CN110003539A - Anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground of one kind and preparation method thereof - Google Patents
Anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground of one kind and preparation method thereof Download PDFInfo
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- CN110003539A CN110003539A CN201910325272.1A CN201910325272A CN110003539A CN 110003539 A CN110003539 A CN 110003539A CN 201910325272 A CN201910325272 A CN 201910325272A CN 110003539 A CN110003539 A CN 110003539A
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber grounds and preparation method thereof.The anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground of one kind of the invention, by weight, including following components: 100 parts of rubber material, 40~50 parts of white carbon black, 2~3 parts of sulphur, 3~5 parts of complex antiager, 1~3 part of promotor, 10~15 parts of activating agent, 0.5~1 part of silane coupling agent, 10~15 parts of naphthenic oil, 1~3 part of C5 resin, wherein, it is in terms of 100 parts by the parts by weight of rubber material, the rubber material is made of 50~60 parts of natural rubbers, 30~40 parts of solution polymerized butadiene styrene rubbers and 5~15 parts of butadiene rubbers.Preparation method of the invention is easy, and person in middle and old age's shoes for walking with vigorous strides rubber ground obtained has good anti-slippery, adherence properties and ageing resistance, improves the safety in utilization and its service life of product shoes.
Description
Technical field
The present invention relates to rubber ground technical fields, more particularly to a kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber
Ground and preparation method thereof.
Background technique
As the mankind participate in sports, the promotion of body building degree, the place of sport footwear dress is no longer limited to body
Race is educated, crowd is worn and has also penetrated into middle-aged and old fitness group.From 1868 since pair of trainers occurs in the U.S.,
Its development history has exceeded a century；The research and development of domestic sport footwear start to walk from the eighties in last century, also there is more than 30 years history so far.But
Be, at present both at home and abroad the contention emphasis of Research Emphasis and the leading market power of branding campaign shoes manufacturer still concentrate on
Lower aspect: first is that the middle and high end professional motion shoes of athletic training and match are directed to, second is that for the common of young and middle-aged leisure
Sport footwear；Rarely have enterprise to carry out case study for the physiology and psychological characteristics of the middle-aged and the old, thus develop be suitable in it is old
The sport footwear ground of year people, be also difficult to see in the market with it is good it is anti-skidding, durable, safe, comfortable, wear off and the spies such as facilitate
The dedicated sport footwear of the middle-aged and the old of property, this just affects the moving-mass of the middle-aged and the old.
Therefore, the new change of world population ages how is complied with, the middle-aged and the old is complied with and plays an active part in the new of body building
Situation, to develop a kind of strong anti-skidding, age inhibiting sport footwear rubber ground walked with vigorous strides suitable for the middle-aged and the old, this representative
Current sport footwear rubber ground expand a kind of new invention of application field, represent a kind of new trend for leading industry development.
Light China elderly population have exceeded 1.6 hundred million according to statistics, and year increases 8,000,000；Middle-aged and old fitness group is extended from city to rural area；
The channel that the middle-aged and the old purchases shoes is extended from solid shop/brick and mortar store to online shopping shop.Due to the decline of middle-aged and the old's lower limb muscles, podarthrum pine
Relax, arch of foot stays, heel fat pad atrophy, above-mentioned physiological characteristic determines that the stability of middle-aged and the old's gait is poor, thus
It is required that strengthening anti-slippery, the adherence properties of ground；The middle-aged and the old's walks with vigorous strides to move, and rule is different from general sports,
Its exercise intensity, amount of exercise are little, and service life needed for shoes for walking with vigorous strides is then relatively long.Therefore when its formula design, in addition to
Ensure outside certain wearability, one of emphasis will have breakthrough in terms of anti-slippery and adherence properties, it is ensured that safe handling；
Secondly to have breakthrough in terms of ageing resistance, performance is higher than general professional motion shoes, it is ensured that service life reaches 5 years
Even 5 years or more.
Rubber clone as material for shoes generally selects unsaturated alkadiene rubber, these olefinic rubbers contain greatly
The unsaturated double bond of amount, and the active site of vulcanization reaction is just in these double bonds, to react sulfur vulcanization, create must
The condition wanted.But these double bonds also play conclusive effect to the aging of rubber simultaneously, and have seriously affected the use of rubber
Service life.After ageing of rubber, product can harden, become fragile, and substantially reduce the coefficient of friction of rubber ground, the adherence properties of rubber,
Anti-slippery degradation, and accelerate the rate of wear of rubber exponentially, so that making for rubber ground can be highly impacted
With the service life and wear safety.In general the aging life-span of sport footwear ground is designed as 2-3, but strong according to the middle-aged and the old
The manufacture claim of shoes is walked, ground service life should ensure that at 5 years or more.
Therefore, it is necessary to develop anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground of one kind and preparation method thereof.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides
Rubber ground and preparation method thereof, person in middle and old age's shoes for walking with vigorous strides rubber ground obtained have good anti-slippery, adherence properties and resist
Aging improves the safety in utilization and its service life of product shoes.
One of the objects of the present invention is to provide a kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground, for up to this
Purpose, the invention adopts the following technical scheme:
A kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground, by weight, including following components:
Wherein, by the parts by weight of rubber material be 100 parts in terms of, the rubber material by 50~60 parts of natural rubbers, 30~
40 parts of solution polymerized butadiene styrene rubbers and 5~15 parts of butadiene rubber compositions.
In the present invention, rubber material is used cooperatively using natural rubber, solution polymerized butadiene styrene rubber and butadiene rubber, and is passed through
The proportion for adjusting natural rubber, solution polymerized butadiene styrene rubber and butadiene rubber in rubber material, enhances the anti-slippery of ground and grabs
Ground；The addition of complex antiager improves the anti ageing property of rubber ground, passes through white carbon black, promotor, activating agent, silicon
The addition of alkane coupling agent, naphthenic oil and C5 resin, synthesis improve the anti-slippery of rubber ground, adherence properties, anti-aging.
Specifically, anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground, by weight, including following components:
100 parts of rubber material,
40~50 parts of white carbon black, such as the parts by weight of white carbon black are 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46
Part, 47 parts, 48 parts, 49 parts, 50 parts etc..
2~3 parts of sulphur, such as the parts by weight of sulphur are 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6
Part, 2.7 parts, 2.8 parts, 2.9 parts, 3 parts etc..
3~5 parts of complex antiager, such as the parts by weight of complex antiager are 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4
Part, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7
Part, 4.8 parts, 4.9 parts, 5 parts etc..
1~3 part of promotor, for example, promotor parts by weight be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts,
1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts,
2.9 parts, 3 parts etc..
10~15 parts of activating agent, such as the parts by weight of activating agent are 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts etc..
0.5~1 part of silane coupling agent, for example, silane coupling agent parts by weight be 0.5 part, 0.6 part, 0.7 part, 0.8 part,
0.9 part, 1 part etc..
10~15 parts of naphthenic oil, such as the parts by weight of naphthenic oil are 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts etc..
1~3 part of C5 resin, for example, C5 resin parts by weight be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts,
1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts,
2.9 parts, 3 parts etc..
Wherein, by the parts by weight of rubber material be 100 parts in terms of, the rubber material by 50~60 parts of natural rubbers, 30~
40 parts of solution polymerized butadiene styrene rubbers and 5~15 parts of butadiene rubbers composition, for example, the parts by weight of natural rubber are 50 parts, 51 parts, 52 parts,
53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts etc., the parts by weight of solution polymerized butadiene styrene rubber are 30 parts, 31 parts, 32
Part, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts etc., the parts by weight of butadiene rubber are 5 parts, 6 parts, 7 parts,
8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts etc..
It is used to characterize rubber soles abrasion resistance index both at home and abroad at present, generally be tested using AKR or DIN Abrasion Tester,
The country, China footwear major part stands its test method into standard, but is actually a reference data, wherein there is very big difference
The opposite sex, both testers are used primarily for the wearability of test tire, and the friction abrasion that it can embody rubber are worn away with rolling
Amount.But the abrasion of footwear is friction abrasion and the combination of pounding wear, be with tire it is discrepant, in its formula design
Consider certain tensile strength, it, can't doing with reduction coefficient of friction in order to ensure good anti-slippery and adherence properties
Method improves the wearability of rubber, thus the variety selection of rubber and and with proportion, the physical property of ground is played decisive
Effect.
The kind of rubber determines the physical characteristic of its ground, but single rubber is difficult to meet the physics of Project Product
Performance.So having finally chosen natural rubber (NR)/solution polymerized butadiene styrene rubber (SSBR)/butadiene rubber (BR) by a large number of experiments
Three kinds of rubber blendings, constitute excellent elastomer blended system, mixing ratio be (50~60)/(30~40)/(5~
15), preferably 55/35/10, to realize its mutual supplement with each other's advantages；Meanwhile it being facilitated to form the island phase structure of rubber molecular chain, reach
Elastomer blended connects skill Modification effect, enhances the anti-slippery and adherence properties of ground.
The aging of rubber is a more complicated chemical reaction process, it includes thermo-oxidative ageing, ozone aging, ultraviolet
Line is catalyzed the series of factors such as aging, dynamic fatigue aging.Variety selection and dosage as footwear ground to anti-aging agent, phase
More to be worth weighing for.Because the effect of anti-aging agent is the surface for making it move to rubber, preferentially acted on oxygen, thus
Attack of the oxygen to rubber surface is greatly reduced, oxidation is weakened；In view of polluting the influence to environmental protection, so choosing
The kind selected can only be confined to protect effect slightly worse and the anti-aging agent of without pollution again.
In order to make product reach protection effect of design, anti-aging agent of the invention is using physical protection agent and anti-with chemistry
Old agent system, and chemical antiager then uses antioxidant/anti-foul smell agent/heat resistance anti-aging agent paralled system, makes various anti-aging agents
The synergistic effect that protection is formd in rubber, optimizes protective action.By a large amount of degradation, finally determines and matched
The basic cooperation of the aging protection system of side are as follows: the complex antiager is physics and chemically composited anti-aging agent；Further,
The complex antiager is the mixture of BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline and paraffin；Further
Ground, in terms of 100 parts of rubber material, the BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline and paraffin weight part ratio
For (0.7~1): (0.4~0.6): 0.5:1.5:0.5, the weight part ratio can be 0.7:0.4:0.5:1.5:0.5,0.7:
0.5:0.5:1.5:0.5、0.7:0.6:0.5:1.5:0.5、0.8:0.4:0.5:1.5:0.5、0.9:0.4:0.5:1.5:0.5、
1:0.4:0.5:1.5:0.5 waiting.
In the present invention, which is characterized in that by weight, the promotor by 1~2 part of altax -80,0.2~
0.5 part of promotor ZDTP-50 and 0.1~0.3 part of diphenylguanidine -80 form.Such as the parts by weight of altax -80 be 1 part,
1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts etc., promotor ZDTP-50's
Parts by weight are 0.2 part, 0.3 part, 0.4 part, 0.5 part etc..
In the present invention, by weight, the activating agent is by 2~6 parts of zinc oxide, 1~2 part of stearic acid and 2~5 parts
PEG-4000 surfactant composition.Such as the parts by weight of zinc oxide are 2 parts, 3 parts, 4 parts, 5 parts, 6 parts etc., it is stearic heavy
Measuring part is 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts etc., PEG-
The parts by weight of 4000 surfactants are 2 parts, 3 parts, 4 parts, 5 parts etc..
It in the present invention, is used cooperatively, the surface of white carbon black is modified, simultaneously by silane coupling agent and activating agent
There are also graft effects in modifying process, so that the skid resistance of rubber be made to greatly improve.
It also include 1~5 part of colorant, such as the parts by weight of colorant are 1 part, 2 parts, 3 parts, 4 parts, 5 parts in the present invention
Deng.
The second object of the present invention is to provide a kind of preparation of person in middle and old age's shoes for walking with vigorous strides rubber ground described in the first purpose
Method, the preparation method include the following steps: after according to the ratio mixing natural rubber, solution polymerized butadiene styrene rubber and butadiene rubber
Refining is closed, white carbon black, complex antiager, promotor, activating agent, silane coupling agent, naphthenic oil and C5 resin is added, optional adds
Enter colorant, be kneaded, add sulfur cross-linking, obtains person in middle and old age's shoes for walking with vigorous strides rubber ground.
As a preferred solution of the present invention, person in middle and old age's shoes for walking with vigorous strides rubber ground preparation method the following steps are included:
1) according to the ratio by solution polymerized butadiene styrene rubber and butadiene rubber mixing, addition natural rubber, which close refining, obtains mixing mother
Material；
2) be added according to the ratio into the mixing masterbatch that step 1) obtains white carbon black, complex antiager, promotor, activating agent,
Silane coupling agent, naphthenic oil and C5 resin are kneaded, and mixture sizing material is obtained；
3) sulfur cross-linking is added according to the ratio into the mixture sizing material that step 2) obtains and carries out conjunction refining, obtain described anti-skidding
Age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground.
In step 1), it is described close refining time be 1~3min, such as close refining time be 1min, 1.5min, 2min,
2.5min or 3min etc..
Preferably, in step 2), the temperature of the mixing is 100~120 DEG C, such as the temperature of mixing is 100 DEG C, 105
DEG C, 110 DEG C, 115 DEG C, 120 DEG C etc.；The time of the mixing be 1~5min, such as mixing time be 1min, 2min,
3min, 4min, 5min etc..
Preferably, in step 3), time of the vulcanization is 0.5~1h, for example, vulcanization time be 0.5h, 0.6h,
0.7h,0.8h,0.9h,1h；The temperature of the vulcanization be 80~120 DEG C, such as vulcanize steady temperature be 80 DEG C, 90 DEG C, 100 DEG C,
110℃、120℃。
Preferably, in step 2), when mixing, is also added into 1~5 part of colorant.
Compared with prior art, the invention has the benefit that
(1) person in middle and old age's shoes for walking with vigorous strides rubber ground of the invention has good non-skid property and anti ageing property, friction
Coefficient (dry type) >=0.9 (national standard is >=0.7)；Tearing strength >=40KN/m；Tensile strength >=12MPa；Elongation at break >=
450%；70 DEG C × 72h of hot air aging, change degree are no more than 10%；Ozone aging 100ppm × for 24 hours, no cracking.
(2) preparation method of the invention is easy, person in middle and old age's shoes for walking with vigorous strides rubber ground obtained, has good anti-slippery
Property, adherence properties and ageing resistance, improve the safety in utilization and its service life of product shoes, service life up to 5 years or more,
It is especially suitable for the production of middle-aged and the old's shoes for walking with vigorous strides.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
Embodiment 1
The preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground of the present embodiment, comprising the following steps:
1) by weight, 30 parts of solution polymerized butadiene styrene rubbers and 10 parts of butadiene rubbers are mixed, be added 60 parts of natural rubbers into
Row closes refining 2min, obtains mixing masterbatch；
2) by weight, into the mixing masterbatch that step 1) obtains be added 40 parts of white carbon blacks, 3.7 parts of complex antiagers,
It is carried out at a temperature of 2.1 parts of promotors, 12 portions of activating agents, 0.6 part of silane coupling agent, 10 parts of naphthenic oils and 2 parts 110 DEG C of C5 resin
It is kneaded 4min, obtains mixture sizing material；Wherein, complex antiager is BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline
With the mixture of paraffin, weight part ratio 0.7:0.5:0.5:1.5:0.5；Promotor is by 1.5 parts of altaxes -80,0.4 part
Promotor ZDTP-50 and 0.2 part of diphenylguanidine -80 form；Activating agent is by 5 parts of zinc oxide, 2 parts of stearic acid and 5 parts of PEG-4000
Surfactant composition；
3) by weight, into the mixture sizing material that step 2) obtains be added 3 parts 100 DEG C of sulfur cross-linking at a temperature of into
Row closes refining 0.6h, obtains anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground.
Embodiment 2
The preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground of the present embodiment, comprising the following steps:
1) by weight, 40 parts of solution polymerized butadiene styrene rubbers and 10 parts of butadiene rubbers are mixed, be added 50 parts of natural rubbers into
Row closes refining 3min, obtains mixing masterbatch；
2) by weight, into the mixing masterbatch that step 1) obtains be added 45 parts of white carbon blacks, 4.1 parts of complex antiagers,
It is carried out at a temperature of 2.7 parts of promotors, 11 portions of activating agents, 0.8 part of silane coupling agent, 12 parts of naphthenic oils and 1 part 120 DEG C of C5 resin
It is kneaded 1min, obtains mixture sizing material；Wherein, complex antiager is BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline
With the mixture of paraffin, weight part ratio 1:0.6:0.5:1.5:0.5；Promotor is by 2 parts of altaxes -80,0.5 part of promotion
Agent ZDTP-50 and 0.2 part of diphenylguanidine -80 form；Activating agent is by 5 parts of zinc oxide, 2 parts of stearic acid and 4 parts of surfaces PEG-4000
Activating agent composition；
3) by weight, into the mixture sizing material that step 2) obtains be added 2.5 parts 80 DEG C of sulfur cross-linking at a temperature of into
Row closes refining 1h, obtains anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground.
Embodiment 3
The preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground of the present embodiment, comprising the following steps:
1) by weight, 35 parts of solution polymerized butadiene styrene rubbers and 10 parts of butadiene rubbers are mixed, be added 55 parts of natural rubbers into
Row closes refining 2min, obtains mixing masterbatch；
2) by weight, into the mixing masterbatch that step 1) obtains be added 50 parts of white carbon blacks, 3.8 parts of complex antiagers,
It is carried out at a temperature of 2.7 parts of promotors, 10 portions of activating agents, 0.8 part of silane coupling agent, 13 parts of naphthenic oils and 2 parts 100 DEG C of C5 resin
It is kneaded 4min, obtains mixture sizing material；Wherein, complex antiager is BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline
With the mixture of paraffin, weight part ratio 0.8:0.5:0.5:1.5:0.5；Promotor is by 2 parts of altaxes -80,0.4 part of rush
It is formed into agent ZDTP-50 and 0.3 part of diphenylguanidine -80；Activating agent is by 3 parts of zinc oxide, 2 parts of stearic acid and 5 parts of PEG-4000 tables
Face activating agent composition；
3) it is carried out at a temperature of by weight, being added 3 parts 90 DEG C of sulfur cross-linking into the mixture sizing material that step 2) obtains
Refining 0.6h is closed, anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground is obtained.
Embodiment 4
The preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground of the present embodiment, comprising the following steps:
1) by weight, 32 parts of solution polymerized butadiene styrene rubbers and 18 parts of butadiene rubbers are mixed, be added 50 parts of natural rubbers into
Row closes refining 1min, obtains mixing masterbatch；
2) by weight, into the mixing masterbatch that step 1) obtains be added 40 parts of white carbon blacks, 4.1 parts of complex antiagers,
It is mixed at a temperature of 2.8 parts of promotors, 13 portions of activating agents, 1 part of silane coupling agent, 12 parts of naphthenic oils and 3 parts 115 DEG C of C5 resin
3min is refined, mixture sizing material is obtained；Wherein, complex antiager be BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline and
The mixture of paraffin, weight part ratio 1:0.6:0.5:1.5:0.5；Promotor is by 2 parts of altaxes -80,0.5 part of promotor
ZDTP-50 and 0.3 part of diphenylguanidine -80 forms；Activating agent is living by 6 parts of zinc oxide, 2 parts of stearic acid and 5 parts of surfaces PEG-4000
Property agent composition；
3) it by weight, is added at a temperature of 2.6 parts 110 DEG C of sulfur cross-linking into the mixture sizing material that step 2) obtains
It carries out closing refining 0.8h, obtains anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground.
Embodiment 5
The preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground of the present embodiment, comprising the following steps:
1) by weight, 35 parts of solution polymerized butadiene styrene rubbers and 15 parts of butadiene rubbers are mixed, be added 50 parts of natural rubbers into
Row closes refining 3min, obtains mixing masterbatch；
2) by weight, into the mixing masterbatch that step 1) obtains be added 45 parts of white carbon blacks, 4 parts of complex antiagers,
It is carried out at a temperature of 1.8 parts of promotors, 11 portions of activating agents, 1 part of silane coupling agent, 12 parts of naphthenic oils and 1.2 parts 120 DEG C of C5 resin
It is kneaded 2min, obtains mixture sizing material；Wherein, complex antiager is BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline
With the mixture of paraffin, weight part ratio 0.9:0.6:0.5:1.5:0.5；Promotor is by 1 part of altax -80,0.5 part of rush
It is formed into agent ZDTP-50 and 0.3 part of diphenylguanidine -80；Activating agent is by 5 parts of zinc oxide, 1 part of stearic acid and 5 parts of PEG-4000 tables
Face activating agent composition；
3) it by weight, is added at a temperature of 2.4 parts 100 DEG C of sulfur cross-linking into the mixture sizing material that step 2) obtains
It carries out closing refining 0.6h, obtains anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground.
Embodiment 6
It is in place of the difference of the present embodiment and embodiment 5, in step 2), when mixing is also added into 4 parts of colorants.
Comparative example 1
It is in place of the rubber material of this comparative example and the difference of embodiment 1, the rubber material is by 60 parts of natural rubbers
It is formed with 40 parts of butadiene rubbers, does not contain solution polymerized butadiene styrene rubber, other components and preparation method are same as Example 1.
Comparative example 2
It is in place of the rubber material of this comparative example and the difference of embodiment 1, the rubber material is by 60 parts of natural rubbers
It is formed with 40 parts of solution polymerized butadiene styrene rubbers, does not contain butadiene rubber, other components and preparation method are same as Example 1.
Comparative example 3
It is in place of the rubber material of this comparative example and the difference of embodiment 1, the anti-aging agent is vaseline and paraffin
Mixture, the parts by weight of anti-aging agent are 3.7 parts, and the parts by weight of vaseline and paraffin are respectively 2.8 parts, 0.9 part, other groups
Divide and preparation method is same as Example 1.
Comparative example 4
It is in place of the difference of the rubber material of this comparative example and embodiment 1, the anti-aging agent is BHT anti-aging agent, MB is anti-
Old agent, 445 anti-aging agents mixture, the parts by weight of anti-aging agent are 3.7 parts, BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents
Parts by weight are respectively 1.4 parts, 1.1 parts, 1.2 parts, and other components and preparation method are same as Example 1.
Comparative example 5
Be in place of the difference of the rubber material of this comparative example and embodiment 1, promotor by 1.5 parts of altaxes -80 and
0.6 part of promotor ZDTP-50 composition, other components and preparation method are same as Example 1.
Comparative example 6
It is in place of the rubber material of this comparative example and the difference of embodiment 1, activating agent is by 7.5 parts of zinc oxide, 4.5 parts
Stearic acid composition, other components and preparation method are same as Example 1.
By rubber material progressive made from person in middle and old age's shoes for walking with vigorous strides rubber ground made from embodiment 1-6 and comparative example 1-6
It can test, test result is as shown in table 1.Wherein, the testing standard of tensile strength and elongation at break is referring to GB/T528-2008
National standard carry out, the testing standard of tearing strength is carried out referring to the national standard of GB/T529-2008, hot air aging
Testing standard is carried out referring to the national standard of GB/T 3512-1983, and the testing standard of ozone aging is referring to GB/T 13642-
1992 national standard carries out.
Table 1
As can be seen from Table 1, relative to embodiment 1, the rubber material of comparative example 1 does not contain solution polymerized butadiene styrene rubber, only by
Natural rubber and butadiene rubber composition, the synthetic rubber of comparative example 2 are only made of natural rubber and solution polymerized butadiene styrene rubber, are free of
There is butadiene rubber, the coefficient of friction of rubber ground obtained decreases, wet-sliding resistant performance decline.
Relative to embodiment 1, the anti-aging agent of comparative example 3 only with vaseline and paraffin mixture, comparative example 4 it is anti-
Old agent BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents mixture, the anti ageing property of rubber ground obtained under
Drop, 70 DEG C × 72h of hot air aging, change rate of strength are 15% or more, ozone aging 100ppm × for 24 hours, and there is slight cracking.
Relative to embodiment 1, the promotor of comparative example 5 is only made of altax -80 and promotor ZDTP-50, comparison
The activating agent of example 6 is only made of zinc oxide, stearic acid, and the tensile strength of manufactured rubber material, pulls apart elongation at tearing strength
Rate is declined；Dry friction coefficient reduces, and anti-slippery also decreases.
In conclusion person in middle and old age's shoes for walking with vigorous strides rubber ground of the invention, has good non-skid property and anti-aging
Can, coefficient of friction (dry type) >=0.9 (national standard is >=0.7)；Tearing strength >=40KN/m；Tensile strength >=12MPa；It pulls apart and stretches
Long rate >=450%；70 DEG C × 72h of hot air aging, change degree are no more than 10%；Ozone aging 100ppm × for 24 hours, no cracking；
The safety in utilization and its service life of product shoes are improved, service life was especially suitable for the middle-aged and the old up to 5 years or more
The production of shoes for walking with vigorous strides.
Detailed process equipment and process flow of the invention that the present invention is explained by the above embodiments, but the present invention is simultaneously
It is not limited to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention must rely on above-mentioned detailed process equipment
It could implement with process flow.It should be clear to those skilled in the art, any improvement in the present invention, to this hair
The equivalence replacement of bright each raw material of product and addition, the selection of concrete mode of auxiliary element etc., all fall within protection model of the invention
Enclose within the open scope.
Claims (10)
1. a kind of anti-skidding age inhibiting person in middle and old age's shoes for walking with vigorous strides rubber ground, which is characterized in that by weight, including with the following group
Point:
It wherein, is in terms of 100 parts by the parts by weight of rubber material, the rubber material is by 50~60 parts of natural rubbers, 30~40 parts
Solution polymerized butadiene styrene rubber and 5~15 parts of butadiene rubber compositions.
2. person in middle and old age's shoes for walking with vigorous strides rubber ground according to claim 1, which is characterized in that the complex antiager is physics
With chemically composited anti-aging agent.
3. person in middle and old age's shoes for walking with vigorous strides rubber ground according to claim 2, which is characterized in that the complex antiager is BHT
Anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline and paraffin mixture.
4. person in middle and old age's shoes for walking with vigorous strides rubber ground according to claim 3, which is characterized in that in terms of 100 parts of rubber material, institute
The weight part ratio for stating BHT anti-aging agent, MB anti-aging agent, 445 anti-aging agents, vaseline and paraffin is (0.7~1): (0.4~0.6):
0.5:1.5:0.5。
5. person in middle and old age's shoes for walking with vigorous strides rubber ground described in one of -4 according to claim 1, which is characterized in that by weight, institute
Promotor is stated by 1~2 part of altax -80,0.2~0.5 part of promotor ZDTP-50 and 0.1~0.3 part of -80 group of diphenylguanidine
At.
6. person in middle and old age's shoes for walking with vigorous strides rubber ground described in one of -5 according to claim 1, which is characterized in that by weight, institute
Activating agent is stated to be made of 2~6 parts of zinc oxide, 1~2 part of stearic acid and 2~5 parts of PEG-4000 surfactants.
7. person in middle and old age's shoes for walking with vigorous strides rubber ground described in one of -6 according to claim 1, which is characterized in that also comprising 1~5 part
Toner.
8. a kind of preparation method of person in middle and old age's shoes for walking with vigorous strides rubber ground as described in one of claim 1-7, which is characterized in that institute
It states preparation method to include the following steps: to close refining after according to the ratio mixing natural rubber, solution polymerized butadiene styrene rubber and butadiene rubber, be added
White carbon black, complex antiager, promotor, activating agent, silane coupling agent, naphthenic oil and C5 resin, optional addition colorant, into
Row is kneaded, and is added sulfur cross-linking, is obtained person in middle and old age's shoes for walking with vigorous strides rubber ground.
9. preparation method according to claim 8, which is characterized in that the preparation method comprises the following steps:
1) solution polymerized butadiene styrene rubber and butadiene rubber are mixed according to the ratio, addition natural rubber, which close refining, obtains mixing masterbatch；
2) white carbon black, complex antiager, promotor, activating agent, silane are added according to the ratio into the mixing masterbatch that step 1) obtains
Coupling agent, naphthenic oil and C5 resin are kneaded, and mixture sizing material is obtained；
3) sulfur cross-linking is added according to the ratio into the mixture sizing material that step 2) obtains and carries out conjunction refining, obtain the anti-skidding anti-aging
Person in middle and old age's shoes for walking with vigorous strides rubber ground.
10. preparation method according to claim 8 or claim 9, which is characterized in that in step 1), it is described close refining time be 1~
3min；
Preferably, in step 2), the temperature of the mixing is 100~120 DEG C, and the time of the mixing is 1~5min；
Preferably, in step 3), the time of the vulcanization is 0.5~1h, and the temperature of the vulcanization is 80~120 DEG C.
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| CN110862586A (en) * | 2019-10-16 | 2020-03-06 | 福建省华昂体育用品有限公司 | Vulcanized sole material with recycled leftover materials and process |
| CN111349277A (en) * | 2020-04-30 | 2020-06-30 | 黄成余 | Low-hardness high-wear-resistance anti-slip sole material for shoes and preparation method thereof |
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Application publication date: 20190712 |