CN102532627A - Air-filled tyre - Google Patents
Air-filled tyre Download PDFInfo
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- CN102532627A CN102532627A CN2011104004313A CN201110400431A CN102532627A CN 102532627 A CN102532627 A CN 102532627A CN 2011104004313 A CN2011104004313 A CN 2011104004313A CN 201110400431 A CN201110400431 A CN 201110400431A CN 102532627 A CN102532627 A CN 102532627A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to an air-filled tyre, i.e., an air-filled tyre having the rubber tyre surface made of tyre crown/tyre surface base. The tyre crown/tyre surface base formation comprises an external rubber tyre crown layer containing external running-in surface and a lower rubber tyre surface base layer, wherein the tyre crown layer comprises at least two ring-shaped vertical rubber tyre crown areas; the tyre crown areas internally extend from the tyre crown running-in layer to the tyre surface base layer respectively; the at least two tyre crown areas comprise a first tyre crown area and a second tyre crown area adjacent to the first tyre crown area; and both the first tyre crown area and the second tyre crown area independently comprise vulcanized rubber compositions.
Description
Technical field
The present invention relates to pneumatic tyre, relate more specifically to have crown/pneumatic tyre of the rubber tread of tread base structure.
Background technology
Hope that highly tire has good anti-slippery, low-rolling-resistance and good antiwear characteristic.Under the prerequisite of not sacrificing its anti-slippery and tractive force characteristic, be difficult to improve the antiwear characteristic of tire traditionally.These performances depend on the dynamic viscoelastic of making the rubber that uses in the tire to a great extent.
In order to reduce rolling resistance and the tyre surface antiwear characteristic that improves tire, in making the tire tread rubber size, used rubber traditionally with high resilience.On the other hand, in order to improve the anti-slippery of tire, in tire tread, used the rubber that stands the macro-energy loss usually.For inconsistent performance on these two kinds of visco-elasticity of balance, usually in tire tread, use the mixture of various types of synthetic and tree elastomers.For example the various mixtures of styrene-butadiene rubber(SBR) and polybutadiene rubber are used as the rubber-like material of doughnut tyre surface usually.
Summary of the invention
The present invention relates to have crown/pneumatic tyre of the rubber tread of tread base structure, said crown/tread base structure comprises outside rubber tyre canopy and the lower floor's rubber tread base layers that contains outside running surface; Wherein said crown layer comprises at least two vertical rubber crown region of annular; Wherein said crown region extends radially inwardly to said tread base layer from said crown running surface respectively; Wherein said at least two crown region comprise first crown region and with second crown region of first crown region adjacency; But first crown region and second crown region comprise vulcanizate compositions independently of one another, but said vulcanizate compositions comprises:
The elastomerics of per 100 weight parts, first kind of styrene-butadiene rubber(SBR) of 30 to 70 weight parts (phr); Wherein this first kind of styrene-butadiene rubber(SBR) is i) based on rubber weight, have the combined styrene content of 30 to 50 wt%, 1 of 10 to 40 wt%, 2-contents of ethylene, and the solution polymerization styrene-butadiene rubber of about-40 ℃ to about-20 ℃ Tg;
Second kind of styrene-butadiene rubber(SBR) of 30 to 70 phr, wherein second kind of styrene-butadiene rubber(SBR) is based on rubber weight, has the combined styrene content of 25 to 45 wt%, 1 of 20 to 60 wt%, 2-contents of ethylene, peace treaty-30 ℃ to-5 ℃ the solution polymerization styrene-butadiene rubber of Tg approximately;
40 to 60 phr have a low PCA treated oil of being measured by the IP346 method less than the polycyclic aromatic hydrocarbon content of 3 wt%, and the resin of 15 to 35 phr, and wherein the total amount of oil and resin is 55 to 75 phr; With
The merging amount is carbon black and the silicon-dioxide of 115 to 135 phr;
Wherein at least a of first kind and second kind styrene-butadiene rubber(SBR) has greater than 1,000,000 weight-average molecular weight;
Wherein first kind of styrene-butadiene rubber(SBR) and second kind of styrene-butadiene rubber(SBR) have 10 to 20 ℃ Tg difference;
Wherein the silicon-dioxide in the rubber combination of first crown region is 4:1 to 6:1 to the sooty weight ratio, and the silicon-dioxide in the rubber combination of second crown region is 0.7:1 to 1.3:1 to the sooty weight ratio.
Description of drawings
Fig. 1 has described the phantom view of the tread portion of airtyred crown/tread base structure.
Embodiment
The present invention relates to have crown/pneumatic tyre of the rubber tread of tread base structure, said crown/tread base structure comprises outside rubber tyre canopy and the lower floor's rubber tread base layers that contains outside running surface; Wherein said crown layer comprises at least two vertical rubber crown region of annular; Wherein said crown region extends radially inwardly to said tread base layer from said crown running surface respectively; Wherein said at least two crown region comprise first crown region and with second crown region of first crown region adjacency; But first crown region and second crown region comprise vulcanizate compositions independently of one another, but said vulcanizate compositions comprises:
The elastomerics of per 100 weight parts, first kind of styrene-butadiene rubber(SBR) of 30 to 70 weight parts (phr); Wherein this first kind of styrene-butadiene rubber(SBR) is i) based on rubber weight, have the combined styrene content of 30 to 50 wt%, 1 of 10 to 40 wt%, 2-contents of ethylene, and the solution polymerization styrene-butadiene rubber of about-40 ℃ to about-20 ℃ Tg;
Second kind of styrene-butadiene rubber(SBR) of 30 to 70 phr, wherein second kind of styrene-butadiene rubber(SBR) is based on rubber weight, has the combined styrene content of 25 to 45 wt%, 1 of 20 to 60 wt%, 2-contents of ethylene, peace treaty-30 ℃ to-5 ℃ the solution polymerization styrene-butadiene rubber of Tg approximately;
40 to 60 phr have a low PCA treated oil of being measured by the IP346 method less than the polycyclic aromatic hydrocarbon content of 3 wt%, and the resin of 15 to 35 phr, and wherein the total amount of oil and resin is 55 to 75 phr; With
The merging amount is carbon black and the silicon-dioxide of 115 to 135 phr;
Wherein at least a of first kind and second kind styrene-butadiene rubber(SBR) has greater than 1,000,000 weight-average molecular weight;
Wherein first kind of styrene-butadiene rubber(SBR) and second kind of styrene-butadiene rubber(SBR) have 10 to 20 ℃ Tg difference;
Wherein the silicon-dioxide in the rubber combination of first crown region is 4:1 to 6:1 to the sooty weight ratio, and the silicon-dioxide in the rubber combination of second crown region is 0.7:1 to 1.3:1 to the sooty weight ratio.
Provide unique Fig. 1 to describe to have crown/phantom view of the tire of the tyre surface of tread base structure, the outside crown layer with first and second crown region wherein is provided.
Particularly; Fig. 1 representes with equatorial plane EP to be the partial cross section of center and the tire (1) with tyre surface (2); Said tyre surface (2) by have be used for kiss the earth running surface (4) crown layer (3) and form as lower floor's tread base layer (5) of the transitional region between said crown layer (3) and the carcass (6), said carcass (6) can comprise the belt (7) that rubber is sealed; Two isolated unaugmentable relatively tyre bead (not shown); Confession is assembled to the usefulness on the rigidity wheel rim (not shown) with tire; The casingply of sealing fabric reinforcement cord body (8) as rubber extends through the crown region of tire (1) between said tyre bead, the sidewall shown in a pair of part (9) extends between the outer periphery of said tyre bead and said tyre surface (2) and rubber liner layer (10) respectively.
Crown layer (3) is made up of the annular of two rubber combinations (side by side or in abutting connection with) longitudinal region.Crown region (11,12) inwardly radially extends to the lower floor's rubber tread base layers (5) that does not contain above-mentioned crown region from the outside running surface (4) of crown layer (3).
The zone of crown layer (3) is formed in abutting connection with setting and by second crown region (12) of its axial displacement by first tread area (11) with first crown region (11).
Subregion node (16) provides between first crown region (11) and second crown region (12), and is positioned at annular groove (15).
In the embodiment shown in Fig. 1; The span (L) of the free running surface (4) of the tyre crown layer (3) of first crown region (11) leap for example about 50%; Said span (L) comprises across any included groove, comprises the distance of the opening of annular groove (15).The said span (L) of the free running surface (4) of the tyre crown layer (3) of the same leap for example about 50% of second crown region (12).
Imagined other embodiment, wherein first arranges with second crown region asymmetricly, promptly wherein for example first crown region cross over about 75% span, second crown region crossed over about 25% span.Usually, first crown region can be crossed over the span of the free running surface of 20 to 80% tyre crown layer, the span that second crown region can corresponding leap 80 to 20%.More generally, it is contemplated that other crown region and first and/or second crown region adjacency, so at least two crown region of first minimum of representing to exist in the crown with second crown region.
The axial width of the span of the free running surface of span (L) expression tyre surface, the axial width of the span of whole running surfaces of span (L') expression tyre surface, said whole running surfaces comprise the extra running surface of crown under the tire steering condition.What the axial span (L') of the axial span (L) of the free running surface of tyre surface and whole running surfaces of tyre surface was directed against is the pneumatic tyre that turns round under 75% scale load; According to Tire and Rim Association; Inc. yearbook; Use 35 psi (240 kPa) inflation pressure for carrying tire (metric system structure carrying tire size 225/55R16 for example, scale load will be 670 kg, it 75% will be 503 kg).According to said " yearbook ",, should use the inflation pressure of 50 psi or 343 kPa for the light lorry-tyre that under 75% scale load, turns round (LT).(wherein tire is the front jockey wheel tire under steering condition; And tire is assemblied on the associated vehicle); At least a portion running surface of one of expection tire shoulder crown region (21) contacts with ground; Though be intermittently, for road the axially extended running surface of at least a portion (L') be provided thus, and for tyre surface the enhanced gripping power be provided thus.Illustrate the span (L) greatly altogether about 10% of the axial span (L') of whole running surfaces than free running surface.
Expression that phrase " contains undersaturated rubber of olefinic or elastomerics " comprises tree elastomer and its various unprocessed and reconstituted form and various viton.In specification sheets of the present invention, unless otherwise prescribed, term " rubber " and " elastomerics " can exchange use.Term " rubber combination ", " mixing of rubber " and " rubber size " interchangeable use, expression with various compositions and material blend or blended rubber, and this term is that the technician is known in rubber mix or the rubber compounding technical field.
When this mentions; The mentioned elastomerics or the second-order transition temperature of elastic composition or Tg represent that each elastomerics or elastic composition, maybe be at the second-order transition temperatures under its solid state under its its uncured state or under the situation at elastic composition.The peak value mid point that Tg can be used as under the temperature rise rate of 10 ℃ of PMs is suitably measured by differential scanning calorimeter (DSC).
By this way; This consideration be that low Tg elastomerics maybe be more incompatible with high Tg elastomerics, as approximately-120 ℃ to about 10 ℃ TR Tan δ to the figure of the solidification value of rubber combination or curve on their Tan δ peaks separately proved.Therefore, the elastomerics of rubber combination may reside at least two mutually in.
For example; The Tan δ of rubber combination of the present invention can produce two peak values to the figure of temperature curve in-120 ℃ to 10 ℃ the wide region in curve; One of them peak value for example-110 ℃ has its vertex to-70 ℃ lower temperature range, second peak value for example-35 ℃ has its vertex to+10 ℃ higher temperatures scope.
Therefore, there are two Tan δ peaks in the elastomerics uncompatibility elastic composition that is designated as sulfur curable.The Tan δ value that in its curve, comprises the peak can be measured by the method for well known to a person skilled in the art through solidifying the dynamic mechanical test of sizing material.
Therefore, solidified mixing of rubber compsn can show at least two Tan δ peaks in the said temperature scope.For the solidified mixing of rubber; In this consideration is that (for example cis 1 for low Tg elastomerics; The 4-polyhutadiene) in the following Tan δ peak of lesser temps (for example-100 ℃ to-50 ℃) (it possibly hint and promote the wear resistance (tire tread wear that promptly improves) improved) and combination by following second the Tan δ peak of the comparatively high temps of high Tg elastomerics (for example SBR) representative (for example-30 ℃ to 10 ℃) (it can hint approximately-30 ℃ of extremely promotion higher hysteresis (being higher tyre surface tractive force) under about 0 ℃ temperature), all these is this wear resistance of particularly tyre surface and the tractive force performance only shows single Tan δ peak than in-90 ℃ to 10 ℃ above-mentioned scope the better equilibrated sign of curing rubber compsn.
First comprises elastomerics with the rubber combination of second crown region; Said elastomerics is by per 100 weight part elastomericss, first kind of styrene-butadiene rubber(SBR) of 30 to 70 weight parts (phr), second kind of styrene-butadiene rubber(SBR) of 30 to 70 phr; Form with cis-1,4 polyhutadiene of optional 5 to 20 phr.First comprises elastomerics independently with the rubber combination of second tread area, and promptly the elastomeric amount in first crown region can be identical or different with the amount in second crown region.
First kind with second kind of complete different its second-order transition temperature that are of styrene-butadiene rubber(SBR).First kind and second kind of styrene-butadiene rubber(SBR) have 10 to 20 ℃ Tg difference.
At least a of first kind and second kind styrene-butadiene rubber(SBR) has greater than 1,000,000 weight-average molecular weight (Mw).Weight-average molecular weight can be by any method as known in the art, and example gel permeation chromatography (GPC) is measured.
A component of rubber combination is first kind of styrene-butadiene rubber(SBR) of 30 to 70 phr; Wherein this first kind of styrene-butadiene rubber(SBR) is i) based on rubber weight; Combined styrene content with 30 to 50 wt%; 1 of 10 to 40 wt%, 2-contents of ethylene, and the solution polymerization styrene-butadiene rubber of about-40 ℃ to about-20 ℃ Tg.
As first kind of styrene-butadiene rubber(SBR), suitable solution polymerization styrene-butadiene rubber can for example prepare through the organic radical lithium catalysis in the presence of organic hydrocarbon solvent.The polymerization of using in the preparation rubbery polymer causes through in containing monomeric organic polymer medium, adding organic lithium initiator usually.This polymerization uses the successive polymerization technology to carry out usually.In this successive polymerization, monomer and initiator join in the organic polymer medium continuously, and discharge the synthetic rubbery polymer continuously.This successive polymerization is carried out in multiple reaction body system usually.Suitable polymerization method is as known in the art, for example in US 4,843,120; 5,137,998; 5,047,483; 5,272,220; 5,239,009; 5,061,765; 5,405,927; 5,654,384; 5,620,939; 5,627,237; 5,677,402; 6,103,842; With 6,559, open in 240.
As first kind of styrene-butadiene rubber(SBR), suitable solution polymerization styrene-butadiene rubber is commercially available, for example Dow SE-SLR 6430 etc.This solution polymerization styrene-butadiene rubber can be tin-or silicon-coupling, as as known in the art.What in one embodiment, suitable SSBR can be for part silicon coupling at least.
Second component of rubber combination is second kind of styrene-butadiene rubber(SBR) of 30 to 70 phr; Wherein this second kind of styrene-butadiene rubber(SBR) is based on rubber weight; Have 25 to 45 wt% combined styrene content, 20 to 60 wt% 1; 2-contents of ethylene, and the solution polymerization styrene-butadiene rubber (SSBR) of about-30 ℃ to about-5 ℃ Tg.As second kind of styrene-butadiene rubber(SBR), suitable solution polymerization styrene-butadiene rubber can for example prepare through the organic radical lithium catalysis in the presence of organic hydrocarbon solvent.The polymerization of using in the preparation rubbery polymer causes through in containing monomeric organic polymer medium, adding organic lithium initiator usually.This polymerization uses the successive polymerization technology to carry out usually.In this successive polymerization, monomer and initiator join in the organic polymer medium continuously, and discharge the synthetic rubbery polymer continuously.This successive polymerization is carried out in multiple reaction body system usually.Suitable polymerization method is as known in the art, for example in US 4,843,120; 5,137,998; 5,047,483; 5,272,220; 5,239,009; 5,061,765; 5,405,927; 5,654,384; 5,620,939; 5,627,237; 5,677,402; 6,103,842; With 6,559, open in 240.
As second kind of styrene-butadiene rubber(SBR), suitable solution polymerization styrene-butadiene rubber is commercially available, for example from Tufdene E680 SSBR of Asahi Chemical etc.This solution polymerization styrene-butadiene rubber can be tin-or silicon-coupling, as as known in the art.What in one embodiment, suitable SSBR can be for part silicon coupling at least.
The optional component of rubber combination is about 5 cis to about 20 phr-1,4 polyhutadiene, also claims polybutadiene rubber or polyhutadiene (BR).Suitable polybutadiene rubber can for example pass through the organic solution polymerization preparation of 1,3-butadiene.BR can be for example by the cis 1 with at least 90%, and 4-content comes to characterize easily with-95 to-105 ℃ glass transition temperature Tg.Suitable polybutadiene rubber is commercially available, for example available from Budene 1207 of Goodyear etc.
Rubber combination comprises that the merging amount is treated oil and the resin of 55 to 75 phr.
Rubber combination comprises the treated oil of 40 to 60 phr.Treated oil can be used as and is generally used for the elastomeric extending oil of increment and is included in the rubber combination.Treated oil also can be included in the rubber combination through in the rubber compounding process, directly adding oil.The treated oil that uses can comprise the treated oil that adds in the extending oil that is present in the elastomerics and the compounding process.In one embodiment, rubber combination comprises low PCA oil.Suitable low PCA oil includes but not limited to gentle extraction solvent thing as known in the art (MES), the distillation aromatics extract of handling (TDAE), residual aromatics extract (RAE), SRAE and heavy NO; For example referring to US 5,504,135; 6,103,808; 6,399,697; 6,410,816; 6,248,929; 6,146,520; US 2001/00023307; 2002/0000280; 2002/0045697; 2001/0007049; EP0839891; JP2002097369; ES2122917.
Suitable low PCA oil comprise have as measure by the IP346 method less than those of the polycyclic aromatic hydrocarbon content of 3 wt%.The step of IP346 method can be by Institute of Petroleum, and United Kingdom publishes
Standard Methods for Analysis & Testing of Petroleum and Related ProductsWith
British Standard 2000 Parts, find in 2003, the 62 editions.
Rubber combination comprises the resin of 15 to 35 phr.
Appropriate resin comprises having 1,000 to 15,000 number-average molecular weight (Mn); The styrene-butadiene copolymer of the contents of ethylene of the styrene content of 17 to 27 wt% and 60 to 80 wt%.Suitable styrene-butadiene copolymer is purchased from Sartomer with Ricon 100.
Appropriate resin also comprises the alpha-methyl styrene resin derived from vinylbenzene and alpha-methyl styrene.In one aspect, with molecular weight (Mn) and MWD (Mw/Mn) bonded second-order transition temperature (Tg) characteristic the suitable consistency of resin in rubber combination is provided according to thinking, the degree of consistency is directly related with the characteristic of rubber combination.
For comprising the elastomeric rubber blend of styrene butadiene; The existing in this and be considered to favourable of vinylbenzene/alpha-methyl styrene resin; Because the viscoelastic property of observed tread rubber compsn; For example complex modulus under different temperature/frequency/strain and storage modulus, out-of-phase modulus tan δ and loss compliance are described like following generality.
It is that those skilled in the art are generally well-known that the performance of complex modulus and storage modulus, out-of-phase modulus, tan δ and loss compliance is interpreted as.Their general hereinafter descriptions.
The MWD of resin manifests with the ratio of resin weight-average molecular weight (Mw) to number-average molecular weight (Mn) value, and thinks that at this this is considered to narrower scope in about 1.5/1 to about 2.5/1 scope.This point it is believed that it is favourable, because for the selection consistency of polymeric matrix, and because tire desired use in doing wet condition in wide temperature range.
The glass transition temperature Tg of copolymer resin this think about 20 ℃ to about 100 ℃ scope, be about 30 ℃ to about 80 ℃ alternatively, depend on the character of blend polymer of intended purpose and tyre surface of the tire of manufacturing to a certain extent.
Vinylbenzene/alpha-methyl styrene resin this think vinylbenzene and alpha-methyl styrene than short chain copolymer, have vinylbenzene/alpha-methyl styrene molar ratio of about 0.40 to about 1.50.In one aspect, this resin can be for example through vinylbenzene and the incompatible preparation aptly of the cationic copolymerization of alpha-methyl styrene in hydrocarbon solvent.
Therefore, the vinylbenzene of expection/alpha-methyl styrene resin can be for example by its chemical structure, i.e. its vinylbenzene and alpha-methyl styrene content, and softening temperature, and if desired, its second-order transition temperature, molecular weight and MWD characterize.
In one embodiment, vinylbenzene/alpha-methyl styrene resin is made up of about 40 to about 70% the unit derived from alpha-methyl styrene derived from cinnamic unit and correspondingly about 60 to about 30%.In one embodiment, vinylbenzene/alpha-methyl styrene resin have according to ASTM No.E-28 about 80 ℃ to about 145 ℃ softening temperature.
Suitable vinylbenzene/alpha-methyl styrene resin can be purchased from Eastman by Resin 2336, has 38 ℃ Tg.
Appropriate resin also comprises dimerization colophonium.This dimerization colophonium can mainly comprise the dipolymer of sylvic acid, and some monomer sylvic acids.Suitable dimerization colophonium can be purchased from Eastman by Dymerex, it is reported to have 412 number-average molecular weight Mn and 487 weight-average molecular weight Mw.
Rubber combination comprises that also the merging amount is carbon black and the silicon-dioxide of 115 to 135 phr.In first crown region, silicon-dioxide is 4:1 to 6:1 to the sooty weight ratio.In second crown region, silicon-dioxide is 0.7:1 to 1.3:1 to the sooty weight ratio.
The silicon-dioxide that can be used for the use of rubber size comprises pyrolysis and precipitated silica.In one embodiment, use precipitated silica.Being used for the siliceous pigment of routine of the present invention is precipitated silica, for example through soluble silicate, for example the water glass acidifying obtain those.
This conventional silicon-dioxide can be for example by characterizing like the BET surface-area that uses nitrogen to measure.In one embodiment, the BET surface-area can be about 40 to about 600 meters
2/ gram.In another embodiment, the BET surface-area can be about 80 to about 300 meters
2/ gram.The BET method of meter area is recorded in
Journal of the American Chemical Society, roll up 60,304 pages (nineteen thirty).
Conventional silicon-dioxide also can be characterized by has about 100 to about 400, about alternatively 150 to about 300 Witcizer 300 (DBP) absorption value.
Conventional silicon-dioxide can expect to have for example 0.01 to 0.05 micron the average final size as with determination of electron microscopy, although silica dioxide granule can have even granularity littler or maybe be bigger.
Can use various commercially available silicon-dioxide, only be used for way of illustration but not limitation, the silicon-dioxide that for example can be purchased with Hi-Sil trade mark and the trade mark 210,243 etc. from PPG Industries at this; Available from Rhodia, for example the trade mark is the silicon-dioxide of Z1165MP and Z165GR, and available from Degussa AG, for example the trade mark is the silicon-dioxide of VN2 and VN3 etc.
Suitable carbon black comprises N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991.The iodine that suitable carbon black has 9 to 220 g/kg absorbs and 34 to 150 cm
3The DBP oil absorption value of/100 g.In one embodiment, carbon black has that iodine according to 130 to 210 g/kg of ASTM-D1510 absorbs and according to the DBP oil absorption value of 110 to the 140 cc/100 g of ASTM D-2414.
But vulcanizate compositions can be chosen crosslinked granulated polymer gel, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) or the plastifying starch that can comprise 1 to 20 phr wantonly.
Other filler can be used for rubber combination, includes but not limited to granulated filler, comprises ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), and the granulated polymer gel includes but not limited to US 6,242,534; 6,207,757; 6,133,364; 6,372,857; Those disclosed and plastifying starch compounded mix include but not limited to US 5,672 in 5,395,891 or 6,127,488, those disclosed in 639.
In one embodiment, the rubber combination that is used for tire tread can comprise conventional sulfur-containing organosilicon compounds.The instance of the sulfur-containing organosilicon compounds that is fit to has following formula:
Z―Alk―S
n―Alk―Z?I
Wherein Z is selected from
R wherein
1Be the alkyl of 1 to 4 carbon atom, cyclohexyl or phenyl; R
2Be the alkoxyl group of 1 to 8 carbon atom, or the cycloalkyloxy of 5 to 8 carbon atoms; Alk is the divalence hydrocarbon of 1 to 18 carbon atom, and n is 2 to 8 integer.
The specific examples of operable sulfur-containing organosilicon compounds comprises according to the present invention: 3, and two (trimethoxy-silylpropyl) disulphide, 3 of 3'-, two (triethoxysilylpropyltetrasulfide) disulphide, 3 of 3'-; Two (triethoxysilylpropyltetrasulfide) tetrasulfides, 3 of 3'-, two (triethoxysilylpropyltetrasulfide) eight sulfide, 3 of 3'-, two (trimethoxy-silylpropyl) tetrasulfides, 2 of 3'-; Two (triethoxysilyl ethyl) tetrasulfides, 3 of 2'-, two (trimethoxy-silylpropyl) trisulphides, 3 of 3'-, two (triethoxysilylpropyltetrasulfide) trisulphides, 3 of 3'-; Two (the three butoxy silyl propyl group) disulphide, 3 of 3'-, two (trimethoxy-silylpropyl) hexasulfides, 3 of 3'-, two (trimethoxy-silylpropyl) eight sulfide, 3 of 3'-; Two (the three octyloxy silyl propyl group) tetrasulfides, 3 of 3'-, two (the three hexyloxy silyl propyl group) disulphide, 3 of 3'-, two (three-2''-ethyl hexyl oxy silyl propyl group) trisulphides, 3 of 3'-; Two (the three different octyloxy silyl propyl group) tetrasulfides, 3 of 3'-, two (three-tert.-butoxy silyl propyl group) disulphide, 2 of 3'-, two (the methoxyl group diethoxy silyl ethyl) tetrasulfides, 2 of 2'-; Two (the tripropoxy-sil(ic)ane base ethyl) pentasulfides, 3 of 2'-, two (the three cyclohexyloxy silyl propyl group) tetrasulfides, 3 of 3'-, two (the three cyclopentyloxy silyl propyl group) trisulphides, 2 of 3'-; Two (three-2''-methyl cyclohexane oxygen base silyl ethyl) tetrasulfide, two (trimethoxysilyl methyl) tetrasulfides of 2'-, 3-methoxy ethoxy propoxy-silyl 3'-diethoxy butoxy-silyl propyl group tetrasulfide, 2, two (dimethylmethoxysilylgroups groups ethyl) disulphide, 2 of 2'-, two (the dimethyl-sec.-butoxy silyl ethyl) trisulphides, 3 of 2'-; Two (the methylbutyl (ethoxymethyl) siloyl group propyl group) tetrasulfides, 3 of 3'-, two (the di-t-butyl methoxy methyl siloyl group propyl group) tetrasulfides, 2 of 3'-, two (the phenyl methyl methoxy methyl siloyl group ethyl) trisulphides, 3 of 2'-; Two (the phenylbenzene isopropoxy silyl propyl group) tetrasulfides, 3 of 3'-, two (the phenylbenzene cyclohexyloxy silyl propyl group) disulphide, 3 of 3'-, two (the dimethyl ethyl sulfydryl silyl propyl group) tetrasulfides, 2 of 3'-; Two (the methyl dimethoxy oxygen base silyl ethyl) trisulphides, 2 of 2'-, two (the methyl ethoxy propoxy-silyl ethyl) tetrasulfides, 3 of 2'-, two (the diethylammonium methoxy methyl siloyl group propyl group) tetrasulfides, 3 of 3'-; Two (the ethyl two sec.-butoxy silyl propyl group) disulphide, 3 of 3'-; Two (the propyl group diethoxy silyl propyl group) disulphide, 3 of 3'-, two (the butyl dimethoxy silyl propyl group) trisulphides, 3 of 3'-, two (the phenyl dimethoxy silyl propyl group) tetrasulfides of 3'-, 3-phenyl ethoxy butoxy silyl 3'-trimethoxy-silylpropyl tetrasulfide, 4; Two (trimethoxysilyl butyl) tetrasulfides, 6 of 4'-; Two (triethoxysilyl hexyl) tetrasulfides, 12 of 6'-, two (the three isopropoxy silyl dodecyls) disulphide, 18 of 12'-, two (trimethoxysilyl octadecyl) tetrasulfides, 18 of 18'-; Two (the tripropoxy-sil(ic)ane base octadecylene base) tetrasulfides, 4 of 18'-; 4'-two (tetrasulfide, 4 of trimethoxysilyl butene-2-yl), two (trimethoxysilyl cyclohexylidene) tetrasulfides, 5 of 4'-, two (the dimethoxy-methyl silyl amyl group) trisulphides, 3 of 5'-; Two (trimethoxysilyl-2-methyl-propyl) tetrasulfides, 3 of 3'-, two (Dimethoxyphenyl silyl-2-methyl-propyl) disulphide of 3'-.
In one embodiment, sulfur-containing organosilicon compounds is 3,3'-two (trimethoxy or triethoxysilylpropyltetrasulfide) sulfide.In one embodiment, sulfur-containing organosilicon compounds is 3, two (triethoxysilylpropyltetrasulfide) disulphide and 3 of 3'-, two (triethoxysilylpropyltetrasulfide) tetrasulfides of 3'-.Therefore, about formula I, Z can for
R wherein
2Be 2 to 4 carbon atoms, the alkoxyl groups of 2 carbon atoms alternatively; Alk is 2 to 4 carbon atoms, the divalence hydrocarbon of 3 carbon atoms alternatively; N is 2 to 5 integer, is 2 or 4 alternatively.
In another embodiment, the sulfur-containing organosilicon compounds that is fit to comprises US 6,608, disclosed compound in 125.Like US 6,608, disclosed in 125, these sulfur-containing organosilicon compounds have formula G-C (==O)-S-CH
2CH
2CH
2SiX
3Wherein each X is the independent RO-group of selecting; Wherein each R is independently selected from hydrogen, can or can contain alkyl, thiazolinyl, aryl and the aralkyl of degree of unsaturation, has 1 to 18 carbon atom beyond this part dehydrogenation and G is the univalent alkyl of 6 to 8 carbon atoms.In one embodiment, sulfur-containing organosilicon compounds comprises 3-(capryloyl sulfo-)-1-propyl-triethoxysilicane, CH
3(CH
2)
6C (=O)-S-CH
2CH
2CH
2Si (OCH
2CH
3)
3, be purchased Silicones from GE with NXT.
In another embodiment, the sulfur-containing organosilicon compounds that is fit to comprises those disclosed among the US 2003/0130535.As disclosed among the US 2003/0130535, these sulfur-containing organosilicon compounds have formula II or III
Wherein: R is methyl or ethyl;
R' is identical or different and be C
9-C
30Branching or not branching univalent alkyl or thiazolinyl, aryl, aralkyl, branching or not branching C
2-C
30Alkyl ether groups, branching or branching C not
2-C
30Alkyl, polyether group or R'''
3Si, wherein R''' is C
1-C
30Branching or not branched-alkyl or thiazolinyl, aralkyl or aryl, R'' are branching or not branching, saturated or unsaturated aliphatic, aromatics or blended aliphatic series/aromatics divalence C
1-C
30Alkyl;
X is SH, and wherein n=1 and m=1 are S, wherein n=2 and m=1-10 and composition thereof, S (C==O)-R''', wherein n=1 and m=1 or H, wherein n=1 and m=1;
R'' can represent CH
2, CH
2CH
2, CH
2CH
2CH
2, CH
2CH
2CH
2CH
2, CH (CH
3), CH
2CH (CH
3), C (CH
3)
2, CH (C
2H
5), CH
2CH
2CH (CH
3), CH
2CH (CH
3) CH
2Or
In one embodiment, sulfur-containing organosilicon compounds has formula II, and R is an ethyl, and R' is C
12-C
14Alkyl, R'' are CH
2CH
2CH
2, X is SH, n be 1 with m be 1.In one embodiment, sulfur-containing organosilicon compounds is the Si-363 available from Degussa.
In one embodiment, sulfur-containing organosilicon compounds is 3, the combination of two (the triethoxy propyl group silyl) tetrasulfides of 3'-and 3-(capryloyl sulfo-)-1-propyl-triethoxysilicane.
The amount of sulfur-containing organosilicon compounds in rubber combination will change according to the level of other additive that uses.Generally speaking, the amount of this compound will be 0.5 to 20 phr.In one embodiment, amount will be 1 to 10 phr.
Those skilled in the art should understand easily, and rubber combination will be by common known method compounding in the rubber compounding field, but for example various sulphur curable component rubber is mixed with various normally used additive materials; Said additive material is sulfur donor, auxiliary curing agent for example; For example acvator, retarding agent and processing additives are for example oily, resin; Comprise tackifying resin and softening agent, filler, pigment, lipid acid, zinc oxide, wax, oxidation inhibitor and antiozonidate and peptizer.As well known by persons skilled in the art, can vulcanize the intended purpose with sulphur sulfurized material (rubber) according to sulphur, select and use above-mentioned additive with the amount of routine usually.The representative example of sulfur donor comprises elementary sulfur (free sulphur), curing amine, polymerization polysulphide and sulphur olefin addition product.In one embodiment, sulphur-vulcanizing agent is an elementary sulfur.Sulphur-vulcanizing agent can be with 0.5 to 8 phr, and the amount of 1.5 to 6 phr is used alternatively.If use, the typical amount of tackifier resins comprises about 0.5 to about 10 phr, is generally about 1 to about 5 phr.The typical amount of processing aid comprises about 1 to about 50 phr.The typical amount of oxidation inhibitor comprises about 1 to about 5 phr.Representational oxidation inhibitor can for example be disclosed in for for example diphenyl-para-phenylene diamine etc.
The Vanderbilt Rubber Handbook(1978), those in 344 to 346 pages.The typical amount of antiozonidate comprises about 1 to 5 phr.If use, can comprise that the typical amount of stearic lipid acid comprises about 0.5 to about 3 phr.Glycerin fatty acid ester can use with about 0.5 to about 3 phr amount.Soap comprises zinc salt, can use with about 0.5 to about 3 phr amount.The typical amount of zinc oxide comprises about 2 to about 5 phr.The typical amount of wax comprises about 1 to about 5 phr.Often use Microcrystalline Wax.The typical amount of peptizer comprises about 0.1 to about 1 phr.Typical peptizer can be for example pentachlorothiophenol and dibenzamidodiphenyl disulfide.
Promotor being used for controlled sulfuration required time and/or temperature, and the performance of improving vulcanizate.In one embodiment, can use single accelerator system, i.e. primary accelerator.One or more primary accelerators can be with about 0.5 to about 4 phr, and about alternatively 0.8 to about 1.5 phr total amount is used.In another embodiment, can use the combination of the secondary accelerator of advocating peace, wherein secondary accelerator is with for example about 0.05 to about 3 phr use more on a small quantity, so that activation and improve the performance of vulcanizate.The combination of these promotor can be expected to final performance generation synergy, and those better effects if that produce than any promotor of independent use slightly.In addition, can use not receive common process temperature effect, but under common curing temperature, produce satisfied solidified delayed action accelerator.Also can use vulcanization retarder.The suitable type that can be used for promotor of the present invention is amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulfinyl amine, dithiocarbamate and xanthate.In one embodiment, primary accelerator is a sulfinyl amine.If the use secondary accelerator, then this secondary accelerator can be guanidine, dithiocarbamate or thiuram compound.
The mixing of rubber combination can use the known method of rubber mix those skilled in the art to accomplish.For example, each component is mixed at least two stages usually, and promptly at least one non-productive stage then is to produce mix stages.The final solidifying agent that comprises sulphur-vulcanizing agent is called the final stage of " production " mix stages usually sneaks in tradition, wherein mixes usually under the temperature of the mixing temperature that is lower than one or more nonproductive mix stages formerly or outlet temperature to take place.Term " nonproductive " and " production " mix stages are that the rubber mix those skilled in the art are known.Rubber combination can carry out hot mechanically mixing step.Hot mechanically mixing step is usually included in one section reasonable time of mechanical workout in mixing tank or the forcing machine, so that produce 140 ℃ to 190 ℃ rubber temperature.The suitable time length of hot machine operation is as the volume of operational conditions and each component and the function of character.For example, hot machine operation can carry out 1 to 20 minute.
Rubber combination can be introduced in the various rubber components of tire.For example, rubber components can be tyre surface (comprising crown and tread base), sidewall, triangle tire core, chafer fabric, sidewall inserts, line infantees or liner.In one embodiment, parts are tyre surface.
Pneumatic tyre of the present invention can be racing-car tyre, tyres for passenger cars, plane tyre, agricultural tire, bull dozer tire, off-the-highway tire, truck tyre etc.In one embodiment, tire is tyres for passenger cars or truck tyre.Tire also can be radial-ply tyre or oblique tire.
Airtyred sulfuration of the present invention is carried out under about 100 ℃ to 200 ℃ conventional temperature usually.In one embodiment, sulfuration is carried out under about 110 ℃ to 180 ℃ temperature.Can use any sulfuration process commonly used, for example in press or mould the heating, with superheated vapour or warm air beating.This tire can be with known and will be conspicuous immediately the whole bag of tricks manufacturing, moulding, moulding and curing to those skilled in the art.
The unrestricted the present invention that provides following examples in order that illustrate.Only if indicate especially in addition, all umbers are weight part.
Embodiment 1
In the present embodiment, compare two kinds of sizing materials.Sample 1 expression control sample.Sample 2 and 3 is represented the present invention.
Elastomerics and conventional solidifying agent and processing aid compounding in the multistep mixing step (all are measured in phr) like the normal content indicated in the table 1, and solidify with the standard cure cycle.According to various physicalies like the standard testing rules evaluate cure sample that shows in the table 2.To the various standard of performance as shown in table 3 of the Tire testing with tyre surface of making by the sizing material of sample 1 and 2 (each value is according to control=100 stdn).
Table 1
Sizing compound formula
1Budene1207 is available from Goodyear Tire & Rubber Chemical
2SE SLR6430 solution polymerization styrene-butadiene rubber, 40% vinylbenzene, 14% vinyl, Tg (OE)=-34 ℃, 37.5 phr TDAE oil is available from Styron
3Tufdene E680 solution polymerization styrene-butadiene rubber, 34% vinylbenzene, 38% vinyl, Tg (OE)=-25 ℃, 37.5 phr SRAE oil is available from Asahi Chemical
4SE SLR 4630; The solution polymerization styrene-butadiene rubber of part silicon coupling; With 37.5 phr TDAE oil increment, typical performance report is the vinylbenzene of 25 wt% and the vinyl of 63 wt% (divinyl segment), Tg=-28.9 ℃; Mooney ML 1+4 (100 ℃)=55 is available from Dow Chemical Company
5Precipitated silica, BET nitrogen surface-area=160 m
2/ g
6Furnace black, iodine absorption value=202 g/kg (ASTM D-1510), oily absorption value=134 cc/kg (ASTM D-2414)
7?RAE，SRAE?&?TDAE?oil
8The alpha-methyl styrene resin, with Resin 2336 available from Eastman
9Dimerization colophonium, with Dymerex available from Eastman
10Coumarone-indene resin
11Ricon 100, low molecular weight phenylethylene-butadienecopolymer, and 25% vinylbenzene, 70% vinyl, Mw=4500 are available from Cray Valley
1250% pair of (triethoxysilylpropyltetrasulfide) tetrasulfide on the carbon black
13Microcrystalline Wax and alkane wax
14Lipid acid, fatty acid zinc salt and glycerin fatty acid ester
15Ursol D and quinoline type
16Sulfinyl amine and guanidine type.
Table 2
。
Table 3
Though purpose has in order to demonstrate the invention shown some typical embodiments and details, it will be apparent to one skilled in the art that without departing from the present invention, can carry out various changes and modifications therein.
Claims (3)
1. pneumatic tyre is characterised in that to have crown/rubber tread of tread base structure that said crown/tread base structure comprises outside rubber tyre canopy and the lower floor's rubber tread base layers that contains outside running surface; Wherein said crown layer comprises at least two vertical rubber crown region of annular; Wherein said crown region extends radially inwardly to said tread base layer from said crown running surface respectively; Wherein said at least two crown region comprise first crown region and with second crown region of first crown region adjacency; But first crown region and second crown region comprise vulcanizate compositions independently of one another, but said vulcanizate compositions comprises:
The elastomerics of per 100 weight parts, first kind of styrene-butadiene rubber(SBR) of 30 to 70 weight parts (phr); Wherein this first kind of styrene-butadiene rubber(SBR) is i) based on rubber weight, have the combined styrene content of 30 to 50 wt%, 1 of 10 to 40 wt%, 2-contents of ethylene, and the solution polymerization styrene-butadiene rubber of about-40 ℃ to about-20 ℃ Tg;
Second kind of styrene-butadiene rubber(SBR) of 30 to 70 phr; Wherein this second kind of styrene-butadiene rubber(SBR) is based on rubber weight, has the combined styrene content of 25 to 45 wt%, 1 of 20 to 60 wt%; The 2-contents of ethylene, peace treaty-30 ℃ to-5 ℃ the solution polymerization styrene-butadiene rubber of Tg approximately;
40 to 60 phr have a low PCA treated oil of being measured by the IP346 method less than the polycyclic aromatic hydrocarbon content of 3 wt%, and the resin of 15 to 35 phr, and wherein the total amount of oil and resin is 55 to 75 phr; With
The merging amount is carbon black and the silicon-dioxide of 115 to 135 phr;
Wherein at least a of first kind and second kind styrene-butadiene rubber(SBR) has greater than 1,000,000 weight-average molecular weight;
Wherein first kind of styrene-butadiene rubber(SBR) and second kind of styrene-butadiene rubber(SBR) have 10 to 20 ℃ Tg difference;
Wherein the silicon-dioxide in the rubber combination of first crown region is 4:1 to 6:1 to the sooty weight ratio, and the silicon-dioxide in the rubber combination of second crown region is 0.7:1 to 1.3:1 to the sooty weight ratio.
2. the pneumatic tyre of claim 1 is characterised in that resin is selected from i) have 1,000 to 15,000 number-average molecular weight (Mn), a styrene-butadiene copolymer of the contents of ethylene of the styrene content of 17 to 27 wt% and 60 to 80 wt%; Ii) dimerization colophonium; (iii) vinylbenzene/alpha-methyl styrene resin.
3. the pneumatic tyre of claim 1 is characterised in that rubber combination further comprises cis-1,4 polyhutadiene with Tg of-110 ℃ to-90 ℃ of 5 to 20 phr.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41992610P | 2010-12-06 | 2010-12-06 | |
| US61/419926 | 2010-12-06 |
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| CN102532627A true CN102532627A (en) | 2012-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104004313A Pending CN102532627A (en) | 2010-12-06 | 2011-12-06 | Air-filled tyre |
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| CN107912044A (en) * | 2015-06-18 | 2018-04-13 | 米其林集团总公司 | Include styrene-butadiene-copolymer and the rubber composition of the filler of high-content and plasticizer with lower glass transition temperatures |
| CN109422939A (en) * | 2017-08-30 | 2019-03-05 | 固特异轮胎和橡胶公司 | Pneumatic tire |
| CN109641480A (en) * | 2016-08-17 | 2019-04-16 | 大陆轮胎德国有限公司 | The crosslinkable rubber composition of sulphur and vehicle tyre |
| CN113861530A (en) * | 2020-06-30 | 2021-12-31 | 固特异轮胎和橡胶公司 | Tire with a multilayer tread |
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| EP2147806A1 (en) * | 2008-07-24 | 2010-01-27 | The Goodyear Tire & Rubber Company | Tire with tread having a two-ply tread cap layer |
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| EP1398182A2 (en) * | 2002-09-13 | 2004-03-17 | The Goodyear Tire & Rubber Company | tire with a multi-layered tread |
| US20040261927A1 (en) * | 2003-06-30 | 2004-12-30 | Marc Weydert | Pneumatic tire having a component containing a rubber triblend and silica |
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Application publication date: 20120704 |