CN101445622A - Tire with silica tread having self condensing resin - Google Patents
Tire with silica tread having self condensing resin Download PDFInfo
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- CN101445622A CN101445622A CNA2008101786919A CN200810178691A CN101445622A CN 101445622 A CN101445622 A CN 101445622A CN A2008101786919 A CNA2008101786919 A CN A2008101786919A CN 200810178691 A CN200810178691 A CN 200810178691A CN 101445622 A CN101445622 A CN 101445622A
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- resin
- carbon atom
- pneumatic tyre
- sulfur
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Abstract
The present invention relates to tire with silica tread having self condensing resin. The present invention is directed to a tire comprising a ground contacting tread, the ground contacting tread comprising a rubber composition, the rubber composition comprising a diene based elastomer, from 60 to 120 parts by weight, per 100 parts by weight of elastomer (phr) of silica, from 1 to 10 phr of a sulfur-containing organosilicon compound, and from 1 to 5 phr of a resin derived from monomers of formula I wherein R 1 is an alkyl group having 1 to 12 carbon atoms, and each of R2 to R6 is independently selected from the group consisting of hydrogen, --CH2OH, and-CH2OR 1 wherein R1 is as previously described; provided that at least one of R2 to R6 is hydrogen, and at least one of R2 to R6 is -CH2OH.
Description
Cross reference to other application
The application requires the sequence number No.60/990 of submission on November 27th, 2007,321 rights and interests.
Technical field
The present invention relates to have the tire of the silica tread that contains self condensing resin (self condensing resin).
Background technology
Compare with carbon black enhanced tyre surface, the tyre surface of pneumatic tyre kiss the earth strengthens with silicon-dioxide usually, to improve rolling resistance (rolling resistance) and to improve wet braking ability (wet brakingperformance).For the dispersion that improves silicon-dioxide and with the interaction of tread-rubber, use silane coupling agent.But silane/silica tread is compared with carbon black enhanced tyre surface, and typically dynamic stiffness (dynamic stiffness) is relatively poor, causes poor-performing in some aspects, as handling (handling) and turn (cornering).Therefore, need improve the performance of the tyre surface of the kiss the earth that contains silicon-dioxide and silane toughener.
Summary of the invention
The present invention relates to a kind of pneumatic tyre that comprises the tyre surface of kiss the earth, the tyre surface of described kiss the earth comprises rubber combination, described rubber combination comprises diene based elastomer, the silicon-dioxide of per 100 weight part elastomerics (phr) 60-120 weight parts, the monomeric self condensing resin of the sulfur-containing organosilicon compounds of 1-10phr and 1-5phr derived from formula I
R wherein
1Be alkyl group with 1-12 carbon atom, R
2-R
6Each be independently selected from by hydrogen ,-CH
2OH and-CH
2OR
1The group of forming, wherein R
1Be as mentioned above; Condition is R
2-R
6In at least one is a hydrogen, and R
2-R
6In at least one is-CH
2OH.
Embodiment
A kind of pneumatic tyre that comprises the tyre surface of kiss the earth is disclosed, the tyre surface of described kiss the earth comprises rubber combination, described rubber combination comprises diene based elastomer, the silicon-dioxide of per 100 weight part elastomerics (phr) 60-120 weight parts, the monomeric self condensing resin of the sulfur-containing organosilicon compounds of 1-10phr and 1-5phr derived from formula I
R wherein
1Be alkyl group with 1-12 carbon atom, R
2-R
6Each be independently selected from by hydrogen ,-CH
2OH and-CH
2OR
1The group of forming, wherein R
1Be as mentioned above; Condition is R
2-R
6In at least one is a hydrogen, and R
2-R
6In at least one is-CH
2OH.Described self condensing resin can also be the monomeric oligopolymer of formula I or the mixture of described monomer and their oligopolymer.Oligopolymer of the present invention comprises dipolymer, trimer, tetramer of the compound of formula I or the like.Usually, this quasi-oligomer is by methylene group or group-CH
2OCH
2-connecting, at least one R group of wherein said oligopolymer is a hydrogen.
In one embodiment, R
1It is methyl.
In one embodiment, combination (R
3And R
4) or (R
5And R
6) in all be hydrogen one of at least.
In one embodiment, described self condensing resin is such resin, has every unit trimeric cyanamide 3.8 unit bound formaldehyde (combined formaldehyde) and 2.8 unit methyl group (MF
3.8Me
2.8), 34molar%NH, 56molar% methylate (methylation), 10molar% methylol and the polymerization degree are 1.8;
In one embodiment, self condensing resin is such resin, has every unit trimeric cyanamide 3.8 unit bound formaldehyde, 1.7 unit methyl groups and 1.6 unit normal-butyl group (MF
3.8Me
1.7Bu
1.6), 31molar%NH, 34molar% methoxyl group, 32molar% n-butoxy; The 3molar% methylol and the polymerization degree are 2.3.
In one embodiment, self condensing resin is such resin, has every unit trimeric cyanamide 4.0 unit bound formaldehyde and 2.8 unit methyl group (MF
4.0Me
2.8), 30molar%NH, 58molar% methylate, 12molar% methylol and the polymerization degree are 2.3.
In one embodiment, self condensing resin is such resin, has every unit trimeric cyanamide 4.4 unit bound formaldehyde and 3.3 unit methyl group (MF
4.4Me
3.3), 22molar%NH, 66molar% methylate, 18molar% methylol and the polymerization degree are 1.75.
In one embodiment, the resin that self condensing resin is such has every unit trimeric cyanamide 4.1 unit bound formaldehyde and 2.7 unit normal-butyl group (MF
4.1Bu
2.7), 26molar%NH, 58molar% butylation (butylation), 16molar% methylol and the polymerization degree are 2.7.
In one embodiment, be such resin from the resin of condensation, have every unit trimeric cyanamide 4.9 unit bound formaldehyde and 2.4 unit methyl group (MF
4.9Me
2.4), 12molar%NH, 48molar% methyl, 40molar% methylol and the polymerization degree are 2.0.
In one embodiment, self condensing resin is such resin, has every unit trimeric cyanamide 5.3 unit bound formaldehyde and 3.3 unit methyl group (MF
5.3Me
3.3), 4molar%NH, 66molar% methylate, 30molar% methylol and the polymerization degree are 2.5.
In one embodiment, be the melamine formaldehyde resin of part methylization from the resin of condensation, have every unit trimeric cyanamide 3.6 unit bound formaldehyde and 2.0 unit methyl group (MF
3.6Me
2.0), 38molar%NH, 40molar% methyl, 22molar% methylol and 1.8 the polymerization degree.
The self condensing resin that is fit to is commercially available, for example as Cyrez CRA-132S from CytecIndustries, Inc commerce is buied.
In one embodiment, described rubber combination comprises the described self condensing resin of 0.5-5phr.In another embodiment, described rubber combination comprises the described self condensing resin of 1-3phr.
Described rubber combination be substantially free of can with the methylene acceptor (methylene acceptors) of described self condensing resin reaction.Term " methylene acceptor " be well known to those skilled in the art and be used for describing with methylene donor as six-(methoxymethyl) trimeric cyanamides, N, N ', N ＂-trimethylammonium/N, N ', N ＂-trimethylol melamine, hexamethylolmelamine, N, N ', N ＂-dihydroxymethyl trimeric cyanamide, the N-melamine methylol, N, N '-dihydroxymethyl trimeric cyanamide, N, N ', N ＂-three (methoxymethyl) trimeric cyanamide, N, N ' N ＂-tributyl-N, N ', N ＂-trishydroxymethyl-trimeric cyanamide, HMMM and the reaction of six ethoxyl methyl trimeric cyanamides are considered to the reactant of the monomeric product of methylol with formation.Generate resin by forming the monomeric described condensation of the described methylol of methylene bridge.The initial action that the part of described methylene bridge is provided after providing is described methylene donor, and wherein the another one reactant is described methylene acceptor.The representative compounds that can think methylene acceptor that is excluded includes but not limited to Resorcinol, resorcinol derivatives (resorcinolic derivatives), mono-hydroxy phenol and their derivative, dihydric phenol and their derivative, polyhydroxy phenol and their derivative, the phenol novolac resin of non-modified (phenol novolak resins), phenol novolac resin through modification, Resorcinol novolac resin (resorcinol novolak resins) and their mixture.The example of the methylene acceptor that is excluded includes but not limited at U.S.6,605,670, U.S.6,541,551, U.S.6,472,457, U.S.5,945,500, U.S.5,936,056, U.S.5,688,871, U.S.5,665,799, U.S.5,504,127, U.S.5,405,897, U.S.5,244,725, U.S.5,206,289, U.S.5,194,513, U.S.5,030,692, U.S.4,889,481, U.S.4,605,696, U.S.4,436, those disclosed in 853 and U.S.4,092,455.Example through the phenol novolac resin of modification includes but not limited to through the phenol novolac resin of cashew nut oil (cashew nut oil) modification, through tall oil modified phenol novolac resin with through alkyl-modified phenol novolac resin.Other example of the methylene acceptor that is excluded comprises by ring replacement activatory phenol with through cashew nut oil modified phenolic varnish class resol.The exemplary that replaces activatory phenol by ring comprises Resorcinol, cresols, tert.-butyl phenol, isopropyl-phenol, ethylphenol and their mixture.Can buy with trade mark SP6700 commerce from Schenectady Chemical Inc through cashew nut oil modified phenolic varnish class resol.Based on whole phenolic varnish class resol, oily degree of modification can be in the scope of 10-50%.Produce describedly, can make in all sorts of ways through cashew nut oil modified phenolic varnish class resol.For example, can use acid catalyst to make phenol such as phenol, cresols and Resorcinol and aldehyde such as formaldehyde, Paraformaldehyde 96 and phenyl aldehyde reaction.The example of acid catalyst comprises oxalic acid, hydrochloric acid, sulfuric acid and right-toluenesulphonic acids.After the catalyzed reaction, resin is carried out modification with described oil.
Substantially do not contain methylene acceptor, meaning does not promptly join methylene acceptor in the rubber combination intentionally, but this compounds that should understand some minute quantity can be used as impurity to be present in rubber and the rubber accelerator, or is present in the rubber mix equipment as resistates.In one embodiment, rubber combination comprises the methylene acceptor that is less than 0.1phr.
Described rubber combination can use with the rubber or the elastomerics that contain olefinic degree of unsaturation (olefinic unsaturation).Term " rubber or the elastomerics that contain the olefinic degree of unsaturation " or " diene based elastomer " are intended to comprise natural rubber and its various original and reconstituted form (raw andreclaim forms) and various synthetic rubber.In specification sheets of the present invention, unless otherwise indicated, otherwise term " rubber " and " elastomerics " can exchange use.Term " rubber combination ", " compounded rubber " and " rubber compounding thing " can exchange use, refer to and various compositions and material blend or blended rubber that this type of term is known by the technician in rubber mix or rubber compounding field.Representational synthetic polymer is divinyl and its homologue and the homopolymerization product of derivative such as dimethyl butadiene, dimethylbutadiene and pentadiene, and multipolymer, those as forming by divinyl or its homologue or derivative and other unsaturated monomer.The latter comprises acetylene class, for example vinylacetylene; Alkene, iso-butylene for example, thus itself and isoprene copolymer close and form isoprene-isobutylene rubber; Vinyl compound, for example vinylformic acid, vinyl cyanide (thereby itself and polymerizing butadiene form NBR), methacrylic acid and vinylbenzene (thereby back one compound and polymerizing butadiene formation SBR), and vinyl ester and various unsaturated aldehyde, ketone and ether, for example propenal, methyl isopropenyl ketone and EVE.Elastomeric object lesson comprises chloroprene rubber (sovprene), polyhutadiene (comprises cis-1, the 4-polyhutadiene), polyisoprene (comprises cis-1, the 4-polyisoprene), isoprene-isobutylene rubber, halogenated butyl rubber (halobutyl rubber) is as chlorinated butyl rubber or brominated butyl rubber, styrene/isoprene/butadiene rubber, 1,3-divinyl or isoprene and monomer such as vinylbenzene, the multipolymer of vinyl cyanide and methyl methacrylate, and ethylene/propene terpolymer, be also referred to as ethylene/propylene/diene monomer (EPDM), particularly ethylene/propene/Dicyclopentadiene (DCPD) terpolymer.The extra example of operable rubber comprises the starlike-branched polymer of polymkeric substance (SBR, PBR, IBR and SIBR), silicon bonded (silicon-coupled) and the tin bonded (tin-coupled) of the solution polymerization of alkoxyl group-silyl end-functionalization.Preferred rubber or elastomerics are polyhutadiene and SBR.
On the one hand, rubber preferably has at least two kinds of diene rubbers.For example, the combination of preferred two or more rubber, as cis 1, the 4-polyisoprene rubber is (though preferred natural, but natural or synthetic all can), 3, the butadiene/acrylonitrile copolymer of 4-polyisoprene rubber, styrene/isoprene/butadiene rubber, the styrene/butadiene rubbers, cis 1 rubber and the emulsion polymerization prepared that obtain by emulsion and solution polymerization.
In one aspect of the invention, can use the phenylethylene/butadiene (E-SBR) that obtains by letex polymerization, this E-SBR has the conventional relatively styrene content of the about 28% one-tenth key vinylbenzene of about 20-(bound styrene), perhaps for some application, can use and have medium or higher one-tenth key styrene content, the E-SBR of the one-tenth key styrene content of promptly about 30-about 45%.
The E-SBR of emulsion polymerization prepared means vinylbenzene and 1,3-butadiene and carries out copolymerization as water miscible liquid.This is known by those skilled in the art.Become the key styrene content to change, for example from about 5-about 50%.On the one hand, described E-SBR can also contain vinyl cyanide to form ter-polymers rubber, and E-SBAR contains quantity and for example is the one-tenth key vinyl cyanide of the about 30wt% of about 2-in this ter-polymers.
Phenylethylene/butadiene/acrylonitrile copolymer the rubber of the one-tenth key vinyl cyanide that contains the about 40wt% of 2-that has an appointment in multipolymer of emulsion polymerization prepared also is intended to be diene rubber and is used for the present invention.
It is about 50% that the SBR of solution polymerization (S-SBR) typically has about 5-, is preferably about the one-tenth key styrene content of 9-about 36%.S-SBR can prepare easily, for example passes through the organolithium catalytic preparation in the presence of organic hydrocarbon solvent.
In one embodiment, can use cis 1 rubber (BR).These BR can for example pass through the organic solution polymerization preparation of 1,3-butadiene.Described BR can be easily for example to have at least 90% cis 1, and 4-content is feature.
Cis 1,4-polyisoprene and cis 1,4-polyisoprene natural rubber is that the technician of rubber materials is known.
The term that uses in the literary composition " phr ", and, refer to " weight part of the rubber of per 100 weight parts or certain material of elastomerics " according to conventional practice.
Rubber combination also can comprise the treated oil (processing oil) that is no more than 70phr.Treated oil can be used as the extending oil (extending oil) that typically is used for filled elastomer and is included in rubber combination.Treated oil can also be included in the rubber combination by the direct interpolation of oil in the rubber compounding process.The treated oil that uses can comprise the extending oil that is present in the elastomerics and the treated oil that in the compounding process, adds the two.The treated oil that is fit to comprises various oil as known in the art, comprises aromatic series, paraffinic, cycloparaffin series, vegetables oil and low PCA oil, as MES, TDAE, SRAE and heavy naphthenic oil.The low PCA oil that is fit to comprises by the IP346 method measures those with Ppolynuclear aromatic content of being less than 3wt%.The step of IP346 method can be at United Kingdom, and the Institute of Petroleum publishes
Standard Methods for Analysis ﹠amp; Testing of Petroleum and Related ProductsWith
British Standard 2000 Parts, find in 2003,62 editions.
Term " rubber or the elastomerics that contain the olefinic degree of unsaturation " is intended to comprise natural rubber and its various original and reconstituted form, and various synthetic rubber.In specification sheets of the present invention, unless otherwise indicated, otherwise term " rubber " and " elastomerics " can exchange use.Term " rubber combination ", " compounded rubber " and " rubber compounding thing " can exchange use, refer to and various compositions and material blend or blended rubber, and this type of term are known by the technician in rubber mix or rubber compounding field.
In one embodiment, rubber combination comprises the silicon-dioxide of the about 120phr of about 60-.In another embodiment, rubber combination comprises the silicon-dioxide of the about 100phr of about 80-.
The siliceous pigment that can generally use in the rubber compounding thing comprises conventional pyrogene (pyrogenic) and precipitation siliceous pigment (silicon-dioxide).In one embodiment, use precipitated silica.The conventional siliceous pigment that uses among the present invention is precipitated silica, as by the acidifying soluble silicate for example water glass obtain those.
This type of conventional silicon-dioxide can for example pass through BET surface-area (use radon survey) and characterize.In one embodiment, the BET surface-area can be about 600 meters squared per gram of about 40-.In another embodiment, the BET surface-area can be about 300 meters squared per gram of about 80-.The BET method of meter area is at Journal of the American Chemical Society, and 60 volumes are described in 304 pages (1930).
It is about 400 that conventional silicon dioxide features can also be to have about 100-, or dibutyl phthalate (DBP) absorption value of about 150-about 300.
Although silica dioxide granule dimensionally even can be littler or can be bigger, expects that conventional silicon-dioxide has for example average ultimate particle size of 0.01-0.05 micron (averageultimate particle size), passes through determination of electron microscopy.
Can use the various silicon-dioxide that can commercial buy, the trade mark is the silicon-dioxide of 210,243 grades under the Hi-Sil trade mark that can buy from PPG Industries commerce as (only be used for for example and non-limiting) herein; The for example trade mark that obtains from Rhodia is that the silicon-dioxide of Z1165MP and Z165GR and for example trade mark that obtains from Degussa AG are the silicon-dioxide of VN2 and VN3, or the like.
Compositions of vulcanize rubbers can comprise 1-30phr be selected from carbon black, through crosslinked particulate polymers gel, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) or through the extra filler of plastifying starch.
Can be with normally used carbon black as conventional fillers.The representative example of this type of carbon black comprises N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991.These carbon blacks have scope the iodine of 9-145g/kg absorb and scope at 34-150cm
3The DBP number of/100g.
Other filler that can use in rubber combination includes but not limited to granular filler, comprises ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE)), the particulate polymers gel includes but not limited at United States Patent(USP) Nos. 6,242,534,6,207,757,6,133,364,6,372,857,5,395,891 or 6, those disclosed and through plastifying starch composite material filler in 127,488, include but not limited in U.S. Patent No. 5,672 those disclosed in 639.
In one embodiment, rubber combination comprises conventional sulfur-containing organosilicon compounds or based on the silicoorganic compound of sulfydryl.The example of the conventional sulfur-containing organosilicon compounds that is fit to meets following formula:
Z—Alk—S
n—Alk—Z II
Wherein Z be selected from by
The group of forming, wherein R
2Be alkyl group, cyclohexyl or phenyl with 1-4 carbon atom; R
3Be alkoxyl group, or have the cycloalkyloxy of 5-8 carbon atom with 1-8 carbon atom; Alk is the bivalent hydrocarbon radical with 1-18 carbon atom, and n is the integer of 2-8.
In one embodiment, described sulfur-containing organosilicon compounds is 3,3 '-two (trimethoxy or triethoxysilylpropyltetrasulfide) polysulphide.In one embodiment, described sulfur-containing organosilicon compounds is 3,3 '-two (triethoxysilylpropyltetrasulfide) disulphide and/or 3,3 '-two (triethoxysilylpropyltetrasulfide) tetrasulfide.Therefore, for formula II, Z can be
R wherein
3Be to have 2-4 carbon atom, the perhaps alkoxyl group of 2 carbon atoms; Alk has 2-4 carbon atom, perhaps has the divalence hydrocarbon of 3 carbon atoms; N is the integer of 2-5, or 2 or 4.
In another embodiment, the sulfur-containing organosilicon compounds that is fit to is included in U.S. Patent No. 6,608, disclosed compound in 125.In one embodiment, sulfur-containing organosilicon compounds comprises 3-(capryloyl sulfenyl (octanoylthio))-1-propyl-triethoxysilicane, CH
3(CH
2)
6C (=O)-S-CH
2CH
2CH
2Si (OCH
2CH
3)
3, it can be used as NXT
TMBuy from GESilicones commerce.
In another embodiment, the sulfur-containing organosilicon compounds of Shi Heing is included in those disclosed among the U.S. Patent Publication No.2003/0130535.In one embodiment, sulfur-containing organosilicon compounds is the Si-363 from Degussa.
The amount of sulfur-containing organosilicon compounds will change according to the level of other additive that uses in the rubber combination.Generally speaking, the amount of described compound is 0.5-20phr.In one embodiment, described weight range is at 1-10phr.
Those skilled in the art understand easily, described rubber combination will be by common known method compounding in the rubber compounding field, as the vulcanizable composition rubber of various sulphur is mixed with the various additive materials that generally use, described additive material such as sulphur donor (sulfur donors), auxiliary curing agent such as activator and retarding agent (retarders), and processing additives such as oil, resin comprises tackifying resin, and softening agent, filler, pigment, lipid acid, zinc oxide, wax, antioxidant and antiozonidate and peptizing agent.Such as known for those skilled in the art, the desired use of the material of crossing according to the vulcanizable and sulfur vulcanization of sulphur (rubber), select above-mentioned additive and usually routinely amount use.The representative example of sulphur donor comprises elementary sulfur (free sulphur), amine disulphide, polymeric polysulphide and sulphur olefin adducts (sulfur olefin adduct).In one embodiment, sulphur-vulcanizing agent (sulfur-vulcanizing agent) is an elementary sulfur.Sulphur-vulcanizing agent can be with 0.5-8phr, and perhaps the amount of 1.5-6phr is used.If use, the typical amount of tackifier resins comprises the about 10phr of about 0.5-, is generally the about 5phr of about 1-.The typical amount of processing aid comprises the about 50phr of about 1-.The typical amount of antioxidant comprises the about 5phr of about 1-.Representative antioxidants can be for example phenylbenzene-p-phenylenediamine and other antioxidant, as
The Vanderbilt Rubber Handbook (1978), those disclosed in the 344-346 page or leaf.The typical amount of antiozonidate comprises about 1-5phr.If use, the typical amount of lipid acid (can comprise stearic acid) comprises the about 3phr of about 0.5-.The typical amount of zinc oxide comprises the about 5phr of about 2-.The typical amount of wax comprises the about 5phr of about 1-.Usually use Microcrystalline Wax.The typical amount of peptizing agent comprises the about 1phr of about 0.1-.Typical peptizing agent can be for example reptazin and dibenzamidodiphenyl disulfide (dibenzamidodiphenyl disulfide).
Promotor being used to controlled sulfuration required time and/or temperature and is used to improve the performance of vulcanized rubber.In one embodiment, can use single accelerator system, i.e. primary accelerator.Can use total weight range at the about 4phr of about 0.5-, one or more primary accelerators of the about 1.5phr of perhaps about 0.8-.In another embodiment, in order to activate and in order to improve the performance of vulcanized rubber, can to use the combination of primary accelerator and less important promotor, wherein the consumption of less important promotor is less, according to appointment the about 3phr of 0.05-.The combination of these promotor expection can produce synergy to final performance, and be better than to a certain extent producing by the arbitrary promotor of independent use those.In addition, can use delayed action (delayed action) promotor, it is not subjected to the normal process Temperature Influence, but produces gratifying curing at common curing temperature.Can also use VULCANIZATION RETARDER C.T.P/PVI.The suitable type of the promotor that can use in the present invention is amine, disulphide, guanidine class, Thiourea, thiazoles, thiurams, sulfinylamines, dithiocarbamate(s) and xanthate (xanthates).In one embodiment, primary accelerator is the sulfinyl amine compound.If use less important promotor, this less important promotor can be guanidine, dithiocar-bamate or thiuram compound.
Can finish the mixing of rubber combination by the known method of the technician in rubber mix field.For example, described composition typically mixes at least two stages, and promptly at least one unproductive stage then is the productivity mix stages.The final solidifying agent (finalcurative) that comprises sulphur-vulcanizing agent typically mixes in terminal stage, described terminal stage is commonly referred to " productivity " mix stages, wherein mixes typically under the temperature of the mixing temperature that is lower than the one or more unproductive mix stages in front or outlet temperature to take place.Term " unproductive " and " productivity " mix stages are known by the technician in rubber mix field.Can make rubber combination through the mechanically mixing step of being heated.Described hot mechanically mixing step is usually included in the one suitable period of mechanical workout in mixing machine or the forcing machine to produce 140 ℃-190 ℃ rubber temperature.The suitable time length of hot mechanical workout is as the function of the volume of operational condition and component and character and change.For example, hot mechanical workout can be 1-20 minute.
Pneumatic tyre of the present invention can be racing-car tyre (race tire), tyres for passenger cars (passengertire), aircraft tyre (aircraft tire), agricultural tire (agricultural), bull dozer tire (earthmover), off-the-road tyre (off-the-road), truck tyre (truck tire) or the like.In one embodiment, tire is tyres for passenger cars or truck tyre.Tire can also be radial or bias tyre.
Airtyred sulfuration of the present invention is implemented in about 100 ℃-200 ℃ conventional temperature in scope usually.In one embodiment, sulfuration is implemented in about 110 ℃-180 ℃ temperature.Any general vulcanization process be can use,, superheated vapour or warm air beating used as in pressing machine or mould, heating.These tires can by those skilled in the art know and to those skilled in the art will conspicuous the whole bag of tricks structure, moulding, molding and curing.
To further specify the present invention by the embodiment of following indefiniteness.
Embodiment 1
In this embodiment, illustrate self condensing resin is joined effect in the silicon-dioxide enhanced rubber combination.The rubber combination that contains diene based elastomer, filler, processing aid, anti degradant and solidifying agent according to the formulation shown in the table 1.Sample 1 is contrast, and sample 2 is except the self condensing resin that adds 1.5phr, and is identical with sample 1 aspect composition.
Use the viscoelastic property of RPA specimen." RPA " refers to rubber machining analyzer (RubberProcess Analyzer), as the RPA 2000 of Alpha Technologies (Flexsys Company in the past, former Monsanto Company) production
TMInstrument.Reference about RPA 2000 instruments can find in following publication: H.A.Palowski etc.,
Rubber World, 1992 06 month and 1997 01 month and
Rubber ﹠amp; Plastics News, on 04 26th, 1993 and 05 month 10 days.
" RPA " test result in the table 2 is under 1.6 hertz the dynamic shearing pattern in frequency and the data report that obtains under the dynamic strain value of report as coming comfortable 100 ℃.Stretching and hardness performance have also been measured and report in table 2.
Table 1
The edition with parallel text invention
Sample number into spectrum 12
Unproductive mixing step
Styrene butadiene rubbers
168.78 68.78
Polyhutadiene
250 50
Silicon-dioxide
383 83
Multi-sulfur silane (polysulfidic silane)
46.64 6.64
(active quantities)
Treated oil 4.84 4.84
Wax
51.5 1.5
6-PPD 2.25 2.25
Self condensing resin
6, phr 0 1.5
The productivity mixing step
Sulphur 22
Promotor
71.6 1.6
Promotor
81.8 1.8
Zinc oxide 2.5 2.5
Stearic acid 33
1The emulsion styrene butadiene ribber has 37.5phr distillation aromatic series extract oil (distillatearomatic extract oil), has 31.5% vinylbenzene and 50 Mooney
2Nickel cis-BR Budene 1207 from the Goodyear acquisition
3High dispersive silicon-dioxide Zeosil 1165MP from the Rhodia acquisition
4Two (triethoxysilylpropyltetrasulfide) disulphide 50wt% on the CB carrier
5Paraffin and Microcrystalline Wax
7Sulfinylamines
8The guanidine class
Table 2
Sample number into spectrum 12
Self condensing resin
1, phr 0 1.5
RPA，100℃，1.6Hz
G ', 1% strain (MPa) 2.35 2.8
G ', 10% strain (MPa) 1.62 1.78
G ', 50% strain (MPa) 0.87 0.93
Tan δ, 10% strain 0.15 0.15
23 ℃ 65 68 of Xiao A hardness
The Zwick resilience, 100 ℃ 57 59
Ring modulus, 23 ℃
Extension at break, % 580 490
Modulus 100%, MPa 1.7 2.1
Modulus 300%, MPa 7.9 10.4
Tensile strength, MPa 19.1 18.8
The DIN wearing and tearing
Volumetric wear (mm
3) 42 43
In table 2, see one group of special performance of the high strain modulus of the hardness that the interpolation of self condensing resin causes increasing, the rebound resilience of improvement and increase.Do not wish to be bound by any theory, it is believed that, described self condensing resin can stand to interact with the hydrogen bonding of the silanol of silicon-dioxide, and its catalysis silane condensation on silica sphere in addition of amine moiety (aminic moieties) by it causes wonderful and unexpected better properties as shown in table 2.
When some representational embodiment and details are shown for the purpose of illustrating the invention, it will be readily apparent to one skilled in the art that and under the situation that does not deviate from the subject or scope of the present invention, to make various changes and improvements it.
Claims (7)
1. pneumatic tyre, be characterised in that the tyre surface of kiss the earth, the tyre surface of this kiss the earth comprises rubber combination, described rubber combination comprises diene based elastomer, the silicon-dioxide of per 100 weight part elastomerics (phr) 60-120 weight parts, the monomeric self condensing resin of the sulfur-containing organosilicon compounds of 1-10phr and 1-5phr derived from formula I
R wherein
1Be alkyl group with 1-12 carbon atom, R
2-R
6Each be independently selected from by hydrogen ,-CH
2OH and-CH
2OR
1The group of forming, wherein R
1Be as mentioned above; Condition is R
2-R
6In at least one is a hydrogen, and R
2-R
6In at least one is-CH
2OH.
2. the pneumatic tyre of claim 1 is characterized in that described rubber combination is substantially free of additional methylene acceptor.
3. the pneumatic tyre of claim 1 is characterized in that described rubber combination comprises the additional methylene acceptor that is less than 0.1phr.
4. the pneumatic tyre of claim 1 is characterized in that R1 is a methyl.
5. the pneumatic tyre of claim 1 is characterized in that combination (R
3And R
4) or (R
5And R
6) in all be hydrogen one of at least.
6. the pneumatic tyre of claim 1 is characterized in that described sulfur-containing organosilicon compounds comprises the compound of following formula:
Z—Alk—S
n—Alk—Z II
Wherein Z be selected from by
The group of forming, wherein R
7Be alkyl group, cyclohexyl or phenyl with 1-4 carbon atom; R
8It is the cycloalkyloxy that has the alkoxyl group of 1-8 carbon atom or have 5-8 carbon atom; Alk is the divalence hydrocarbon with 1-18 carbon atom, and n is the integer of 2-8.
7. the pneumatic tyre of claim 1 is characterized in that described sulfur-containing organosilicon compounds comprises 3,3 '-two (triethoxysilylpropyltetrasulfide) disulphide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99032107P | 2007-11-27 | 2007-11-27 | |
| US60/990321 | 2007-11-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101445622A true CN101445622A (en) | 2009-06-03 |
Family
ID=40741520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101786919A Pending CN101445622A (en) | 2007-11-27 | 2008-11-27 | Tire with silica tread having self condensing resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5460033B2 (en) |
| CN (1) | CN101445622A (en) |
| BR (1) | BRPI0805232A2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4092455A (en) * | 1976-03-08 | 1978-05-30 | American Cyanamid Company | Use of methylenebis- and thiobisnaphthols as promoters in tire cord adhesion to rubber |
| JP2862563B2 (en) * | 1989-06-05 | 1999-03-03 | 東洋ゴム工業株式会社 | Cap-based tires |
| US5641820A (en) * | 1995-12-26 | 1997-06-24 | The Goodyear Tire & Rubber Company | Silica-filled rubber compositions containing dialkyleneamide polysulfides |
| US6269858B1 (en) * | 1999-08-06 | 2001-08-07 | The Goodyear Tire & Rubber Company | Rubber containing starch reinforcement and tire having component thereof |
| JP4634181B2 (en) * | 2005-02-15 | 2011-02-16 | 東洋ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire |
-
2008
- 2008-11-26 BR BRPI0805232 patent/BRPI0805232A2/en not_active Application Discontinuation
- 2008-11-27 JP JP2008302772A patent/JP5460033B2/en not_active Expired - Fee Related
- 2008-11-27 CN CNA2008101786919A patent/CN101445622A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP5460033B2 (en) | 2014-04-02 |
| BRPI0805232A2 (en) | 2009-09-15 |
| JP2009127055A (en) | 2009-06-11 |
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| PB01 | Publication | ||
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Open date: 20090603 |