizing time are regulated the curing time of oil press according to record time of scorch and sulfurizing time, above material is cut into the sole shape with the die of rubber soles puts into the moulding of rubber boots mould oil pressure.Will check oil pressure platform temperature (160 ℃) when adding sulphur earlier, pressure (150MPA) whether reaches standard and whether curing time (sulfurizing time) is set correct.Sulphur to be added finishes, and presses setting-up time (270 seconds), opens mould and takes out sole.Promptly get the sole sample.
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| CN101897494A (en) * | 2010-07-05 | 2010-12-01 | 孙福标 | Aromatized rubber sole |
| CN102181083A (en) * | 2011-05-05 | 2011-09-14 | 茂泰(福建)鞋材有限公司 | Oil-resistant anti-slip rubber for soles and preparation method thereof |
| CN102488348A (en) * | 2011-12-09 | 2012-06-13 | 际华三五一七橡胶制品有限公司 | Rubber shoes with oilproof and antiskid functions |
| CN102796292A (en) * | 2012-08-09 | 2012-11-28 | 际华三五三七制鞋有限责任公司 | High-elongation wear-resistant oil-resistant rubber sole and preparation method thereof |
| CN102816358A (en) * | 2012-09-04 | 2012-12-12 | 苏州伟伦运动休闲用品有限公司 | Transparent antistatic shoe sole and production method thereof |
| CN103450518A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Highly wear resistant rubber and preparation method thereof |
| CN103450519A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Antiskid rubber and manufacturing method thereof |
| CN103772763A (en) * | 2013-12-25 | 2014-05-07 | 泉州鑫泰鞋材有限公司 | Rubber composite and preparation process thereof |
| CN104140577A (en) * | 2014-08-08 | 2014-11-12 | 温州市海滨秀龙鞋材有限公司 | Formula of anti-skid shoe soles and shoe soles and shoes based on formula |
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| CN104710658A (en) * | 2013-12-16 | 2015-06-17 | 天津市星兴橡胶制品有限公司 | Antislip rubber sole material |
| CN104817734A (en) * | 2015-05-04 | 2015-08-05 | 安庆泰亚鞋业有限公司 | Anti-cracking rubber sport shoes sole and manufacturing method of same |
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| CN105873995A (en) * | 2013-12-30 | 2016-08-17 | 阿朗新科德国有限责任公司 | Nitrile-butadiene rubbers that are stable in storage and method for producing same |
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| CN101897494A (en) * | 2010-07-05 | 2010-12-01 | 孙福标 | Aromatized rubber sole |
| CN102181083A (en) * | 2011-05-05 | 2011-09-14 | 茂泰(福建)鞋材有限公司 | Oil-resistant anti-slip rubber for soles and preparation method thereof |
| CN102488348A (en) * | 2011-12-09 | 2012-06-13 | 际华三五一七橡胶制品有限公司 | Rubber shoes with oilproof and antiskid functions |
| CN103450518A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Highly wear resistant rubber and preparation method thereof |
| CN103450519A (en) * | 2012-06-04 | 2013-12-18 | 特步(中国)有限公司 | Antiskid rubber and manufacturing method thereof |
| CN102796292A (en) * | 2012-08-09 | 2012-11-28 | 际华三五三七制鞋有限责任公司 | High-elongation wear-resistant oil-resistant rubber sole and preparation method thereof |
| CN102796292B (en) * | 2012-08-09 | 2014-08-20 | 际华三五三七制鞋有限责任公司 | High-elongation wear-resistant oil-resistant rubber sole and preparation method thereof |
| CN102816358A (en) * | 2012-09-04 | 2012-12-12 | 苏州伟伦运动休闲用品有限公司 | Transparent antistatic shoe sole and production method thereof |
| CN104710658A (en) * | 2013-12-16 | 2015-06-17 | 天津市星兴橡胶制品有限公司 | Antislip rubber sole material |
| CN103772763A (en) * | 2013-12-25 | 2014-05-07 | 泉州鑫泰鞋材有限公司 | Rubber composite and preparation process thereof |
| CN105873995A (en) * | 2013-12-30 | 2016-08-17 | 阿朗新科德国有限责任公司 | Nitrile-butadiene rubbers that are stable in storage and method for producing same |
| TWI653271B (en) | 2013-12-30 | 2019-03-11 | 艾朗希歐德意志有限公司 | Storage-stable nitrile rubbers and process for production thereof |
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Application publication date: 20100616 |