CN103788439A - Wide-temperature domain high-shock absorbance sports footwear sole rubber material and its preparation method - Google Patents
Wide-temperature domain high-shock absorbance sports footwear sole rubber material and its preparation method Download PDFInfo
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- CN103788439A CN103788439A CN201210408660.4A CN201210408660A CN103788439A CN 103788439 A CN103788439 A CN 103788439A CN 201210408660 A CN201210408660 A CN 201210408660A CN 103788439 A CN103788439 A CN 103788439A
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Abstract
The invention relates to a wide-temperature domain high-shock absorbance sports footwear sole rubber material and its preparation method. The material is suitable for sports footwear soles with wide temperature domain requirement and high shock absorbance performance requirement. The wide-temperature domain high-shock absorbance sports footwear sole rubber material is composed of brominated butyl rubber, BR, a strengthening agent, a vulcanizing agent and a sulfuration promoter, and petroleum resin. The maximum loss factor value of the wide-temperature domain high-shock absorbance sports footwear sole rubber material is 0.34-0.45, the damping temperature domain (tan delta is greater than or equal to 0.2) is -44-53 DEG C, DIN abrasion is less than or equal to 100mm<3>. The material has the advantage for keeping good shock absorbance performance in wide temperature domain.
Description
(1) technical field
The present invention relates to the high shock-absorbing sport shoes sole rubber of a kind of wide temperature range material and preparation method thereof, this material is applicable to temperature range to require the medium-to-high grade athletic shoe sole wider, damping performance is had relatively high expectations.
(2) background technology
With the continuous progress of science and technology, the scientific and technological content of current sports shoes is also improving day by day, and wherein the development and application of cushion technique more enjoys people's concern.Good damping performance can improve the wearing comfort of sports shoes, the concussion that when kicking motion, surging force causes health, and protection skeleton and joint are without prejudice.The damping performance of footwear depends primarily on material and the structure of sole, the structural damping technology of sports shoes is more ripe at present, " Zoom Air ", " the Max Air " of for example Nike, the new texture footwear such as " ADIPRENE ", " ADIPRENE+ ", " torsion rod " and the Li Ning bow of Adidas have all been come out one after another, and the end and shoe-pad in the foaming that mainly concentrates on sports shoes reported in the material damping of sports shoes research, less to the research report of outer bottom damping.
In 201010248174.1 patents, adopt cis-butadiene cement/brominated butyl rubber take different proportionings as main ingredient, prepare high damping abrasive rubber soling materials, but due to the dissipation factor that has reduced material that adds of a large amount of cis-butadiene cements, and damping temperature domain is narrower, make the damping performance of material for sole of shoe be subject to certain restriction.China north and south is across wide (3 ° 52 ', 53 ° of 33 '～Nansha Islands of Mo River north latitude) of latitude, according to the difference of various places >=10 ℃ accumulated temperature size, China is from north and there are cool temperature zone, middle temperate zone, warm temperate zone, subtropics, tropical equitemperature band in south, and special High-cold regions, Qinghai-Tibet, therefore the temperature contrast of various places is very large, for example winter Mo River minimum temperature reach-50 ℃ of left and right, and summer Turpan Basin extreme maximum temperature up to 48.9 ℃.Temperature variation is comparatively remarkable on the damping characteristics impact of material for sole of shoe.How making pair of trainers keep to greatest extent good damping performance in different geographical, Various Seasonal, is the focus that shoe-making industry researcher merits attention.
Can pair of trainers keep good damping performance to depend primarily on material for sole of shoe characteristic under different geographical and weather condition.This just requires rubber soles material can in wide temperature range, keep higher damping performance, is not subject to the impact of region (south and the north) and weather (winter and summer).Therefore, the preparation of wide temperature range yielding rubber sole has a good application prospect.
The present invention proposes the high shock-absorbing sport shoes sole rubber of a kind of wide temperature range material, keeps good damping performance in wide temperature range.
(3) summary of the invention
The present invention aims to provide the high shock-absorbing sport shoes sole rubber of a kind of wide temperature range material and preparation method thereof.In order to realize foregoing invention object, the invention provides following technical scheme: the high shock-absorbing sport shoes sole rubber of a kind of wide temperature range material, is made up of the component of following mass ratio:
The present invention adopts the brominated butyl rubber (being called for short BIIR) of damping characteristics excellence, coordinates the cis-butadiene cement (being called for short BR) with good abrasion resistance for matrix, to make material have good wear resistance and damping property.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, is characterized in that strengthening agent is precipitator method hydrated SiO 2, claims again white carbon black, white cigarette.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, is characterized in that promoting agent is glycol ether, polyoxyethylene glycol, zinc oxide, wherein at least one of magnesium oxide.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, it is characterized in that described coupling agent is tetra-sulfurized pair (triethoxy propyl group) silane, two-(3-triethoxyl silane propyl group)-disulphide, 3-aminopropyl triethoxysilane, 3-mercaptopropyltriethoxysilane, hexamethyldisilazane, N, at least one in N-dimethylaminoethanol and homologue thereof.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, is characterized in that described vulcanizing agent is at least one in sulphur, poly-hydroxyl cresol resin and halide derivative thereof.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, it is characterized in that described promotor is wherein two or more composition of N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, 2,2 '-dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-benzothiazolyl mercaptan, tetramethyl-thiuram disulfide.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, it is characterized in that described anti-aging agent is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester (abbreviation antioxidant 1010), N-sec.-propyl-N '-diphenyl-para-phenylene diamine (being called for short 4010NA), and at least one in alkane hydrocarbon chain, Microcrystalline Wax, antifog wax.
The high shock-absorbing sport shoes sole rubber of the wide temperature range of described one material, is characterized in that described petroleum resin are at least one in aliphatic carbon five resins (C5 resin), aromatic series carbon nine resins (C9 resin).
The present invention can also add other conventional processing aids of this area, as pigment, white dyes, photostabilizer etc.
The high shock-absorbing sport shoes sole rubber of wide temperature range of the present invention material, its manufacture method is as follows:
(1) order of addition(of ingredients): 1. add base rubber; 2. add petroleum resin; 3. add white carbon black; 4. add zinc oxide, stearic acid, polyoxyethylene glycol, anti-aging agent; 5. add promotor; 6. add sulphur.
(2) preparation technology: the cis-butadiene cement in above-mentioned weight proportion and brominated butyl rubber are plasticated with mill within the scope of 45～55 ℃, the roll spacing of mill is adjusted into 2～4mm, making it reach respectively certain plasticity number takes off stand-by, then two kinds of base rubber are carried out mixing, mixing roller temperature control is within the scope of 55～65 ℃, mixing time 2～3min, then add petroleum resin, mixing 3～5min is dispersed to resin, add various Synergist S-421 95s by said sequence again, roller temperature is still controlled within the scope of 55～65 ℃.Finally treating that sulphur is mixing gets final product slice after evenly, and after at room temperature parking 24h, carries out molded vulcanization moulding on vulcanizing press, preparation athletic shoe sole.
The present invention has mainly prepared the high shock-absorbing sport shoes sole rubber of a series of wide temperature ranges material, refers to embodiment 1～5.The high shock-absorbing sport shoes material for sole of shoe of this wide temperature range possesses following advantage: (1) has wider glass transition temperature range and higher dissipation factor, can in wide temperature range, keep good damping performance; (2) wear resisting property is good, and work-ing life is longer; (3) hardness is suitable, and higher wearing comfort is provided.
The present invention can adopt mill, Banbury mixer to carry out blend, slice.Adopt the processing modes such as injection moulding, mold pressing, note pressure, its Application Areas relates to sole, rubber pad and all kinds of rubber items etc.
(4) embodiment
Embodiment 1:
Composition (mass ratio) is: BIIR30 part, BR70 part, 50 parts of white carbon blacks, Si693.0 part, PEG5.0 part, 5.0 parts, magnesium oxide, 3.0 parts, zinc oxide, 1.7 parts of stearic acid, DM1.0 part, TMTM0.3 part, NS0.63 part, 1.5 parts, sulphur, oxidation inhibitor 4010NA1.0 part.
By said ratio weighing, and carry out according to described before order of addition(of ingredients) and preparation technology mixing, through record the engineering sulfurizing time (t of rubber unvulcanizate without rotor rheometer
90) be 360s 150 ℃ times, then compression molding under 150 ℃ of conditions, carries out performance test after parking 24h.
Embodiment 2:
Composition (mass ratio) is: 5.0 parts of BIIR30 parts, BR70 part, 50 parts of white carbon blacks, Si693.0 part, PEG5.0 part, 5.0 parts, magnesium oxide, 3.0 parts, zinc oxide, 1.7 parts of stearic acid, DM1.0 part, TMTM0.3 part, NS0.63 part, 1.5 parts, sulphur, oxidation inhibitor 4010NA1.0 part, C5 petroleum resin.
By said ratio weighing, and carry out according to described before order of addition(of ingredients) and preparation technology mixing, through record the engineering sulfurizing time (t of rubber unvulcanizate without rotor rheometer
90) be 348s 150 ℃ times, then compression molding under 150 ℃ of conditions, carries out performance test after parking 24h.
Embodiment 3:
Composition (mass ratio) is: 10.0 parts of BIIR30 parts, BR70 part, 50 parts of white carbon blacks, Si693.0 part, PEG5.0 part, 5.0 parts, magnesium oxide, 3.0 parts, zinc oxide, 1.7 parts of stearic acid, DM1.0 part, TMTM0.3 part, NS0.63 part, 1.5 parts, sulphur, oxidation inhibitor 4010NA1.0 part, C5 petroleum resin.
By said ratio weighing, and carry out according to described before order of addition(of ingredients) and preparation technology mixing, through record the engineering sulfurizing time (t of rubber unvulcanizate without rotor rheometer
90) be 360s 150 ℃ times, then compression molding under 150 ℃ of conditions, carries out performance test after parking 24h.
Embodiment 4:
Composition (mass ratio) is: 15.0 parts of BIIR30 parts, BR70 part, 50 parts of white carbon blacks, Si693.0 part, PEG5.0 part, 5.0 parts, magnesium oxide, 3.0 parts, zinc oxide, 1.7 parts of stearic acid, DM1.0 part, TMTM0.3 part, NS0.63 part, 1.5 parts, sulphur, oxidation inhibitor 4010NA1.0 part, C5 petroleum resin.
By said ratio weighing, and carry out according to described before order of addition(of ingredients) and preparation technology mixing, through record the engineering sulfurizing time (t of rubber unvulcanizate without rotor rheometer
90) be 402s 150 ℃ times, then compression molding under 150 ℃ of conditions, carries out performance test after parking 24h.
Embodiment 5:
Composition (mass ratio) is: 20.0 parts of BIIR30 parts, BR70 part, 50 parts of white carbon blacks, Si693.0 part, PEG5.0 part, 5.0 parts, magnesium oxide, 3.0 parts, zinc oxide, 1.7 parts of stearic acid, DM1.0 part, TMTM0.3 part, NS0.63 part, 1.5 parts, sulphur, oxidation inhibitor 4010NA1.0 part, C5 petroleum resin.
By said ratio weighing, and carry out according to described before order of addition(of ingredients) and preparation technology mixing, through record the engineering sulfurizing time (t of rubber unvulcanizate without rotor rheometer
90) be 414s 150 ℃ times, then compression molding under 150 ℃ of conditions, carries out performance test after parking 24h.
The high shock-absorbing sport shoes sole rubber of the wide temperature range material property indices that embodiment 1～5 makes is as shown in table 1.
Table 1 embodiment 1～5 and currently available products performance index
As can be seen from Table 1, the high shock-absorbing sport shoes sole rubber of wide temperature range material prepared by the present invention, compared with currently available products, its maximum loss factor (tan δ
max) and damping temperature domain (tan δ>=0.20) obtained respectively significant raising and widened, improved the deficiency of the wide temperature range damping performance of currently available products, simultaneously the wear resisting property of product is good, DIN wears away at 84～99mm
3between, exceed the wear resisting property index request (DIN abrasion≤120mm of Nike, Adidas rubber soles in the market
3).Embodiment 3,4 in the present invention and currently available products contrast are known, tensile strength, elongation at break all increase, and impact rebound degree and hardness and all slightly decline, the descension theory that impacts rebound degree understands that material damping capaicty improves, and the decline of hardness can improve the comfort level of dress.In addition, compared with currently available products, declining to some extent has all appearred in the tear strength of embodiment 1～5 material for sole of shoe, requires (angle tear strength >=45N/mm) but embodiment 1～5 has reached the performance index of the direct tear strength of existing athletic shoe sole.
The prepared high shock-absorbing sport shoes sole rubber of the wide temperature range material of embodiment 3～5 in the present invention, can keep higher damping performance in-49 ℃～53 ℃ temperature ranges in, mechanical strength and wear resisting property are good and hardness is moderate, under the wear resisting property and tear resistance prerequisite that meet existing sports shoes, give again sole good wide temperature range damping performance.
In sum, the prepared high shock-absorbing sport shoes sole rubber of the wide temperature range material of the present invention has possessed the stronger market competitiveness and good future develop.
The present invention's starting material used are commercial prod.Cis-butadiene cement is that Beijing Yanshan Mountain branch office of petrochemical complex limited-liability company produces, trade mark BR9000.Brominated butyl rubber (BIIR) is american exxon (EXXON) product, the trade mark 2255.
The dynamic thermomechanometry test condition that the present invention carries out and instrument title, model details are as follows:
(1) sample size: 10mm × 10mm × 2mm
(2) testing tool: Dynamic Mechanical Thermal Spectrometer (DMTS); Model: EPLEXOR500N
(3) test pattern: compact model
Test condition: frequency: 10Hz; Static strain: 5%; Dynamic strain: 0.5%; 2 ℃/min of temperature rise rate, intensification scope :-130 ℃～100 ℃.
Claims (9)
1. the high shock-absorbing sport shoes sole rubber of a wide temperature range material, is characterized in that its component and mass ratio are:
2. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, is characterized in that strengthening agent is precipitator method hydrated SiO 2, claims again white carbon black, white cigarette.
3. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, is characterized in that promoting agent is glycol ether, polyoxyethylene glycol, zinc oxide, wherein at least one of magnesium oxide.
4. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, it is characterized in that described coupling agent is tetra-sulfurized pair (triethoxy propyl group) silane, two-(3-triethoxyl silane propyl group)-disulphide, 3-aminopropyl triethoxysilane, 3-mercaptopropyltriethoxysilane, hexamethyldisilazane, N, at least one in N-dimethylaminoethanol and homologue thereof.
5. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, is characterized in that described vulcanizing agent is at least one in sulphur, poly-hydroxyl cresol resin and halide derivative thereof.
6. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, it is characterized in that described promotor is wherein two or more composition of N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, 2,2 '-dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-benzothiazolyl mercaptan, tetramethyl-thiuram disulfide.
7. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, it is characterized in that described anti-aging agent is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester (abbreviation antioxidant 1010), N-sec.-propyl-N '-diphenyl-para-phenylene diamine (being called for short 4010NA), and at least one in alkane hydrocarbon chain, Microcrystalline Wax, antifog wax.
8. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, is characterized in that described petroleum resin are at least one in aliphatic carbon five resins (C5 resin), aromatic series carbon nine resins (C9 resin).
9. the high shock-absorbing sport shoes sole rubber of the wide temperature range of one as claimed in claim 1 material, its preparation method is as follows:
(1) order of addition(of ingredients): 1. add base rubber; 2. add petroleum resin; 3. add white carbon black; 4. add zinc oxide, stearic acid, polyoxyethylene glycol, anti-aging agent; 5. add promotor; 6. add sulphur.
(2) preparation technology: the cis-butadiene cement in above-mentioned weight proportion and brominated butyl rubber are plasticated with mill within the scope of 45～55 ℃, the roll spacing of mill is adjusted into 2～4mm, making it reach respectively certain plasticity number takes off stand-by, then two kinds of base rubber are carried out mixing, mixing roller temperature control is within the scope of 55～65 ℃, mixing time 2～3min, then add petroleum resin, mixing 3～5min is dispersed to resin, and then add white carbon black by above-mentioned order of addition(of ingredients), promoting agent, anti-aging agent and promotor, finally add sulphur, roller temperature is still controlled within the scope of 55～65 ℃.Finally treating that sulphur is mixing gets final product slice after evenly, and after at room temperature parking 24h, carries out molded vulcanization moulding on vulcanizing press, preparation athletic shoe sole.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861318A (en) * | 2015-05-15 | 2015-08-26 | 中国皮革和制鞋工业研究院 | Recyclable rubber foaming sole material and preparation method thereof |
| CN104927217A (en) * | 2015-05-12 | 2015-09-23 | 蚌埠市耀得保温容器有限公司 | Heat-resistant and aging-resistant vacuum flask |
| CN104927218A (en) * | 2015-07-09 | 2015-09-23 | 际华三五三九制鞋有限公司 | Anti-skid wear-resisting rubber shoe sole |
| CN105566696A (en) * | 2016-01-29 | 2016-05-11 | 朱海燕 | Formula and preparation process of wear-resistant rubber shoe sole material |
| CN106750704A (en) * | 2017-01-11 | 2017-05-31 | 上海正村橡塑工业有限公司 | A kind of formula for improving rubber damping characteristic |
| CN108948548A (en) * | 2018-05-29 | 2018-12-07 | 广州丽泰鞋业有限公司 | A kind of sole material and wet type anti-slip sole production method |
| CN109897385A (en) * | 2019-03-11 | 2019-06-18 | 安踏（中国）有限公司 | A kind of vibration-damping foamed middle bottom material and preparation method thereof of width temperature range |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
| CN112625371A (en) * | 2020-12-17 | 2021-04-09 | 宁波柯林斯橡塑科技有限公司 | Damping sucker composite material and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927217A (en) * | 2015-05-12 | 2015-09-23 | 蚌埠市耀得保温容器有限公司 | Heat-resistant and aging-resistant vacuum flask |
| CN104861318A (en) * | 2015-05-15 | 2015-08-26 | 中国皮革和制鞋工业研究院 | Recyclable rubber foaming sole material and preparation method thereof |
| CN104927218A (en) * | 2015-07-09 | 2015-09-23 | 际华三五三九制鞋有限公司 | Anti-skid wear-resisting rubber shoe sole |
| CN105566696A (en) * | 2016-01-29 | 2016-05-11 | 朱海燕 | Formula and preparation process of wear-resistant rubber shoe sole material |
| CN106750704A (en) * | 2017-01-11 | 2017-05-31 | 上海正村橡塑工业有限公司 | A kind of formula for improving rubber damping characteristic |
| CN108948548A (en) * | 2018-05-29 | 2018-12-07 | 广州丽泰鞋业有限公司 | A kind of sole material and wet type anti-slip sole production method |
| CN109897385A (en) * | 2019-03-11 | 2019-06-18 | 安踏（中国）有限公司 | A kind of vibration-damping foamed middle bottom material and preparation method thereof of width temperature range |
| CN109897385B (en) * | 2019-03-11 | 2021-08-17 | 安踏（中国）有限公司 | Wide-temperature-range shock-absorption foaming insole material and preparation method thereof |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
| CN112625371A (en) * | 2020-12-17 | 2021-04-09 | 宁波柯林斯橡塑科技有限公司 | Damping sucker composite material and preparation method thereof |
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