CN1157131C - Sole - Google Patents
Sole Download PDFInfo
- Publication number
- CN1157131C CN1157131C CNB961115289A CN96111528A CN1157131C CN 1157131 C CN1157131 C CN 1157131C CN B961115289 A CNB961115289 A CN B961115289A CN 96111528 A CN96111528 A CN 96111528A CN 1157131 C CN1157131 C CN 1157131C
- Authority
- CN
- China
- Prior art keywords
- rubber
- sole
- rubber composition
- weight
- weight portion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
To make wet-gripping properties on a wet floor excellent and to make shoes difficult to slip even on a wet floor surface by making shoes out of a vulcanized molded product of a rubber composition containing a specified amount by weight of a silylating agent per 100 pt.wt. a rubber. An outsole 2 is made out of a vulcanized molded product of a rubber composition containing 1 to 15 pt.wt. silylating agent per 100 pts.wt. rubber. If the content of the silylating agent is less than 1 pt.wt. per 100 pts.wt. rubber, the effect of making the outsole water-repellent cannot be exhibited satisfactorily whereas if the content of the silylating agent is over 15 pt.wt. per 100 pts.wt. rubber, the silylating agent deposits on the surface of the outsole, making the outsole slippery on a usual smooth surface. Thus, the wet gripping properties on a wet floor surface can be made excellent and shoes can be made hard to slip even on a wet floor surface.
Description
The present invention relates to a kind of sole, in more detail, even relate to the sole that also can not skid on wet ground.
The skid resistance of footwear is one of key properties to footwear, works hard and makes its various footwear that are difficult to skid that mass selling be arranged on market being located at pattern on the sole bottom surface (part that sole and ground directly contact).
Yet, they be with the road surface of doing as object, the rainfall or the road surface in rain stopping time are wet state, its pavement characteristics is obviously inequality, wear these footwear and skid easily, therefore, must contest interruped, games results are descended, also may cause injured under the worst situation.
For example, when playing tennis, in hard concrete place (if rain during the match of Ha-De コ-ト), can be because the sliding adventurous reason in road surface and contest interruped, even and can proceed match, but physical demands is big, and games results are descended.
If the road surface is dampness, then footwear skid easily, this be because the moisture film on the road surface between sole and road surface, hinder sole and road surface contact the cause that adhesion friction power between the two diminishes.
Therefore,, maybe will to have absorptive material and be used for sole because the adhesion friction power that causes of moisture film on this road surface reduces, and for example the someone advises being provided with zanjon and improves draining on sole in order suppressing to draw scheme such as moisture film.
Yet, as the former, be provided with under the situation of zanjon at sole, owing to frictional force on the road surface of doing cross produces by force dangerous, and problem such as sole abrasion is too fast in addition; Be used under the situation of sole if resemble the material that will have the suction bosom the latter, restricted to the water yield that sucks, and produce the problem that footwear are increased the weight of owing to absorb water.
The objective of the invention is to provide a kind of and can overcome above-mentioned prior art problems, even the sole that also can not skid on the road surface of humidity.
The present invention, as the method that solves above-mentioned problem, be use on the sole a kind of water absorption rate by weight benchmark be the material that is difficult to attached water below 1% more than 0%.
Just, if on sole, use the material that is difficult to attached water, water is adhered to from the teeth outwards, and when sole is stepped on the road surface, be not easy to get rid of the water on its road surface.
And, among the present invention,, be conceived to water absorption rate as the selected yardstick that is difficult to the material of attached water, and the water absorption rate of finding sole by weight benchmark be 1% o'clock, even wet road surface also is difficult to skid.
In the present invention, water absorption rate is to try to achieve according to 24 hours weight rate of dipping under room temperature in the distilled water, and, among the present invention, the water absorption rate of sole is specific for below 1%, be because when water absorption rate is higher than 1%, skid easily on the road surface of wetting by torrent; And water absorption rate is lower than at 1% o'clock, even wet road surface also is difficult to skid.By the way,, seldom see below 1% all more than 1.5% as the most water absorption rate of vulcanization forming thing of the rubber composition that uses at the bottom of the city shoe.
Among the present invention, sole hardness is pressed JIS-A hardness (promptly pressing the fixed hardness of JIS-A type hardness tester instrumentation) must be in the scope of 40-95, preferred 50-95, more preferably 60-90.Just, the hardness of sole is lower than at 40 o'clock by JIS-A hardness, and sole is too soft and unstable, and when the hardness of sole was higher than 95 by JIS-A hardness, sole caused being through feeling under the weather on the pin too firmly.
As above-mentioned water absorption rate by weight benchmark be the low sole of water absorption rate below 1%, in order to improve the hydrophobicity of rubber constituent, can be by the rubber composition that has cooperated silane-based agent, or cooperate the various compositions such as composition of fillers such as silica and clay to form in a large number.For example, by with respect to 100 parts by weight of rubber, contain 1-15 weight portion silane-based agent and just can obtain the low rubber composition of water absorption rate.And under the use level of the filler situation how, for example the use amount of silica is in the scope of 30-80 weight portion with respect to rubber 100 weight portions.Also can use silane-based agent or organosilan coupling agent in such cases, the use amount of organosilan coupling agent is generally in the scope of 0.1-15 weight portion with respect to rubber 100 weight portions.As water absorption rate is the preferred example of the low rubber composition of the following so-called water absorption rate of 1 (weight) %, for example can enumerate: the rubber composition that cooperates silane-based agent 1-15 weight portion with respect to rubber 100 weight portions; Being combined with kaolin with respect to rubber 100 weight portions is that the clay 10-40 weight portion and the organosilan coupling agent of principal component is the rubber composition of 0.1-15 weight portion; Base-material rubber is the mixture formation by specific solution styrene-butadiene rubber 60-85 (weight) % and butadiene rubber 15-40 (weight) %, with respect to this base-material rubber rubber 100 weight portions that are principal component, be combined with 55-70 weight portion silica, cooperating organic silane coupling agent is more than 1/15 below 1/5 of silica weight, preferred rubber composition below 1/5 more than 1/12.
Below preferred compositions is wherein described.
At first the situation that contains silane-based agent is described in detail.
Owing to be combined with silane-based agent in rubber constituent, therefore can make the gained vulcanized rubber is water repellency.Among the present invention, as silane-based agent, for example can be with the compound of following general formula (1) expression.
R
1 aSiX
4-a (1)
(in the formula, a is the integer of 0-3, R
1Be-H or-CH
3,-C
6H
5Deng organic group, X is-Cl ,-OCH
3,-CO
2H
5Etc. water-disintegrable base).
The object lesson of above-mentioned silane-based agent for example can be enumerated: phenyl trichlorosilane (C
6H
5SiCl
3), diphenyl dichlorosilane ((C
6H
5)
2SiCl
2), phenyl triethoxysilane (C
6H
5Si (OC
2H
5)
3), isobutyl group trimethoxy silane ((CH
3)
2CHCH
2Si (OCH
3)
3), hexyl trimethoxy silane ((CH
3(CH
2)
5Si (OCH
3)
3), dimethoxydiphenylsilane ((C
6H
5)
2Si (OCH
3)
2) etc.Also can use hexamethyldisilazane ((CH
3)
3SiNHSi (CH
3)
3) wait the silazane compound, N, O-(two three silicyls) acetamide (CH
3C (OSi (CH
3)
3) NSi (CH
3)
3), tert-butyl chloro-silicane (uncle-C
4H
9(CH
3)
2Silane-based agent such as SiCl).
This silane-based agent can be with various blenders and rubber mix with compounding ingredient with other rubber, and silane-based agent at room temperature is liquid, and is therefore also very good to the dispersiveness of rubber.And, can not damage other character like this owing to sneaking into silane-based agent, rubber hardening, intensity are significantly reduced, and just give so-called water repellency this special nature, and water absorption rate is reduced common sole.
Above-mentioned silane-based agent with respect to rubber 100 weight portions, contains the 1-15 weight portion, and it be the reasons are as follows.When the content of silane-based agent was less than 1 weight portion with respect to rubber 100 weight portions, sole was owing to the effect that water repellency causes the sole water absorption rate to reduce is not enough; If the content of silane-based agent is higher than 15 weight deals with respect to rubber 100 weight portions, then silane-based agent is separated out on the surface of sole, even common like this even surface also skids easily.
And if cooperate silica in containing the rubber composition of above-mentioned silane-based agent, when rubbery intensity increased, water repellency further improved, and adhesion (the グ リ Star プ) property on wet road surface further improves, more difficult skidding on wet road surface.The content of this silica in rubber composition is with respect to rubber 100 weight portions, fits best 30-80 weight portion.The content of silica with respect to rubber 100 weight portions, when being lower than 30 weight portions, might can not be given full play to the effect that contains silica.The content of silica, with respect to rubber 100 weight portions, when being higher than 80 weight portions, the sole hardening, adherence reduces on the contrary, skid easily, and processability also may have problems.
Owing in the rubber composition that above-mentioned sole is used, be combined with carbon, thereby further improve wearability, be suitable for carrying out the shoes of vigorous exercise.The content of this carbon in rubber composition is with respect to rubber 100 weight portions, fits best 30-80 weight portion.The content of carbon with respect to rubber 100 weight portions, when being less than 30 weight portions, might be able to not be given full play to for the reinforcing effect that improves wearability; When the content of carbon, with respect to rubber 100 weight portions, when being higher than 80 weight portions, sole is too hard, might be unsuitable for doing sole and use.This carbon and silica and with can not producing any problem, thus both can and usefulness.
As above-mentioned sole with the rubber that uses in the rubber composition, for example can use natural rubber, isoprene rubber, butadiene rubber, SBR styrene butadiene rubbers, chloroprene rubber, acrylonitrile-butadiene rubber etc., normally used any rubber is all right when making sole, when the preparation rubber composition, these rubber both can use separately separately, also can more than 2 kinds and use.
Sole also can suit to cooperate some compounding ingredient of use, i.e. sulphur, promoter, zinc oxide, stearic acid, softening agent or plasticizer, antiaging agents etc. in sole cooperates with rubber usually as required with in the rubber composition.For example with respect to rubber 100 weight portions, best use level scope is: sulphur is the 0.5-5 weight portion, and promoter is the 0.3-5 weight portion, and zinc oxide is the 0.5-10 weight portion, stearic acid is that 0.5-10 weight portion, softening agent or plasticizer are the 0-40 weight portion, and antiaging agent is the 0-5 weight portion; But it is also harmless that use level exceeds this scope.
Below the situation that contains clay and organosilan coupling agent is described in detail it.
As previously mentioned, as long as with respect to rubber 100 weight portions, containing with kaolin is the clay 10-40 weight portion of main component, and organosilan coupling agent 0.1-15 weight portion, promptly can obtain the low sole of water absorption rate.As rubber in such cases, diene series rubber is especially suitable.
Above-mentioned clay, so long as with kaolin be principal component clay just, have no particular limits, but preferably at 600 ℃-800 ℃ baked clays down.Just, the clay that with kaolin is principal component often has the situation that contains constitution water in hydrophilic group exposing surface, the crystallization, by the roasting under 600 ℃-800 ℃, loses constitution water and improves its hydrophobicity, the effect of giving the sole water repellency improves, and the water absorption rate of sole is reduced.Yet the roasting that less than is 600 ℃ is difficult to remove the constitution water in the crystallization, and in case above 800 ℃, kaolinic crystal structure changes easily, might lose the original characteristic of kaolin.In order further to improve the water repellency of clay, the most handy organosilan coupling agent is handled after the roasting.
The content of this clay with respect to rubber 100 weight portions, is the 10-40 weight portion, preferred 10-30 weight portion.The content of clay with respect to rubber 100 weight portions, when being less than 10 weight portions, can not give full play to making sole have the effect that reduces the sole water absorption rate behind the water repellency, therefore can not justice divides and improve the effect that is difficult to skid on warm road surface; If the content of clay, with respect to rubber 100 weight portions, when being higher than 40 weight portions, then the tension resistance to spalling might reduce.
Also contain the organosilan coupling agent with above-mentioned clay, but, for example preferably use with Y as this organosilan coupling agent
3SiR
2(in the formula, Y represents alkoxyl or chlorine atom, R to the organosilan coupling agent of expression
2Represent any a kind in vinyl, glycidyl, methylpropenyl, amino, sulfydryl, epoxy radicals or the imino group) and with (C
nH
2n+1O)
3-Si-(CH
2)
m-S
k-(CH
2)
m-Si-(C
nH
2n+1O)
3The organosilan coupling agent of (in the formula, n represents the integer of 1-4, and m, k represent the integer of 1-6 respectively) expression.
As the concrete example of this organosilan coupling agent, can enumerate: vinyltrimethoxy silane, VTES, ethene-three (2-methoxy ethoxy) silane, vinyl trichlorosilane, γ-metacryloxy propyl trimethoxy silicane, γ-metacryloxy propyl-triethoxysilicane, γ-An Bingjisanjiayangjiguiwan, γ-mercaptopropyl trimethoxysilane, two (3-triethoxysilylpropyltetrasulfide) tetrasulfide [bis (3-triethoxysilylproyl) tetrasul fide] etc.
Above-mentioned organosilan coupling agent, in rubber composition, can cooperate by any form, but preferably cooperate with the state of anticipating, just, the organosilan coupling agent play a part with rubber composition in inanimate matter and organic carrying out after the chemical bond with inanimate matter and organic bonding together, if therefore cooperate to give the state of with the organosilan coupling agent clay being handled earlier, make clay performance hydrophobicity by the organosilan coupling agent, the water repellency effect, hydrophilic segment in the rubber composition is transformed into hydrophobicity, then can give water repellency preferably, the water absorption rate of sole is reduced sole.As mentioned above, in case give sole with water repellency, then can suppress to be clipped in moisture film between sole and the road surface attached on the sole, discharge was attached to the water droplet of sole surface originally easily simultaneously.Consequently, increased the real contact area on sole and road surface, strengthened adhesion friction power, improved the wet adherence (to the adherence on wet road surface) of sole, even wet road surface also is difficult to skid.
The content of this organosilan coupling agent with respect to rubber 100 weight portions, is the 0.1-15 weight portion, preferred 0.1-0.8 weight portion.The content of organosilan coupling agent with respect to rubber 100 weight portions, when being less than 0.1 weight portion, can not be given full play to the effect that makes sole have water repellency and make the water absorption rate reduction of sole; When the content of organic silane coupling agent, with respect to rubber 100 weight portions, when being higher than 15 weight, cost can raise, and processability might have problems.
Under the situation that contains this clay and organosilan coupling agent, as rubber, for example can mainly use natural rubber, isoprene rubber, butadiene rubber, SBR styrene butadiene rubbers, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, diene series rubbers such as butyl rubber.When the preparation rubber composition, these rubber can use separately separately, also can more than 2 kinds and use.
Yet, cooperating under the situation of clay, clay generally has the tendency that the intensity of making reduces, and therefore preferably further cooperates reinforcing agents such as carbon black or silica at above-mentioned sole in rubber composition.At this moment, with respect to the content (reinforcing agent total amount) of reinforcing agents such as carbon black or silica and the total amount of clay content, the containing ratio of clay is preferably 15-80 weight %.The reinforcing agent total amount with respect to rubber 100 weight portions, is preferably the 50-90 weight portion.
The mixture that below describes in detail specific solution styrene-butadiene rubber and butadiene rubber is used as base-material rubber, make and contain silica in the rubber composition, and contain the organosilan coupling agent according to special ratios, thereby obtain the situation of water absorption rate at the low sole of the water absorption rate below 1% with respect to silica.
By in diene series rubbers such as emulsion polymerization SBR styrene butadiene rubbers, butadiene rubber, natural rubber, cooperating silica or organosilan coupling agent just can obtain the low rubber composition of water absorption rate, but use specific solvent polymeric SBR styrene butadiene rubbers can further improve its skid resistance, and can improve the wearability on dry pavement.
As solution styrene-butadiene rubber, can use its sulfide is that the dynamic strain of the dynamic viscoelastic temperature distribution history of the frequency measured of 2 ℃/timesharing during as 10Hz is present in solution styrene-butadiene rubber in-10 ℃～-30 ℃ at the peak value of 0.25% o'clock loss coefficient (tan δ) in the intensification temperature.But, the loss coefficient of this solution styrene-butadiene rubber (tan δ) is to measure with following method: with respect to solution styrene-butadiene rubber 100 weight portions, cooperate zinc oxide 3 weight portions, stearic acid 1 weight portion, silica 40 weight portions, sulphur 2 weight portions and promoter 1.5 weight portions [accelerator NS (the N-tert-butyl group-2-[4-morpholinodithio base sulfenamide 1 weight portion and diphenylguanidine (diphenylguanidine) 0.5 weight portion], obtain rubber composition, pressurization was vulcanized and sulphidisation in 30 minutes under 160 ℃, dynamic visco-elastic property when 10Hz is measured in 2 ℃/timesharing of programming rate, make its temperature dispersion curve, the mensuration dynamic strain is 0.25% o'clock a loss coefficient (tan δ).Solution styrene-butadiene rubber, from the curring time viewpoint, special optimal ethylene content is below 50%.
Above-mentioned solution styrene-butadiene rubber, thereby mainly to making the suitable skid resistance that improves of loss coefficient of sole play advantageous effect, and, the wearability of sole also can be improved.But this solution styrene-butadiene rubber is if use separately, then produces sclerosis during low temperature, might crack, and therefore should and use with butadiene.As this butadiene, preferably using cis-1,4 content is more than 90%.Be in for the peak value of loss coefficient (tan δ) and be lower than-30 ℃ of polymerisation in solution polyethylene-butadiene rubbers in the temperature,, can not expect to have the effect of skid resistance and mar proof based on this rubber.Be higher than-10 ℃ of solution styrene-butadiene rubbers in the temperature and be in,, also can not fully prevent the sclerosis under the low temperature and crack even for example as butadiene rubber and admixture for the peak value of loss coefficient (tan δ).
With the usage rate of butadiene rubber, preferably solution styrene-butadiene rubber is 60-85 (weight) %, and butadiene rubber is 15-40 (weight) %.When being less than 60 (weight) %, can not give full play to above-mentioned solution styrene-butadiene the effect that improves skid resistance; When if solution styrene-butadiene is higher than 85 (weight) %, then can might when low temperature, produce sclerosis or crackle owing to the minimizing of butadiene.The ratio of this solution styrene-butadiene rubber and butadiene rubber, special preferred solution polymerizing styrene-butadiene rubber is 70-80 (weight) %, butadiene rubber is 20-30 (weight) %.
The so-called base-material rubber of forming with the mixture of above-mentioned solution styrene-butadiene rubber and butadiene rubber is the rubber of main component, be meant that its integral body is the situation of using the base-material rubber be made up of the mixture of above-mentioned solution styrene-butadiene rubber and butadiene rubber to constitute, with, the base-material rubber of forming with the mixture of above-mentioned solution styrene-butadiene rubber and butadiene rubber is main component, in the scope of not damaging above-mentioned base-material rubber property, also mix other rubber and constitute rubber situation this aspect two.From give full play to the effect viewpoint based on solution styrene-butadiene rubber, the rubber use amount except that this base-material rubber preferably accounts for 10 (weight) of rubber constituent total amount below the %.
And, with respect to being rubber 100 weight portions of main component with the base-material rubber of forming by the mixture of this solution styrene-butadiene rubber and butadiene rubber, the content of silica is the 55-70 weight portion, and the content of organosilan coupling agent is more than 1/15 below 1/5 of silica weight, and is preferred more than 1/12 below 1/5.Can think that the main effect of this silica and organosilan coupling agent is to make sole have water repellency, the water absorption rate of sole is reduced.
As mentioned above, silica, the also usefulness with the organosilan coupling agent has the effect that reduces the sole water absorption rate, but with the exception of this, also has the effect of rubber sclerosis when giving rubber appropriateness reinforcing effect and preventing low temperature.Dioxide-containing silica, with respect to rubber 100 weight portions, when being less than 55 weight portions, the effect of rubber sclerosis when can not get the reinforcing effect of appropriateness and preventing low temperature; If dioxide-containing silica, with respect to rubber 100 weight portions, its processability worsens when being higher than 70 weight portions.As this silica, preferably aqueous silicon dioxide.
And, because the interpolation of organosilan coupling agent at the reinforcing effect of bringing into play silica more significantly simultaneously, also can make sole be water repellency, and the water absorption rate of sole is reduced.The addition of this organosilan coupling agent is more than 1/15 below 1/5 of silica weight.
The addition of organosilan coupling agent is less than 1/15 o'clock of silica weight, can not give full play to the additive effect of organosilan coupling agent; When the addition of organic silane coupling agent more than silica weight 1/5 the time, along with addition increases, its effect improves seldom, causes cost to increase.As this organosilan coupling agent, preferably use above-mentioned illustrative two (3-triethoxysilylpropyltetrasulfide) tetrasulfides, vinyltrimethoxy silane, γ-metacryloxy propyl trimethoxy silicane, γ-An Bingjisanjiayangjiguiwan, γ-thin propyl trimethoxy silicane etc.
And then, with the viscous-elastic behaviour and the frictional behavior of material very big relation is arranged also, the sole distortion frequency of shoes, in the determination of viscoelasticity device for the frequency field that may measure (～100Hz) bigger, by temperature in the macromolecule viscoelastic body-frequency number conversion rule, loss coefficient (tan δ) under low temperature during high frequency 10Hz also can be learnt under the situation of the wet adherence (promptly in the adherence on the wet road surface) at sole by inquiry, with loss coefficient (tan δ) value under-15 ℃ very big relation is arranged.
Just, as material for sole of shoe, in the temperature dispersion curve of the dynamic viscoelastic when 2 ℃ of/minute frequency number 10Hz that measure of programming rate, dynamic strain is that the loss coefficient (tan δ) of 0.25% o'clock temperature-15 ℃ is 1 to produce wet adhesion effect when following more than 0.2, the preferred especially above-mentioned loss coefficient of 0.4-0.5. was less than 0.2 o'clock, temperature adhesion effect reduces, and skids easily on wet road surface; Above-mentioned loss coefficient is greater than under 1 the situation, rubber hardening during low temperature, and the feel when wearing footwear is uncomfortable.
Side view shown in Figure 1 represents to use shoes (but not shown shoestring) example of sole of the present invention, among the figure, and the 1st, footwear main part, the 2nd, sole, the 3rd, middle level.
This sole 2, as previously mentioned, the part that to be sole directly contact with ground.This sole 2 must be to have material that the present invention constitutes (promptly, by water absorption rate by weight benchmark be more than 0% below 1%, and hardness is the material that is sulfided into the body composition of the rubber composition of 40-95 by JIS-A hardness), and footwear main part 1 and middle level 3 can be known formations.And, not necessarily needing middle level 3, sole 2 and footwear main part 1 directly can be bonded together.
Sole of the present invention, especially sport footwear (for example, training with footwear, race with footwear, tennis with footwear etc.) or the spikes used of golf, winter with the suitable use of footwear, be limited to these footwear but have more than.
Among the present invention, sole has good adherence to wet road surface, on wet road surface, also be difficult to the effect of skidding even enumerated the shoes that use this sole, but said herein road surface only typically illustration the face that directly contacts of the sole of shoes, and sole of the present invention, not only for the face of road, to wet floor or wet sports with ground etc., all have adherence good, the effect that is difficult to skid is certain.
Below, enumerate embodiment and be described more specifically the present invention.But the present invention is not limited in these embodiment.
Embodiment 1-4 and comparative example 1-3
The sole composition of forming shown in the preparation table 1.The use level of each composition is a weight portion in the table, and the project that project that each symbol or contracted notation are represented in the table and general name are represented has its detailed description after table 1.
Table 1
| Embodiment | Comparative example | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| BR ※ 1 NR ※ 2 SBR ※ 3 SSBR ※ 4 resin ※ 5 zinc oxide stearic acid softening agent ※ 6 filler ※ 7 organosilan coupling agent ※ 8 sulphur promoter ※ 9 antiaging agent ※ 10 | 25 0 0 75 0 3 1 5 60 4 2 1.8 2 | 25 0 0 65 10 3 1 5 60 4 2 1.8 2 | 25 0 75 0 0 3 1 5 50 4 2 1.8 2 | 25 10 65 0 0 3 1 5 40 4 2 1.8 2 | 15 15 70 0 0 3 1 10 60 0 2 1.8 2 | 35 50 15 0 0 3 1 13 45 0 2 1.8 2 | 0 25 0 75 0 3 1 5 40 0 2 1.8 2 |
※1：BR
Butadiene uses Japan to synthesize the JSR BR-11 (trade name) of go system society system
※2：NR
Natural rubber uses RSS3 number
※3：SBR
SBR styrene butadiene rubbers uses Japan to synthesize the JSR 1502 (SBR 1502 of trade name, emulsion polymerization type) of go system society system
※4：SSBR
Use SBR styrene butadiene rubbers (styrene-content=29 (weight) %, ethylene contents=39.5 (weight) %, the Mooney viscosity) (ML of polymerisation in solution type
1+4(100 ℃)=65, glass transition temperature=-34 ℃).
※ 5: resin
Use the NIPOL 2007J (trade name, Ha イ ス チ レ Application レ ジ Application) of Japanese セ オ Application society system
※ 6: softening agent
Use the ダ イ ア Na プ ロ セ ス オ イ Le of the emerging product of bright dipping society system
PW 380 (trade name)
※ 7: filler
Use the ニ Star プ シ-Le VN3 (trade name) of Japanese シ リ カ society system
※ 8: the organosilan coupling agent
Use Si69 (trade name, the bis(3-tri-ethoxy silylpropyl)tetrasulfide of テ ゲ サ society system
※ 9: promoter
Use the emerging chemical industry of imperial palace society system ノ Network セ ラ-NS (trade name) 1 weight portion and
ノ Network セ ラ-D (trade name) 0.8 weight portion
※ 10: antiaging agent
Use imperial palace Xinghua to learn ノ Network ラ Star Network 200 (trade names) of industrial society system
The sole that resulting composition is injected tennis shoes is with metal pattern, in 160 ℃ behind 20 minutes vulcanization forming, make sole.
The hardness of the sole that mensuration makes (JIS-A hardness), loss coefficient (tan δ), water absorption rate and coefficient of friction.And, the gained sole is bonded together with bonding agent and footwear main part (but, be the part that is bonded with the middle level), make tennis shoes, the adherence on the road surface of wetting is carried out monitoring test.It the results are shown in table 2.The mensuration of hardness (JIS-A hardness) is undertaken by the method for stipulating among the JIS-K-6301.Loss coefficient (tan δ), water absorption rate, Determination of Friction Coefficient method are as follows.
Loss coefficient (tan δ):
(size: 4mm * 4mm * 2mm), measure the dynamic viscoelastic of 2 ℃ of/minute following 10Hz of programming rate makes its temperature dispersion curve, obtains dynamic strain and be the loss coefficient of 0.25% o'clock temperature-15 ℃ to the test film that takes off from sole.
Water absorption rate:
(dipping 4 hours in the distilled water of 23 ℃ of 100ml of size: 20mm * 20mm * 2mm) is obtained the weight rate of this moment to the test film that will take off from sole.
Coefficient of friction:
Put the weight of 2kg on the top of sole, measure the coefficient of kinetic friction when wet even surface (ceramic tile face) is slided.Consequently with comparative example as 100, use exponential representation.This coefficient of friction illustrates, and index is big more, and the situation of skidding on wet road surface is few more.
Monitoring test:
Allow observer 10 people put on tennis shoes, on the road surface (concrete surface) that water drenches, carry out various motions, the degree of skidding with 5 grade evaluations with the foregoing description 1-4 and comparative example 1-3 sole.Be defined as 5 points with preferably the time, the mean value when being defined as at 1 when the poorest is represented.In this monitoring test, it is high more to estimate point, even the wet road surface of expression also is difficult to skid.
Table 2
| Embodiment | Comparative example | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| Water absorption rate (%) | 0.41 | 0.24 | 0.45 | 0.93 | 2.74 | 1.87 | 1.30 |
| Hardness (JIS-A) | 80 | 85 | 76 | 69 | 81 | 72 | 68 |
| Loss coefficient (tan δ) | 0.42 | 0.28 | 0.12 | 0.01 | 0.13 | 0.14 | 0.38 |
| Coefficient of friction (index) | 120 | 118 | 115 | 110 | 100 | 102 | 104 |
| Monitoring test (evaluation point) | 4.3 | 4.1 | 3.9 | 3.7 | 3.0 | 3.3 | 3.3 |
As shown in table 2, water absorption rate is the embodiment 1-4 below 1%, compares greater than 1% comparative example 1-3 with water absorption rate, and it is big to demonstrate coefficient of friction, and the evaluation point of monitoring test is also high, even wet road surface also is difficult to skid.
In the scope of embodiment 1-4, (tan δ) is big more for loss coefficient, and coefficient of friction is big more, and the evaluation point of monitoring test is high more, has improved the degree that is difficult to skid on the wet road surface.
Embodiment 5-13 and comparative example 4-6
The sole rubber composition of forming shown in the preparation table 3-table 4.Use level in the table is a weight portion, and the project that project of representing about symbol or contracted notation in the table or generic name are represented illustrates its detailed content in the back of table 4.
Table 3
| Embodiment | ||||||
| 5 | 6 | 7 | 8 | 9 | 10 | |
| NR ※ 11 BR ※ 12 SBR ※ 13 carbon ※ 14 silica ※ 15 silylation agent are 2. ※ 17 stearic acid zinc oxide softening agent ※ 18 antiaging agent ※ 19 sulphur promoter ※ 20 of ※ 16 | 70 30 0 50 0 15 0 1 3 5 1 2 1 | 70 30 0 50 0 5 0 1 3 5 1 2 1 | 70 30 0 0 50 5 0 1 3 5 1 2 1 | 70 30 0 50 0 0 5 1 3 5 1 2 1 | 70 30 0 50 0 1 0 1 3 5 1 2 1 | 70 30 0 80 0 5 0 1 3 5 1 2 1 |
Table 4
| Embodiment | Comparative example | |||||
| 11 | 12 | 13 | 4 | 5 | 6 | |
| NR ※ 11 BR ※ 12 SBR ※ 13 carbon ※ 14 silica ※ 15 silylation agent are 2. ※ 17 stearic acid zinc oxide softening agent ※ 18 antiaging agent ※ 19 sulphur promoter ※ 20 of ※ 16 | 70 30 0 0 80 5 0 1 3 5 1 2 1 | 70 30 0 20 30 5 0 1 3 5 1 2 1 | 50 20 30 0 50 5 0 1 3 5 1 2 1 | 70 30 0 50 0 0 0 1 3 5 1 2 1 | 70 30 0 50 0 0.5 0 1 3 5 1 2 1 | 50 20 30 0 50 0 0 1 3 5 1 2 1 |
※11：NR
Natural rubber uses RSS3 number
※12：BR
Butadiene rubber uses the JSR BR-11 (trade name) of Japanese synthetic rubber system
※13：SBR
Styrene butadiene ribber uses the SBR 1502 (trade name) of Japanese synthetic rubber system
※ 14: carbon
Use ニ テ ロ Application 55 (trade names) of chemistry society of Nippon Steel system
※ 15: silica
Use the ニ Star プ シ-Le VN3 (trade name) of Japanese シ シ リ power society system
※ 16: the silylation agent 1.
Use the KBE 103 (trade name) of the シ リ コ of SHIN-ETSU HANTOTAI Application society system
(phenyl triethoxysilane)
※ 17: the silylation agent 2.
Use the KBM 3063 (trade name) (hexyl trimethoxy silane) of the シ リ コ of SHIN-ETSU HANTOTAI-Application society system
※ 18: softening agent
Use ダ イ ア Na プ ロ セ ス オ イ Le PW 380 (trade names) of the emerging product of bright dipping society system
※ 19: antiaging agent
Use ノ Network ラ Star Network 200 (trade names) of the emerging chemical industry of imperial palace society system
※ 20: promoter
Use the ノ Network セ ラ-NS (trade name) of the emerging chemical industry of imperial palace society system
The sole that the rubber composition that makes is filled into tennis shoes makes sole with in the metal pattern behind the vulcanization forming.The same with the situation of embodiment 1, hardness (JIS-A-hardness), loss coefficient (tan δ) and the coefficient of friction of the sole that mensuration makes.And, with bonding agent the sole that makes is bonded to shoes main part (but, be to be bonded with the middle level) thereby goes up and make tennis shoes, the adherence on the wet road surface is carried out and same monitoring test such as embodiment 1 grade.It is the results are shown in the table 5-table 6.
But, represent in the table that coefficient of friction is to use the coefficient of friction of comparative example 4 to be defined as 100 o'clock exponential representation.Conditions of vulcanization is: embodiment 5, embodiment 6, embodiment 8, embodiment 9, embodiment 10, comparative example 4 and comparative example 5 be 160 ℃ following 8 minutes; Embodiment 12 be 160 ℃ following 20 minutes; Embodiment 7, embodiment 13 and comparative example 6 be 160 ℃ following 40 minutes; Embodiment 11 be 160 ℃ following 60 minutes.Conditions of vulcanization is so different, is in order to make rubber composition complete cure separately.
Table 5
| Embodiment | ||||||
| 5 | 6 | 7 | 8 | 9 | 10 | |
| Water absorption rate (%) | 0.20 | 0.61 | 0.35 | 0.70 | 0.88 | 0.68 |
| Hardness (JIS-A) | 60 | 65 | 72 | 65 | 67 | 77 |
| Loss coefficient (tan δ) | 0.16 | 0.14 | 0.18 | 0.14 | 0.12 | 0.18 |
| Coefficient of friction (index) | 125 | 110 | 114 | 130 | 106 | 108 |
| Monitoring test (evaluation point) | 4.5 | 4.1 | 4.3 | 4.1 | 3.7 | 4.0 |
Table 6
| Embodiment | Comparative example | |||||
| 11 | 12 | 13 | 4 | 5 | 6 | |
| Water absorption rate (%) | 0.58 | 0.63 | 0.65 | 2.10 | 1.24 | 1.71 |
| Hardness (JIS-A) | 82 | 70 | 71 | 67 | 67 | 69 |
| Loss coefficient (tan δ) | 0.19 | 0.14 | 0.17 | 0.13 | 0.14 | 0.12 |
| Coefficient of friction (index) | 108 | 110 | 115 | 100 | 102 | 102 |
| Monitoring test (evaluation point) | 4.0 | 3.9 | 4.2 | 3.1 | 3.3 | 3.2 |
As show shown in the 5-table 6, water absorption rate is at the embodiment 5-13 below 1%, compares greater than 1% comparative example 4-6 with water absorption rate, and it is big to demonstrate coefficient of friction, and the evaluation point in the monitoring test is also high, even wet road surface also is difficult to skid.
Embodiment 14-20 and comparative example 7-9
The sole rubber composition of forming shown in the preparation table 7-table 8.Use level in the table is a weight portion, and the project that project of representing about symbol or contracted notation in the table or generic name are represented illustrates its detailed content behind table 8.
Table 7
| Embodiment | |||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
| NR ※ 21 BR ※ 22 stearic acid zinc oxide clays are 2. 3. ※ 25 organosilan coupling agent ※ 26 carbon ※ 27 antiaging agent ※ 28 sulphur promoter ※ 29 of ※ 24 clays of ※ 23 | 70 30 1 3 30 0 0 3 50 1 2 1.5 | 70 30 1 3 30 0 0 0.1 50 1 2 1.5 | 70 30 1 3 30 0 0 15 50 1 2 1.5 | 70 30 1 3 40 0 0 3 50 1 2 1.5 | 70 30 1 3 10 0 0 3 50 1 2 1.5 | 70 30 1 3 0 30 0 1 50 1 2 1.5 | 70 30 1 3 0 0 30 1 50 1 2 1.5 |
Table 8
| Comparative example | |||
| 7 | 8 | 9 | |
| NR ※ 21 BR ※ 22 stearic acid zinc oxide clays are 2. 3. ※ 25 organosilan coupling agent ※ 26 carbon ※ 27 antiaging agent ※ 28 sulphur promoter ※ 29 of ※ 24 clays of ※ 23 | 70 30 1 3 0 0 0 0 50 1 2 1.5 | 70 30 1 3 30 0 0 0 50 1 2 1.5 | 70 30 1 3 5 0 0 3 50 1 2 1.5 |
※21：NR
Natural rubber: use RSS3 number
※22：BR
Butadiene rubber uses Japan to synthesize the JSR of go system society system
BR-11 (trade name)
※ 23: clay 1.
Use the No.80 (with the clay of kaolin) of white stone カ Le シ ウ system society system, handle without the organosilan coupling agent as main component
※ 24: clay 2.
Use in advance the No.80 (with the clay of kaolin) of the white stone カ Le シ ウ system society system of handling with the organosilan coupling agent as main component
※ 25: clay 3.
Use in advance the ア イ ス キ キ Star プ k (trade name, 700 ℃ of following roastings) of the white stone カ Le シ ウ system society system of handling with the organosilan coupling agent
※ 26: carbon
Use ニ テ ロ Application 55 (trade names) of chemistry society of Nippon Steel system
※ 27: the organosilan coupling agent
Use Si60 (trade name, the bis(3-tri-ethoxy silylpropyl)tetrasulfide [bis (3-triethoxysilylpropyl) tetrasulfide] of テ グ サ system
※ 28: antiaging agent
Use ノ Network ラ Star Network 200 (trade names) of the emerging chemical industry of imperial palace society system
※ 29: promoter
Use the ノ Network セ ラ-NS (trade name) of the emerging chemical industry of imperial palace society system
The sole that the rubber composition that makes is filled into tennis shoes behind 160 ℃ of 10 minutes vulcanization formings, makes sole with in the metal pattern.
Measure hardness (JIS-A hardness), loss coefficient (tan δ), water absorption rate and the coefficient of friction of the sole that makes by the method identical with embodiment 1 etc.And, with bonding agent the main part of the sole that makes and shoes (but, be to be bonded with the middle level) is bonded together, thereby make tennis shoes, the adherence on the wet road surface is carried out the identical monitoring test with embodiment 1 etc.It is the results are shown in the table 9-table 10.But, represent in the table that coefficient of friction is to use the coefficient of friction of comparative example 7 is represented as 100 o'clock index.
Table 9
| Embodiment | |||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
| Water absorption rate (%) | 0.62 | 0.92 | 0.51 | 0.60 | 0.71 | 0.40 | 0.20 |
| Hardness (JIS-A) | 70 | 69 | 71 | 73 | 68 | 72 | 72 |
| Loss coefficient (tan δ) | 0.16 | 0.18 | 0.11 | 0.15 | 0.17 | 0.14 | 0.14 |
| Coefficient of friction (index) | 114 | 107 | 121 | 107 | 108 | 129 | 136 |
| Monitoring test (evaluation point) | 4.1 | 3.9 | 4.1 | 4.1 | 3.9 | 4.3 | 4.5 |
Table 10
| Comparative example | |||
| 7 | 8 | 9 | |
| Water absorption rate (%) | 2.10 | 2.02 | 1.41 |
| Hardness (JIS-A) | 67 | 69 | 67 |
| Loss coefficient (tan δ)- | 0.13 | 0.12 | 0.12 |
| Coefficient of friction (index) | 100 | 98 | 104 |
| Monitoring test (evaluation point) | 3.1 | 2.8 | 3.3 |
As show shown in the 9-table 10, water absorption rate is at the embodiment 14-20 below 1%, compares greater than 1% comparative example 7-9 with water absorption rate, and it is big to demonstrate coefficient of friction, and the evaluation point in the monitoring test is also high, even wet road surface also is difficult to skid.
Embodiment 21-25 and comparative example 10-11
The sole rubber composition of forming shown in the preparation table 11-table 12.Use level in the table is a weight portion, and the project that project of representing about symbol or contracted notation in the table or generic name are represented illustrates its detailed content behind table 12.
Table 11
| Embodiment | |||||
| 21 | 22 | 23 | 24 | 25 | |
| SSBR is 2. 3. 4. ※ 33 BR ※ 34 IR ※ 35 zinc oxide stearic acid softening agent ※ 36 silica ※ 37 organosilan coupling agent ※ 38 sulphur promoter ※ 39 antiaging agent ※ 40 of ※ 32 SBR of ※ 31 SSBR of ※ 30 | 75 0 0 0 25 0 3 1 5 60 6 2 1.5 2 | 60 0 0 0 40 0 3 1 5 60 6 2 1.5 2 | 85 0 0 0 15 0 3 1 5 60 6 2 1.5 2 | 0 75 0 0 25 0 3 1 5 60 6 2 1.5 2 | 75 0 0 0 25 0 3 1 5 70 7 2 1.5 2 |
Table 12
| Comparative example | ||
| 10 | 11 | |
| SBR is ※ 33 BR ※ 34 IR ※ 35 zinc oxide stearic acid softening agent ※ 36 silica ※ 37 organosilan coupling agent ※ 38 sulphur promoter ※ 39 antiaging agent ※ 40 4. | 75 25 0 3 1 5 60 0 2 1.5 2 | 0 25 75 3 1 5 60 0 2 1.5 2 |
※30：SSBR
Solution styrene-the butadiene rubber of peak value in the time of-10 ℃ of loss coefficient (tan δ)
※31：SSBR②
Solution styrene-the butadiene rubber of loss coefficient (tan δ) in the time of-25 ℃
※32：SSBR③
Solution styrene-the butadiene rubber of loss coefficient (tan δ) in the time of-35 ℃
※33：SBR④
The emulsion polymerization SBR styrene butadiene rubbers uses Japan to synthesize the JSR1502 (trade name) of go system society system
※34：BR
Butadiene rubber uses Japan to synthesize the JSR of go system society system
BR-11 (trade name)
※35：IR
Isoprene rubber, the synthetic go system society of use Japan system
JSR IR 2200 (trade name)
※ 36: softening agent
Use the ダ イ ア Na プ ロ セ ス オ イ Le PW380 (trade name) of the emerging product of bright dipping society system
※ 37: silica
Use the ニ Star プ シ-Le VN3 (trade name) of Japanese シ リ カ society system
※ 38: the organosilan coupling agent
Use Si69 (trade name, the bis(3-tri-ethoxy silylpropyl)tetrasulfide of テ グ サ system
※ 39: promoter
Use the ノ Network セ ラ-NS (trade name) of the emerging chemical industry of imperial palace society system
※ 40: antiaging agent
Use ノ Network ラ Star Network 200 (trade names) of the emerging chemical industry of imperial palace society system
The loss coefficient of above-mentioned SSBR (tan δ), just, the loss coefficient of polymerisation in solution polyethylene-butadiene rubber (tan δ), be will be with respect to solution styrene-butadiene 100 weight portions separately, zinc oxide is 3 weight portions, stearic acid is 1 weight portion, silica (ニ Star プ Star-Le VN3 (trade name)) 40 weight portions, sulphur 2 weight portions and promoter 1.5 weight portions (ノ Network セ ラ-NS (trade name) 1.0 weight portions and ノ Network セ ラ-D (trade name, the emerging chemical industry of imperial palace society system) sulfide that cooperates the rubber composition form to form in 160 ℃ of 30 minutes press cures is 2 ℃/minute at above-mentioned the sort of programming rate, mensuration is come out under the condition of frequency 10Hz.
The sole that the rubber composition that makes is packed into tennis shoes behind the vulcanization forming, is made sole with in the metal pattern, and conditions of vulcanization is: embodiment 21-25 and comparative example 10 be 160 ℃ following 30 minutes, comparative example 11 be 160 ℃ following 7 minutes.Conditions of vulcanization is so inequality to be in order to make rubber composition complete cure separately.
Measure hardness (JIS-A hardness), loss coefficient (tan δ), water absorption rate and the coefficient of friction that makes sole by the method identical with embodiment 1 etc.And, with bonding agent the main part of the sole that makes and shoes (but, be to be bonded with the middle level) is bonded together, thereby make tennis shoes, the adherence on the wet road surface is carried out the identical monitoring test with embodiment 1 etc.It is the results are shown in the table 13.But the coefficient of friction of representing in the table is to use the coefficient of friction of comparative example 10 is represented as 100 o'clock index.
Table 13
| Embodiment | Comparative example | ||||||
| 21 | 22 | 23 | 24 | 25 | 10 | 11 | |
| Water absorption rate (%) | 0.41 | 0.48 | 0.44 | 0.51 | 0.39 | 2.20 | 2.52 |
| Hardness (JIS-A) | 80 | 77 | 82 | 79 | 83 | 81 | 79 |
| Loss coefficient (tan δ) | 0.42 | 0.31 | 0.48 | 0.31 | 0.45 | 0.14 | 0.16 |
| Coefficient of friction (index) | 123 | 119 | 125 | 126 | 124 | 100 | 98 |
| Monitoring test (evaluation point) | 4.0 | 3.9 | 4.2 | 4.0 | 3.8 | 3.2 | 2.7 |
As shown in table 13, water absorption rate is at the embodiment 21-25 below 1%, compares greater than 1% comparative example 10-11 with water absorption rate, and it is big to demonstrate coefficient of friction, and the evaluation in the monitoring test is also high, even wet road surface also is difficult to skid.
As mentioned above, according to the present invention, even a kind of sole of skidding of also being difficult on wet road surface then can be provided.
Fig. 1 is the side view that shoes one example of sole of the present invention is used in expression.Symbol 1 is the shoes main parts among the figure, the 2nd, and sole.
Claims (6)
1. the sole of shoes, it is characterized in that, it be by water absorption rate by weight benchmark be more than 0%, below 1%, and hardness is that the body that is sulfided into of the rubber composition of 40-95 constitutes by JIS-A hardness, described rubber composition is selected from by rubber composition (A), rubber composition (B), one group of material that rubber composition (C) and rubber composition (D) constitute, described rubber composition (A), with respect to rubber 100 weight portions, contain silylation agent 1-15 weight portion, described rubber composition (B), with respect to rubber 100 weight portions, contain silica 30-80 weight portion and organosilan coupling agent 0.1-15 weight portion, described rubber composition (C), with respect to rubber 100 weight portions, contain with kaolin is the clay 10-40 weight portion and the organosilan coupling agent 0.1-15 weight portion of main component, described rubber composition (D), be present in respect to the peak value that only contains loss coefficient tan δ-10 ℃～-30 ℃ solution styrene-butadiene rubber 60-85 weight % and butadiene rubber 15-40 weight % mixture rubber or be rubber 100 weight portions of principal component with described mixture, contain silica 55-70 weight portion and organosilan coupling agent, and the amount of organosilan coupling agent is more than 1/15 of silica weight, below 1/5.
2. the sole of the described shoes of claim 1, wherein, rubber composition (A) with respect to rubber 100 weight portions, contains silica 30-80 weight portion.
3. the sole of the described shoes of claim 1, wherein, rubber composition (A) with respect to rubber 100 weight portions, contains carbon 30-80 weight portion.
4. the sole of the described shoes of claim 1, wherein, the clay in the rubber composition (C) is in 600-800 ℃ of baked clay down.
5. the sole of the described shoes of claim 1, wherein, the organosilan coupling agent in the rubber composition (C) is to handle in clay in advance.
6. the sole of the described shoes of claim 1, wherein, programming rate is that the dynamic strain of the temperature dispersion curve of the dynamic viscoelastic of 2 ℃ of/minute frequencies of measuring when being 10Hz is more than 0.2, below 1 0.25% o'clock temperature for-15 ℃ the loss coefficient tan δ that is sulfided into body.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8166749A JP2915349B2 (en) | 1996-06-05 | 1996-06-05 | Shoe outsole |
| JP166751/1996 | 1996-06-05 | ||
| JP166750/1996 | 1996-06-05 | ||
| JP166749/96 | 1996-06-05 | ||
| JP166751/96 | 1996-06-05 | ||
| JP166749/1996 | 1996-06-05 | ||
| JP16675196A JPH09322807A (en) | 1996-06-05 | 1996-06-05 | Outsole of shoes |
| JP16675096A JPH09322806A (en) | 1996-06-05 | 1996-06-05 | Outsole of shoes |
| JP166750/96 | 1996-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166948A CN1166948A (en) | 1997-12-10 |
| CN1157131C true CN1157131C (en) | 2004-07-14 |
Family
ID=27322743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB961115289A Expired - Fee Related CN1157131C (en) | 1996-06-05 | 1996-08-22 | Sole |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1157131C (en) |
| TW (1) | TW336886B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5002170B2 (en) * | 2005-03-16 | 2012-08-15 | 株式会社シマノ | Sole material and fishing shoes |
-
1996
- 1996-08-10 TW TW085109718A patent/TW336886B/en active
- 1996-08-22 CN CNB961115289A patent/CN1157131C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| TW336886B (en) | 1998-07-21 |
| CN1166948A (en) | 1997-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1120199C (en) | Elastomeric composition useful for tyre treads | |
| JP5915700B2 (en) | Rubber composition for tire | |
| CN1250779A (en) | Thiosilicane | |
| HU221746B1 (en) | New oligomer-organosilane-polisulphanates and their uses in caoutchouc-compounds and for making form bodies | |
| CN1583855A (en) | Rubber composition for tire tread and pneumatic tire using the rubber composition | |
| CN1922258A (en) | Rubber composition and pneumatic tire using the same | |
| CN1842542A (en) | Conjugated-diolefin (co)polymer rubber and process for producing the same | |
| WO1998038246A1 (en) | Rubber composition | |
| CN1266165C (en) | Modified rubber, process for producing the same and composition | |
| US20170130036A1 (en) | Rubber Composition and Pneumatic Tire Including the Same | |
| JP2010155967A (en) | Filler for rubber and rubber composition | |
| JP2006232922A (en) | Rubber composition and racing tire having tread made of the same | |
| CN1203115C (en) | Rubber composition for tyre tread and inflatable tyre using the same composition | |
| CN1583858A (en) | Rubber composition and pneumatic tire using the same | |
| JPH11269313A (en) | Rubber composition mixed with silica and its production | |
| JP2002053700A (en) | Rubber composition, shoe sole using the same rubber composition and shoe | |
| CN1157131C (en) | Sole | |
| JP2016108377A (en) | Rubber composition and pneumatic tire using the same | |
| JP2001226532A (en) | Organic rubber composition | |
| JP2001192454A (en) | Organopolysiloxane, compounding agent for rubber, rubber composition containing the agent and tire | |
| JP2011063690A (en) | Method for producing surface-treated silica | |
| JP3915901B2 (en) | Rubber compounding agent and compounding method | |
| JP4336920B2 (en) | Rubber composition | |
| JP4076611B2 (en) | Rubber composition | |
| JP5725365B2 (en) | Rubber composition, cross-linked product thereof, and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |