CN101589100B - Rubber composition and tire using the same - Google Patents
Rubber composition and tire using the same Download PDFInfo
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- CN101589100B CN101589100B CN200880002192.2A CN200880002192A CN101589100B CN 101589100 B CN101589100 B CN 101589100B CN 200880002192 A CN200880002192 A CN 200880002192A CN 101589100 B CN101589100 B CN 101589100B
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Abstract
Disclosed is a rubber composition which enables, when used in a tread rubber for a tire, to improve initial grip performance and traveling stability of the tire as compared with conventional tires. Specifically disclosed is a rubber composition which is obtained by blending a C9 resin containing indene, which has a softening point of 130 DEG C to 190 DEG C and an indene content of 30-80% by mass, in a rubber component.
Description
Technical field
The tire that the present invention relates to rubber combination and use it, more particularly, compare the initial earth-catching property that improves tire and the rubber combination of riding stability with conventional tire thereby relate in tire tread glue, using, and the tire that in tread rubber, uses this type of rubber combination.
Background technology
Be desirably in the high-performance tire tyre surface that uses in the racing car etc. and keep good control stability (DRY adherence properties) to dry pavement when finishing from the beginning of travelling.Therefore, to be in DRY adherence properties (initial earth-catching property) in the initial travel phase of relative low temperature in order improving at tire, to have studied so far compoundings such as tenderizer that the oil ingredient that will comprise low softening point resin and liquid polymers and occurs at low temperatures wave effect to the rubber combination that is used for tread rubber.
For example, compounding has C
9The rubber combination of aromatic resin etc. is disclosed in JP-A-H05-9336, wherein consider mixing during the dispersiveness of resin, will have softening temperature and not be higher than 140 ℃ C
9The aromatic resin compounding is to said composition.And compounding has the rubber combination of aromatic vinyl compound to be disclosed in JP-A-H10-195238 and JP-A-H10-195242, and wherein compounding has softening temperature and is not higher than 140 ℃ resin.
Yet, when this type of has the standby rubber combination of resin of low softening point by compounding, and when making tire with this rubber combination in tread rubber, initially earth-catching property is improved, but during travelling, earth-catching property raises along with the tire tread temperature and reduces.On the other hand, when for improve travel during tire earth-catching property (riding stability) in the tyre temperature rising situation, separately with high softening point resin such as C
9The compoundings such as resin are during to rubber combination, and the initial earth-catching property of tire on the low temperature road surface significantly reduces.
As the method that solves problems, consider with high softening point resin and low softening point resin both compounding to the method for rubber combination.Therefore yet the resin total amount of compounding is influential to the temperature profile of rubber combination, but compounding to the amount of resin of rubber combination is limited.As a result, the tire that obtains by the method all is being medium aspect initial earth-catching property and the riding stability.Therefore, need to be provided for can be simultaneously taking into account the rubber combination of the tire tread glue of the initial earth-catching property of tire and riding stability with higher level.
Summary of the invention
The inventor has studied rubber combination that how deteriorated use compounding has low softening point resin and have a good initial earth-catching property as the earth-catching property during the travelling of the tire of tread rubber, and find: even on identical distance, significantly change the degree of deteriorated earth-catching property by pavement temperature.That is, find: be not higher than at pavement temperature under 10 ℃ the condition, the riding stability of tire is difficult to reduce, and on the contrary, surpasses under 40 ℃ the condition at pavement temperature, and the riding stability of tire is easy to reduce.
And, find: when the vehicle that is equipped with in tread rubber the tire that uses above-mentioned rubber combination travels in pavement temperature is 42 ℃ annular distance, measure under steam tire internal temperature, behind about 10 circles that travel, tire internal temperature is increased to 100 ℃-110 ℃.Because the measurement to tire internal temperature is carried out after vehicle is sailed the reason place of returning something for repairs, so this internal temperature during prediction is travelled becomes higher.The rubber combination that compounding has a low softening point resin is in that to be higher than dynamic modulus under 100 ℃ (E ') large aspect deteriorated, what therefore worry is when the internal temperature of the tire that obtains by this type of rubber combination of use in tread rubber becomes higher, this rubber combination is softening with resin, thus deteriorated riding stability.
Therefore, the tire that the purpose of this invention is to provide rubber combination and in tread rubber, use this type of rubber combination, described rubber combination can use in tire tread glue, thereby compares initial earth-catching property and the riding stability of improving tire with conventional tire.
For achieving the above object, the inventor has the rubber combination with resin that E ' is high under the high temperature to carry out various researchs to having the effect and the compounding that reduce E ' under the room temperature, and finds: the C that can contain by compounding indenes
9Resinoid to rubber combination production capacity in next life is enough made to be had than the equal tread rubber rubber combination of the tire of higher initial earth-catching property and riding stability of the initial adherence properties of conventional tire and riding stability, finishes thus the present invention.
That is, rubber combination of the present invention be characterised in that with have softening temperature be 130 ℃-190 ℃ and indenes content be 30-80 quality % contain indenes C
9The resinoid compounding is to rubber components.This indenes content is preferably 45-75 quality %.
In rubber combination of the present invention, contain indenes C
9Resinoid softening temperature is preferably in 140-180 ℃ of scope.As containing indenes C
9Resinoid particularly preferably has alpha-methyl styrene-Vinyl toluene-indene copolymer of softening temperature 155-180 ℃.
In another preferred embodiment of rubber combination of the present invention, contain indenes C
9Resinoid is take with respect to the amount compounding of per 100 mass parts rubber components as the 5-80 mass parts.
In an again preferred embodiment of rubber combination of the present invention, contain indenes C
9Resinoid comprises C
5Component.Containing indenes C
9C in the resinoid
5Component concentration is preferably in 0.5-20 quality % scope, more preferably in 1-10 quality % scope.
Rubber combination of the present invention preferably also comprises being selected to have softening temperature and be not less than 135 ℃ the homopolymer resin of aromatic vinyl compound and at least a resin of copolymer resin.
And rubber combination of the present invention comprises also that preferably at least a softening temperature that has that is selected from hydrogenated petroleum resin is not less than 120 ℃ resin, and described hydrogenated petroleum resin comprises C by part or all of hydrogenation
5Component and/or C
9The petroleum resin of component obtain.This softening temperature more preferably is not less than 130 ℃.
In addition, rubber combination of the present invention preferably includes at least a resin that softening temperature is not less than 130 ℃ hydrogenated terpene resin that has that is selected from by part or all of hydrogenated terpene resin acquisition.This hydrogenated terpene resin preferably has softening temperature and is not less than 140 ℃.
Rubber combination of the present invention also preferably further comprises at least a resin that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin.This at least a resin that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin preferably has softening temperature and is not less than 140 ℃.
In addition, rubber combination of the present invention preferably includes one or more resins that are selected from alkyl phenolic resin (A) and at least a resin (B) that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin.In the case, resin (A) and resin (B) are preferably with mass ratio 10: 1-1: 10 compoundings.And the total amount of the resin of compounding (A) and resin (B) is preferably in 3-100 mass parts scope, with respect to per 100 mass parts rubber components.In addition, the primary structure at the phenol position of resin (A) is preferably the p-tert-butylphenol structure.In addition, resin (B) comprises terpenes-phenol copolymer resin at least, and wherein the hydroxyl value of this terpenes-phenol copolymer resin preferably is not more than 170.In addition, resin (A) preferably has softening temperature and is not less than 120 ℃.
In other preferred embodiments of rubber combination of the present invention, rubber components comprises the butadiene type multipolymer that is not less than 70 quality %, and its contents of ethylene that has in the divinyl part is not less than 10%.In the case, the butadiene type multipolymer preferably includes styrene-butadiene copolymer.And it is 20-70 quality % that styrene-butadiene copolymer preferably has styrene content.
In addition, rubber combination of the present invention preferably includes 60-200 mass parts carbon black, with respect to per 100 mass parts rubber components.
In addition, tire characteristics of the present invention is to use with each described rubber combination in beginning a project in tread rubber.
Thereby the present invention can provide and can use the initial earth-catching property of comparing further improvement tire with conventional tire and the rubber combination of riding stability in tire tread glue, and the tire that uses this type of rubber combination in tread rubber.
Embodiment
Rubber combination according to the present invention is by containing indenes C
9The rubber combination that the resinoid compounding forms to the rubber components is characterized in that, contains indenes C
9Resinoid has 130 ℃-190 ℃ of softening temperatures, and indenes content is 30-80 quality %.By in tire tread glue, using this compounding that the indenes of containing C is arranged
9Resinoid rubber combination is compared with conventional tire, can further improve initial earth-catching property and the riding stability of tire.Contain indenes C
9Resinoid preferably has softening temperature 140-180 ℃, more preferably 155-180 ℃.When will have softening temperature be lower than 130 ℃ contain indenes C
9The resinoid compounding is during to rubber combination, and tire running stability can not be improved.Consider the resin dispersion during mixing, this softening temperature preferably is not higher than 190 ℃.In addition, contain indenes C
9Resinoid indenes content is preferably 45-75 quality %.Containing indenes C
9In the resinoid, when indenes content was lower than 30 quality %, riding stability was not enough, and when it surpasses 80 quality %, can not guarantee initial earth-catching property.
Contain indenes C
9The resinoid meaning refers to contain the resin of indenes in initial monomers.As the monomer except indenes, mention Vinyl toluene, alpha-methyl styrene and cumarone etc.As C
9Resinoid is mentioned Vinyl toluene-alpha-methyl styrene-indene resin, Vinyl toluene-indene resin and alpha-methyl styrene-indene resin etc.
As C
9Resinoid particularly preferably has softening temperature and is not less than 155 ℃ and be not higher than alpha-methyl styrene-Vinyl toluene-indene copolymer resin of 180 ℃.Work as C
9When resinoid is alpha-methyl styrene-Vinyl toluene-indene copolymer resin, riding stability under the high temperature is guaranteed, if but softening temperature is lower than 155 ℃, it is little then to improve under the high temperature effect of riding stability, if and softening temperature surpasses 180 ℃, then the breaking property of the resin dispersion reduction in the rubber components and rubber combination is deteriorated.
In rubber combination according to the present invention, compounding contain indenes C
9Resinoid amount is preferably the 5-80 mass parts, and more preferably 5-60 mass parts is with respect to per 100 mass parts rubber components.In order to give rubber combination with the characteristic of resin, require the amount of resin of compounding to be not less than 5 mass parts, with respect to per 100 mass parts rubber components, but when it surpassed 80 mass parts, rubber combination solidified at a lower temperature.
In rubber combination according to the present invention, contain indenes C
9Resinoid preferably includes C
5Component.Contain indenes C
9The dispersing property of resinoid in rubber is by comprising this C
5Component is improved.As this C
5Component, mention alkene such as amylene (1), 2-amylene (2), 2-methyl butene (1) and 3-methyl butene (1) etc., diolefine such as 2-methyl butadiene (1,3), pentadiene (1,3), cyclopentadiene and pentadiene (1,2) etc.Wherein, preferred diolefine, more preferably cyclopentadiene.
And, in rubber combination according to the present invention, contain indenes C
9C in the resinoid
5The content of component is preferably 0.5-20 quality %, more preferably 1-10 quality %.When containing indenes C
9C in the resinoid
5When the content of component is lower than 0.5 quality %, the dispersed variation of resin, and when it surpassed 20 quality %, riding stability was impaired.
In addition, rubber combination according to the present invention preferably includes to be selected from and has softening temperature and be not less than 135 ℃ the homopolymer resin of aromatic vinyl compound and at least a resin of copolymer resin.When compounding has softening temperature when being lower than 135 ℃ resin, the riding stability of tire is impaired.And, consider the dispersiveness in mixing, the softening temperature of above-mentioned resin preferably is not higher than 180 ℃.In order to give rubber combination with the characteristic of resin, require the amount of resin of compounding to be not less than 10 mass parts, with respect to per 100 mass parts rubber components, but when it surpassed 60 mass parts, rubber combination solidified at a lower temperature.As the homopolymer resin or the copolymer resin that have softening temperature and be not less than 135 ℃ aromatic vinyl compound, mention alpha-methyl styrene homopolymer resin, alpha-methyl styrene-styrene copolymer resin and alpha-methyl styrene-vinyl toluene copolymer resin etc.These resins separately compounding or with two or more the combination compounding.
In addition, rubber combination according to the present invention preferably includes to be selected from by part or all of hydrogenation and comprises C
5Component and/or C
9The petroleum resin of component have an at least a resin that softening temperature is not less than 120 ℃ hydrogenated petroleum resin, comprise C by part or all of hydrogenation
5Component and/or C
9The hydrogenated petroleum resin that the petroleum resin of component form more preferably has softening temperature and is not less than 130 ℃.When compounding has softening temperature when being lower than 120 ℃ resin, the riding stability of tire is impaired.And, consider the dispersiveness in mixing, the softening temperature of resin preferably is not higher than 180 ℃.In order to give rubber combination with the characteristic of resin, require the amount of resin of compounding to be not less than 10 mass parts, with respect to per 100 mass parts rubber components, but when it surpassed 80 mass parts, rubber combination solidified at a lower temperature.As comprising C by part or all of hydrogenation
5Component and/or C
9The softening temperature that has of the petroleum resin of component is not less than 120 ℃ hydrogenated petroleum resin, mention the Industries by Arakawa Chemical, Ltd. the ARUKONP125 (softening temperature: 125 ℃) that produces, by Idemitsu Kosan Co., Ltd. the I-MARVY135 that produces, by Arakawa Chemical Industries, Ltd. the ARUKONM135 (softening temperature: 135 ℃) that produces, by Idemitsu Kosan Co., Ltd. the I-MARV P140 (softening temperature: 140 ℃) that produces and by Arakawa Chemical Industries, the ARUKON P140 (softening temperature: 140 ℃) that Ltd. produces etc.Its separately compounding to rubber combination, or with two or more the combination compoundings to rubber combination.
In addition, rubber combination according to the present invention preferably includes at least a resin that softening temperature is not less than 130 ℃ hydrogenated terpene resin that has that is selected from by part or all of hydrogenated terpene resin.Even although by containing indenes C separately
9Resinoid compounding to rubber combination also obtains certain effect, but the effect of improving tire running stability can significantly be improved by further compounding hydrogenated terpene resin.Be lower than 130 ℃ hydrogenated terpene resin if compounding has softening temperature, the initial earth-catching property of tire is improved, but riding stability is impaired.From the viewpoint of riding stability, the softening temperature of hydrogenated terpene resin preferably is not less than 140 ℃.In order to give rubber combination with the characteristic of resin, require the amount of resin of compounding to be not less than 10 mass parts, with respect to per 100 mass parts rubber components, but when it surpassed 60 mass parts, rubber combination solidified at a lower temperature.
In order balancedly to provide earth-catching property and processibility with higher level, in rubber combination according to the present invention, preferred compounding be selected from have softening temperature be not less than 130 ℃ terpenes homopolymer and terpenes-phenol copolymer resin one of at least.In addition, this resinoid softening temperature preferably is not less than 140 ℃.And the amount of this resin of compounding is preferably in 10-100 mass parts scope, with respect to per 100 mass parts rubber components.When amount of resin is lower than 10 mass parts with respect to per 100 mass parts rubber components, the effect that can not obtain to expect, and when it surpasses 100 mass parts, the performance of rubber combination is not improved, mixed refining process is significantly deteriorated, and after sulfuration, solidify deteriorated processibility thereby cause at low temperatures.From the viewpoint of processibility etc., compounding to the amount of resin of rubber combination is preferably the 20-80 mass parts.Terpenes monomer as the starting raw material that is used for resin is not particularly limited, and preferably includes monoterpene alkene such as α-pinene and limonene etc.From the viewpoint of earth-catching property and processibility, more preferably comprise the monomer of α-pinene, most preferably α-pinene.Consider the resin dispersion in mixing, this resinoid softening temperature preferably is not higher than 190 ℃.In addition, it preferably includes at least a resin that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin, and the softening temperature of terpenes homopolymer resin and terpenes-phenol copolymer resin more preferably is not less than 140 ℃.
And rubber combination according to the present invention preferably includes at least a resin (A) and at least a resin (B) that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin that is selected from alkyl phenolic resin.When in tire tread glue, using the rubber combination also comprise at least a resin (A) that is selected from alkyl phenolic resin and at least a resin (B) that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin, can significantly strengthen high earth-catching property greater than before, and operability and wearability under the not deteriorated tire low temperature.In addition, preferred compounding resin (A) and resin (B) both, and if a kind of resin of compounding only then can not obtain the desired effects as the object of the invention.
Preferably, resin (A) and resin (B) are with mass ratio 10: 1-1: 10 compoundings.When compounding is compared 10: 1-1: in the time of beyond 10 scopes, can not fully obtain the desired effects as the object of the invention.
In addition, the total amount of resin (A) and resin (B) is preferably the 3-100 mass parts, more preferably 3-90 mass parts, and 3-80 mass parts most preferably is with respect to per 100 mass parts rubber components.When total amount is lower than 3 mass parts, can not obtains fully the desired effects as the object of the invention, and when it surpasses 100 mass parts, can not fully obtain target capabilities, and also have the poorly worry of the rear performance of impact sulfuration.
About the resin (A) that is selected from alkyl phenolic resin, desirable initial monomers is tert.-butyl phenol or tert-octyl phenol, more preferably p-tert-butylphenol-formaldehyde resin and p-tert-butylphenol-acetaldehyde resin.For the effect of the present invention that obtains to expect, the softening temperature of alkyl phenolic resin preferably is not less than 120 ℃, more preferably 120-160 ℃.When this softening temperature was lower than 120 ℃, riding stability reduced, and when it surpasses 160 ℃, because the polarity of resin is high, so resin is in mixing middle heterogeneity dispersion, and wearability is significantly deteriorated.Alkyl phenolic resin can use separately, or being used in combination with two or more.
As for one or more resins (B) that is selected from terpine resin and terpenes-phenol copolymer resin, initial terpenes can be α-pinene, beta-pinene, limonene He limonene.And for the effect of the present invention that obtains to expect, the hydroxyl value of terpenes-phenol copolymer resin preferably is not higher than 170.Terpine resin and terpenes-phenol copolymer resin can use separately, or being used in combination with two or more.
In addition, rubber components in the rubber combination of the present invention is not particularly limited, but except above-mentioned butadienecopolymer, it can comprise polydiene such as natural rubber, polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-isoprene copolymer and chloroprene rubber etc.
In rubber combination of the present invention, rubber components preferably includes the butadienecopolymer that is not less than 70 quality %, and its vinyl bonds content that has in the divinyl part is not less than 10%.When the vinyl bonds content in the divinyl part is lower than 10%, the rigidity of the rubber combination under the high temperature range reduces, and obtain the effect of expectation, and when the content of butadienecopolymer in the rubber components is lower than 70 quality %, significantly reduce as the basic thermotolerance of rubber combination.
And the butadienecopolymer in the rubber combination of the present invention preferably includes styrene-butadiene copolymer.When butadienecopolymer comprised styrene-butadiene copolymer, the hysteresis loss of rubber combination was improved, and earth-catching property is improved.Styrene-butadiene copolymer can be synthetic by arbitrarily synthetic method such as letex polymerization and solution polymerization etc.As the butadienecopolymer except styrene-butadiene copolymer, mention acrylonitrile butadiene copolymer etc.
Styrene-butadiene copolymer preferably has styrene content 20-70 quality %.When styrene content is lower than 20 quality %, the tire earth-catching property under low temperature and high temperature that can not obtain to expect, and when styrene content surpasses 70 quality %, block rigidity (block rigidity) becomes too high, rubber is lower to the interlock on road surface, the tire earth-catching property that therefore can not obtain to expect.Because the tire earth-catching property significantly increases, the styrene content of styrene-butadiene copolymer is 20-45 quality % more preferably.
In rubber combination of the present invention, preferably take with respect to the amount compounding carbon black of per 100 mass parts rubber components as the 60-200 mass parts.When compounding to the amounts of carbon black of rubber combination is lower than 60 mass parts, insufficient to the improved action of tire DRY adherence properties, and when it surpassed 200 mass parts, the wearability of tire was deteriorated, and processibility is extremely deteriorated in addition.Compounding is to the amounts of carbon black of rubber combination 70-140 mass parts more preferably.Carbon black preferably has the about 80-280m of nitrogen adsorption specific surface area
2/ g.When the nitrogen adsorption specific surface area of carbon black is lower than 80m
2During/g, do not obtain sufficient Young's modulus, and wearability is deteriorated, and surpasses 280m when it
2During/g, can not expect the improvement of earth-grasping force and wearability, and mixed refining process is also deteriorated.As the example of carbon black, mention HAF, ISAF and SAF etc., but from taking into account simultaneously the viewpoint of wearability and earth-catching property, SAF is preferred.Carbon black can use separately, or with two or more be used in combination, can preferably use the carbon black that is obtained commercially.
Except above-mentioned rubber components, resin Composition and carbon black, rubber combination suitably compounding the rubber industry of being generally used for arranged additive such as processing wet goods, vulcanizing agent, vulcanization accelerator, antioxidant, tenderizer, zinc oxide and stearic acid etc., and do not damage purpose of the present invention.As additive, can preferably use the additive that is obtained commercially.
As the oil of processing wet goods is not particularly limited, and it can suitably be selected and use according to application target.As oil, mention aromatic oil, naphthenic oil, paraffin oil, ester oil, liquid conjugated diene rubber and hydrogenated liquid conjugated diene rubber etc.When this oil is included in the rubber combination, can control the flowability of rubber combination, reduce the front rubber combination viscosity of sulfuration to improve flowability, can advantageously carry out very good rubber combination thus and extrude.
Oil-contg in the rubber combination is preferably the 35-200 mass parts, more preferably 40-150 mass parts, and with respect to per 100 mass parts rubber components, this oil-contg comprises the oil that uses when with oil-extender filling rubber components.When oil-contg is lower than 35 mass parts with respect to per 100 mass parts rubber components, the mooney viscosity of unvulcanized rubber becomes too high, and processibility is deteriorated, the DRY adherence properties of this cover may be deteriorated, and when it surpasses 200 mass parts, it is low that mooney viscosity became, and processibility is deteriorated, and this tread crosses soft and therefore wearability may be deteriorated.
As vulcanizing agent, can use sulphur and following one of at least: organic thiosulfate compound (such as 1,6-hexa-methylene dithio sodium sulfate hydrate) and bismaleimide compound (such as the phenylene bismaleimides).
As vulcanization accelerator, mention that thiuram compound is such as four-2-ethylhexyl thiuram disulphide, four-2-sec.-propyl thiuram disulphide, four-dodecyl thiuram disulphide and four-benzyl thiuram disulphide etc.; Dithiocar-bamate compound such as zinc di 2 ethyl hexyldithiocarbamate, dodecyl zinc dithiocarbamate and ZBEC etc.; Benzothiazolyl vulcanization accelerator such as bisbenzothiazole based bisulfide, 4,4 '-dimethyl bisbenzothiazole based bisulfide, N-cyclohexyl-2-[4-morpholinodithio base-sulfinyl amine, the N-tertiary butyl-2-[4-morpholinodithio base-sulfinyl amine, the N-tertiary butyl-2-[4-morpholinodithio base-sulfenimide, N-oxo diethylidene-benzothiazolyl-sulfinyl amine and N, N '-dicyclohexyl-2-[4-morpholinodithio base-sulfinyl amine etc.
Can produce in the following manner according to rubber combination of the present invention: if other additives of the suitable selection of mixing of rubber component, resin and needs, and be heated, extrude and vulcanize.
Mixing condition is not particularly limited, and can suitably select under such as the various conditions such as type of the amount of each component in the mixing facilities of packing into, the rotating speed of rotor (revolution velocity), ram piston pressure (rampressure), melting temperature and mixing facilities.As mixing facilities, mention general mixing Banbury, Banbury mixer (intermix) and the kneader etc. of rubber combination that are used for.
Heating condition is not particularly limited, and can suitably select under various conditions such as Heating temperature, heat-up time and heating installation according to application target.As heating installation, mention roll squeezer (rolling machine) that is generally used for heating rubber combination etc.
Extrusion condition is not particularly limited, can according to various conditions as find time, rate of extrusion, extrusion equipment and extrusion temperature etc. suitably select.As extrusion equipment, mention being generally used for forcing machine of extruding rubber composition for tire etc.Can suitably determine extrusion temperature.
Equipment, system and the condition etc. that are used for sulfuration are not particularly limited, and can suitably select according to application target.As the equipment that is used for sulfuration, mention being generally used for vulcanized tyre with the molding sulfuration machine with mould of rubber combination etc.Curing temperature typically is about 190 ℃ of about 100-.
Rubber combination of the present invention is preferred for the tread rubber of tire, especially at drag racing car that annular distance is up to be used when sailing with the tread rubber of tire etc.In addition, known member can be used as the structural tire part except tread rubber.As the gas that will be filled with tire, except common air or have the air of oxygen partial pressure of adjusting, can use the rare gas elementes such as nitrogen, argon or helium.
As the example according to tire construction of the present invention, mention comprise pair of bead section, ring-type is extended between bead part carcass, the belt of hoop carcass crown part and the tire of tyre surface.In addition, can have meridian structure or oblique configuration according to tire of the present invention.
Be not particularly limited according to the tread structure in the tire of the present invention, and can be single layer structure or multilayered structure or so-called bizet-base portion (cap-base) structure that is consisted of by the upper strata bizet on direct contact road surface and the lower floor's base portion that arranges adjacent to bizet inside.In the present invention, preferably at least bizet made by above-mentioned rubber combination.
Although production method is not particularly limited, can followingly produce according to tire of the present invention.That is, at first prepare according to rubber combination of the present invention, then this rubber combination is affixed to the not sulfuration base portion that is applied in advance green tire tyre cover bizet.After this, tire can under sulfuration, in giving fixed mold, under given temperature and pressure, be produced by the structure green tire.
" embodiment "
The present invention further specifically describes with reference to following examples, but is not limited to these embodiment, can suitably carry out various improvement in the situation that does not depart from the present invention's spirit scope.
＜dynamic modulus E ' (MPa) 〉
The gained rubber combination 145 ℃ of lower sulfurations 45 minutes, is measured the constant stress of gained vulcanized rubber with the Tensile ﹠ Elongation Tester of JIS K6265, to determine until sample interior produces the time of be full of cracks as the time of heat-resistant anti-fatigue.It is that 100 index value represents that this data communication device is crossed example 1 based on the comparison.
＜DRY adherence properties 〉
The tire that will test is installed on the high performance vehicle that can travel with top speed 300km/h, and it is sailed in that annular distance is up, therebetween, according to following standard evaluation test driver to initially grabbing ground (initial earth-catching property) and the sensation of grabbing ground (riding stability) latter stage in the 12 circle in the first lap.Positive is larger, and the DRY adherence properties is better.
+ 3: have the low general officer who drives frequency and can know other degree of cog region
+ 2: have the high general officer who drives frequency and can know other degree of cog region
+ 1: the professional driver can other degree of cog region
0: contrast
-1: the professional driver can other degree of cog region
-2: have the high general officer who drives frequency and can know other degree of cog region
-3: have the low general officer who drives frequency and can know other degree of cog region
＜thermal fatigue resistance 〉
The tire that will test is installed in the racing car, and sails in that annular distance is up, then observes inside tires and outside after travelling, according to following standard evaluation.
0: do not produce the state that tire collapses flower (chunk)
-1: have the state that is lower than the 0.5mm be full of cracks in inside tires
-2: have the state that is not less than the 0.5mm be full of cracks in inside tires
-3: the state that externally has be full of cracks
＜hysteresis quality 〉
About the vulcanized rubber that obtains by each rubber combination of sulfuration, use Rheometric Co., Ltd. the viscoelasticity measurement machine of making is measured at the tan δ under 50 ℃ under 1% dynamic strain, is 100 exponential representation with its tan δ by rubber combination in the example 1 based on the comparison.This index value is larger, and tan δ is larger, and earth-catching property is better.
＜main line sliding property of face 〉
It is estimated at the main line face with Coast-down check instrument (Stanley London manufacturing), is 100 exponential representation by example 1 based on the comparison.This index value is larger, and this performance is better.
＜adherence properties 〉
The adherence properties of rubber combination is estimated by reproducing the main line face with main line face Coast-down check instrument.And the adherence properties of tire is by estimating with the tire that preparation has tire size 225/40R18 with this rubber combination in tyre surface.Four tires are installed on the passenger vehicle and in the test distance of dried bituminous pavement travel, to estimate adherence properties by test driver with following 7 stages:
7: very good, 6: good, 5: slightly good, 4: common, 3: slightly bad, 2: bad, 1: extremely bad ,-: do not estimate
(comparative example 1-5 and embodiment 1-13)
Prepare rubber combination by mixing component according to prescription shown in the table 1 in Banbury.(size: tyre surface 225/40R18) prepares the tire that will test by using this rubber combination to form passenger tyre.After this, about gained rubber combination and the tire that will test, estimate DRY adherence properties etc. by aforesaid method.The results are shown in the table 1.
*1:JSR Corporation make 0120 (styrene content: 35%, vinyl bonds content: the aromatic oil of 16%, 35% filling)
*2:Asahi Chemical Industry Co., and the TAFDEN4350 that Ltd. makes (styrene content: 39%, vinyl bonds content: the aromatic oil of 38%, 50% filling)
*3：SAF(N
2SA：150m
2/g)
*4:Fuji Kosan Co., the FUCOL AROMATICS#3 that Ltd. makes
*5:Seiko Chemical Co., the Microcrystalline Wax that Ltd. makes
*6:Ouchi Shinko Chemical Industrial Co., the N-(1,3-dimethylbutyl) that Ltd. makes-N '-phenyl-Ursol D
*7:Mitsui Chemicals, the FTR0120 that Inc. makes, softening temperature: 120 ℃, indenes content: 0 quality %,
*8:Mitsui Chemicals, the FTR0140 that Inc. makes, softening temperature: 140 ℃, indenes content: 0 quality %,
*9:Mitsui Chemicals, the F TR2140 that Inc. makes, softening temperature: 140 ℃, indenes content: 0 quality %,
*10:Nippon Petrochemicals Co., the NEOPOLYMER170S that Ltd. makes, alpha-methyl styrene-Vinyl toluene-indene copolymer resin, softening temperature: 160 ℃, indenes content: 70 quality %
*11:Rutgers Chemicals Co., the NOBARES C150 that Ltd. makes, coumarone-indene resin, softening temperature: 150 ℃, indenes content: 90 quality %
*12:Rutgers Chemicals Co., the NOBARESTN170 that Ltd. makes, C
9Resin, softening temperature: 170 ℃, indenes content: 70 quality %
*13:Toho Chemical Industry Co., the TOHOHIGHRESIN 150 that Ltd. makes comprises C
5Component contain indenes C
9Resin, softening temperature: 150 ℃, indenes content: 55 quality %, C
5Component concentration: 5 quality %
*14:Ouchi Shinko Chemical Industrial Co., the N-cyclohexyl that Ltd. makes-2-[4-morpholinodithio base sulfinyl amine
*Four-benzyl thiuram disulphide that 15:Flexsys makes
To the measuring result of 120 ℃ of lower E ' by being that 100 index represents based on the situation (comparative example 1) of only using the alpha-methyl styrene resin with 120 ℃ of softening temperatures with respect to the SBR with styrene content 35% and vinyl bonds content 16% of per 135 mass parts.In the formulation of comparative example 1, initial DRY adherence properties is very good, but riding stability is low.Otherwise, contain indenes C when what use had 170 ℃ of softening temperatures
9During resin (embodiment 1), the E ' under 120 ℃ is 150, and riding stability is significantly improved.
On the other hand, have in the situation of the alpha-methyl styrene resin of 140 ℃ of softening temperatures (comparative example 2) or 140 ℃ (comparative examples 3) in compounding only, E ' under the 120 ℃ (comparative example 4 that is improved, 5), and riding stability is improved, and has kept simultaneously initial earth-catching property (comparative example 4).As the C with 170 ℃ of softening temperatures
9The further compounding of resin is during to the formulation of comparative example 4, and riding stability is significantly improved and do not damaged initial DRY adherence properties (embodiment 3-5).Even have in compounding in the situation of the alpha-methyl styrene-Vinyl toluene of 160 ℃ of softening temperatures-indene copolymer resin (comparative example 4), also confirm similar effect.
Even such as embodiment 3-5, as the alpha-methyl styrene resin that will have 140 ℃ of softening temperatures and the C with 170 ℃ of softening temperatures
9Both compounding to 150 mass parts of resin have the SBR of styrene content 39% and vinyl bonds content 38% time, E ' under 120 ℃ also is improved, and (embodiment 6,7), and riding stability significantly improved and do not damaged initial DRY adherence properties (embodiment 6).And, when compounding to the amount of the carbon black of embodiment 7 and aromatic oil increases to respectively 100 mass parts and 30 mass parts (embodiment 8) and 120 mass parts and 50 mass parts (embodiment 9), E ' under 120 ℃ is improved, and (embodiment 8,9), and riding stability significantly improved and do not damaged initial DRY adherence properties (embodiment 9).E ' under 120 ℃ among the embodiment 8 is higher than the E ' under among the embodiment 10 120 ℃.
In that independent compounding is to the comparative example 5 of rubber combination with coumarone-indene resin, the E ' under 120 ℃ is significantly improved, but initial earth-catching property and riding stability are obviously deteriorated.On the other hand, 50 mass parts are being contained indenes C
9Resin (indenes content: 70 quality %, softening temperature: 170 ℃) compounding is to the embodiment 10 of rubber combination, and E ' and riding stability under 120 ℃ are improved, and 20 mass parts are being contained indenes C
9The resin compounding of resin and 30 mass parts aromatic vinyl compounds is to the embodiment 11 of rubber combination, and the E ' under 120 ℃, initial earth-catching property and riding stability are improved simultaneously.As rubber combination of the present invention, what preferably wherein will have 130 ℃-190 ℃ of softening temperatures and indenes content 30-80 quality % contains indenes C
9The resinoid compounding is to the rubber combination of rubber components.More preferably, compounding contains indenes C
9Resinoid amount is the 5-80 mass parts, with respect to per 100 mass parts rubber components.In addition, it more preferably comprises being selected to have softening temperature and be not less than 135 ℃ the homopolymer resin of aromatic vinyl compound and at least a resin of copolymer resin.
To comprise C
5Component contain indenes C
9Resin 50 mass parts compoundings are to the embodiment 12 of rubber combination, and E ' and riding stability under 120 ℃ are improved, and will comprise C
5Component contain indenes C
9The resin 30 mass parts compoundings of resin 20 mass parts and aromatic vinyl compound are to the embodiment 11 of rubber combination, and the E ' under 120 ℃, initial earth-catching property and riding stability are improved simultaneously.Therefore, as rubber combination of the present invention, preferred compounding have have 130 ℃-190 ℃ of softening temperatures and an indenes content 30-80 quality % contain indenes C
9The resinoid compounding is to the rubber combination of rubber components.More preferably, compounding contains indenes C
9The resinoid amount is the 5-80 mass parts, with respect to per 100 mass parts rubber components, and C
5The content of component is 0.5-20 quality %.In addition, it more preferably comprises being selected to have softening temperature and be not less than 135 ℃ the homopolymer resin of aromatic vinyl compound and at least a resin of copolymer resin.
(comparative example 6-8 and embodiment 14-20)
In Banbury, by mixing component according to the A of prescription shown in the table 2 (unit: mass parts) preparation rubber combination.And (size: tyre surface 225/40R18) prepares the tire that will test by using this type of rubber combination to form passenger tyre.After this, about gained rubber combination and the tire that will test, estimate DRY adherence properties etc. by aforesaid method.The results are shown in table 2.
*Identical in 1-15 and the table 1
*16:Arakawa Chemical Industries, the ARUKONM90 that Ltd. makes, partially hydrogenated petroleum resin, softening temperature: 90 ℃
*17:Idemitsu Kosan Co., the I-MARV P140 that Ltd. makes, hydrogenated petroleum resin, softening temperature: 140 ℃
*18:Arakawa Chemical Industries, the ARUKONM135 that Ltd. makes, hydrogenated petroleum resin, softening temperature: 135 ℃
Have in the comparative example 6 of the resin H with 90 ℃ of softening temperatures in compounding only, initial earth-catching property is very good, but riding stability is low.Otherwise, have resin D to contain indenes C as what have 170 ℃ of softening temperatures in compounding
9(indenes content: among the embodiment 14 70 quality %), the E ' under 120 ℃ is 150 to resin, and riding stability is obviously improved.
About these results, compounding has the comparative example 7 of the resin I with 140 ℃ of softening temperatures to improve riding stability, has kept simultaneously initial earth-catching property.In addition, when using together resin D as containing indenes C
9During resin, riding stability is significantly improved and is not damaged initial earth-catching property (embodiment 16-18).
And, therein with 30 mass parts resin F as containing indenes C
9Resin (indenes content: 70 quality %, softening temperature: 170 ℃) and 30 mass parts hydrogenated petroleum resins (softening temperature: 140 ℃) compounding to the tire of the embodiment 19 of rubber combination, and wherein with 30 mass parts resin G as containing C
5Component contain indenes C
9Resin and 30 mass parts hydrogenated petroleum resins (softening temperature: 140 ℃) compounding is to the tire of the embodiment 20 of rubber combination, and the E ' under 120 ℃, initial earth-catching property and riding stability are improved simultaneously.Therefore, contain indenes C except what have 130 ℃-190 ℃ of softening temperatures and an indenes content 30-80 quality %
9Beyond the resinoid, tire of the present invention preferably includes to be selected to have softening temperature and is not less than 135 ℃ the homopolymer resin of aromatic vinyl compound and at least a resin of copolymer resin.
(comparative example 9-11 and embodiment 21-30)
In Banbury, by mixing component (unit: mass parts) prepare rubber combination according to prescription shown in the table 3.And (size: tyre surface 225/40R18) prepares the tire that will test by using this type of rubber combination to form passenger tyre.After this, about gained rubber combination and the tire that will test, estimate DRY adherence properties etc. by aforesaid method.The results are shown in the table 3.
*1-
*14 with table 1 in identical
*19:Yasuhara Chemical Co., the CLEARON P125 that Ltd. makes, hydrogenated terpene resin, softening temperature: 125 ℃
*20:Yasuhara Chemical Co., the CLEARON P150 that Ltd. makes, hydrogenated terpene resin, softening temperature: 150 ℃
*21:Rutgers Chemicals Co., the NOBARES C160 that Ltd. makes, coumarone-indene resin, softening temperature: 160 ℃,
*22: vulkacit D, Sumitomo Chemical Co., Ltd. makes
*23: two (4-methyl-benzyl thiazolyl-2) disulphide, Sanshin ChemicalIndustry Co., Ltd. makes
To the comparative example 9 of rubber combination, initial earth-catching property is very good in the hydrogenated terpene resin compounding that only will have 125 ℃ of softening temperatures, but riding stability is low, and this is because the ground of grabbing during travelling significantly reduces.Even to the comparative example 10 of rubber combination, also obtain similar effect in the hydrogenated terpene resin compounding that will have 150 ℃ of softening temperatures.Therefore think that this is due to the fact that resin by the consistency of hydrogenation enhancing and polymkeric substance, and compounding there is the Young's modulus step-down of the rubber combination of hydrogenated resin.Contain indenes C what will have 160 ℃ of softening temperatures
9Resin compounding is to the embodiment 21 of rubber combination, and the E ' under 120 ℃ is 160, and riding stability is obviously improved.
On the other hand, the hydrogenated terpene resin that will have therein 150 ℃ of softening temperatures merges compounding to the embodiment 23-30 of rubber combination with the alpha-methyl styrene-Vinyl toluene with 160 ℃ of softening temperatures-indene copolymer resin groups, E ' under 120 ℃ is improved, and riding stability is improved, and has kept simultaneously initial earth-catching property.
(comparative example 12-17 and embodiment 31-37)
In Banbury, by mixing component (unit: mass parts) prepare rubber combination according to prescription shown in the table 4.And (size: tyre surface 225/40R18) prepares the tire that will test by using this type of rubber combination to form passenger tyre.About gained rubber combination and the tire that will test, by aforesaid method estimate DRY adherence properties etc. thereafter.The results are shown in table 4.
*4-
*23 is identical among the 1-3 with table
*1712 (the styrene contents: the aromatic oil of 23.5%, 37.5% filling) that 24:JSR Corporation makes
*25:Tokai Carbon Co., the SEAST 9H (nitrogen adsorption specific surface area (N that Ltd. makes
2SA)=142m
2/ g, the dibutyl phthalate adsorption amount=130ml/100g)
*26:Yasuhara Chemical Co., the YS POLYSTART115 that Ltd. makes, terpenes-phenol copolymer resin, softening temperature: 115 ℃
*27:Yasuhara Chemical Co., the YS POLYSTART160 that Ltd. makes, terpenes-phenol copolymer resin, softening temperature: 160 ℃, hydroxyl value: 70
*28:Nippon Petrochemicals Co., the NEOPOLYMERL90 that Ltd. makes contains indenes C
9Resin (indenes content: 38 quality %), softening temperature: 90 ℃
With terpenes-phenol copolymer resin compounding during to rubber combination, when tyre temperature raise, the E ' under 100 ℃ was low when only, and tyre performance (thermal fatigue resistance and riding stability) be not improved (comparative example 13,14).Along with compounding this resinoid amount to rubber combination increases, Young's modulus under the high temperature (E ' under 100 ℃) raises, and the Young's modulus under the low temperature (E ' under 30 ℃) rising, so the initial earth-catching property of tire reduces (comparative example 15).
As the C that will have low softening point
9The independent compounding of resin is during to rubber combination (comparative example 16), and is similar with terpenes-phenol copolymer resin, and the E ' under 100 ℃ is not improved.And, when with terpenes-phenol copolymer resin (softening temperature: 160 °, 70) and contain indenes C hydroxyl value:
9Resin (indenes content: 38 quality %, softening temperature: 90 ℃) compounding is during to rubber combination (comparative example 17), and initial earth-catching property is improved, but riding stability and thermal fatigue resistance are deteriorated.On the other hand, in compounding the indenes of containing C is arranged
9Among the embodiment 37 of resin and terpenes-phenol copolymer resin, initial earth-catching property is good.Therefore, rubber combination of the present invention preferably also comprises being selected from by what part or all of hydriding terpene-phenol copolymer resin formed to have an at least a resin that softening temperature is not less than 130 ℃ hydriding terpene-phenol copolymer resin.
Contain indenes C when what will have a high softening-point
9Resin and have the terpenes of high softening-point-when the phenol copolymer resin is combined compounding to rubber combination, confirmed to improve the DRY adherence properties, E ' and thermal fatigue resistance (embodiment 33-36) under having kept simultaneously 100 ℃.Yet, when compounding during to the amount large (embodiment 36) of the terpenes with high softening-point of rubber combination-phenol copolymer resin, riding stability becomes and is lower than other embodiment those (embodiment 34 and 35), and contains indenes C to rubber combination when compounding
9During the amount of resin large (embodiment 34), initial earth-catching property becomes and is lower than other embodiment those (embodiment 35,36).
(embodiment 38-59)
In Banbury, by the mixing next rubber combination for the preparation of tire tread of component (mass parts) according to filling a prescription shown in the table 5-7.The gained rubber combination was vulcanized 15 minutes under 160 ℃ condition, then estimate earth-catching property.In addition, carry out evaluation to the tire earth-catching property by preceding method.Evaluation result also is shown in table 5-7.
*2-
*10 with table 1 in identical
*29: carbon black is (by the outer surface area of CTAB absorption method: 148m
2/ g, 24M4DBP adsorptive capacity: 102mL/100g)
*30:KORESIN (BASF manufacturing)
*31:DUREZ 32333 (Durez makes, p-tert-butylphenol-formaldehyde resin, softening temperature: 130 ℃)
*32: terpenes-phenol copolymer resin, YS POLYSTAR S145 (YasuharaChemical Co., Ltd. makes, softening temperature: 145 ℃, hydroxyl value: 120)
*33: terpenes-phenol copolymer resin, YS POLYSTAR T145 (YasuharaChemical Co., Ltd. makes, softening temperature: 145 ℃, hydroxyl value: 70)
*34: terpenes-phenol copolymer resin, YS POLYSTAR S100 (YasuharaChemical Co., Ltd. makes, softening temperature: 100 ℃, hydroxyl value: 70)
*35: terpenes-phenol copolymer resin, MAITYACE K125 (YasuharaChemical Co., Ltd. makes, softening temperature: 125 ℃, hydroxyl value: 210)
*36: terpine resin, CLEARON P150 (Yasuhara Chemical Co., Ltd. makes, softening temperature: 150 ℃, hydroxyl value: 0)
*The 37:N-tertiary butyl-2-[4-morpholinodithio base-sulfinyl amine
*38: four-2-ethylhexyl thiuram disulphide
Wherein will comprise and contain indenes C
9Resinoid, at least a resin (A) that is selected from alkyl-resol and at least a rubber combination that is selected from the resin (B) of terpenes homopolymer resin and terpenes-phenol copolymer resin are used for the tire (embodiment 46-59) of tyre surface, and comprising containing indenes C
9Resinoid and at least a resin (A) or at least a rubber combination that is selected from the resin (B) of terpenes homopolymer resin and terpenes-phenol copolymer resin that is selected from alkyl-resol are compared for the tire (embodiment 38-45) of tyre surface, tan δ value under 50 ℃ is high, and main line sliding property of face is good.Therefore, except containing indenes C
9Beyond the resinoid, rubber combination of the present invention preferably also comprises at least a resin (A) and at least a resin (B) that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin that is selected from alkyl-resol.
Claims (21)
1. rubber combination, it contains indenes C by what will have 130 ℃-190 ℃ of softening temperatures and an indenes content 30-80 quality %
9The resinoid compounding forms to rubber components, its also comprise be selected from terpenes homopolymer resin, terpenes-phenol copolymer resin, have softening temperature be not less than 135 ℃ aromatic vinyl compound homopolymer resin and have at least a resin of copolymer resin that softening temperature is not less than 135 ℃ aromatic vinyl compound.
2. rubber combination, it contains indenes C by what will have 130 ℃-190 ℃ of softening temperatures and an indenes content 30-80 quality %
9The resinoid compounding forms to rubber components, wherein also comprises at least a resin (A) and at least a resin (B) that is selected from terpenes homopolymer resin and terpenes-phenol copolymer resin that is selected from alkyl phenolic resin.
3. rubber combination according to claim 1 and 2, wherein terpenes homopolymer resin and terpenes-phenol copolymer resin has and is not less than 130 ℃ softening temperature.
4. rubber combination according to claim 1 and 2, the wherein said indenes C that contains
9Resinoid compounding amount is the 5-80 mass parts, with respect to per 100 mass parts rubber components.
5. rubber combination according to claim 1 and 2, the wherein said indenes C that contains
9Resinoid contains C
5Component.
6. rubber combination according to claim 5, the wherein said indenes C that contains
9C in the resinoid
5The content of component is 0.5-20 quality %.
7. rubber combination according to claim 1 and 2, the wherein said indenes C that contains
9Resinoid softening temperature is 140-180 ℃.
8. rubber combination according to claim 7, the wherein said indenes C that contains
9Resinoid is to have alpha-methyl styrene-Vinyl toluene-indene copolymer resin of softening temperature 155-180 ℃.
9. rubber combination according to claim 1 and 2, it also comprises being selected from by part or all of hydrogenation and comprises C
5Component and/or C
9The petroleum resin of component form has at least a resin that softening temperature is not less than 120 ℃ hydrogenated petroleum resin.
10. rubber combination according to claim 1 and 2, it also comprises being selected from by what part or all of hydrogenated terpene resin formed to have an at least a resin that softening temperature is not less than 130 ℃ hydrogenated terpene resin.
11. rubber combination according to claim 10, the softening temperature of wherein said hydrogenated terpene resin are not less than 140 ℃.
12. rubber combination according to claim 2, wherein with described resin (A) and resin (B) with mass ratio 10: 1-1: 10 compoundings.
13. rubber combination according to claim 2, the compounding total amount of wherein said resin (A) and described resin (B) is the 3-100 mass parts, with respect to the described rubber components of per 100 mass parts.
14. rubber combination according to claim 2, the main structure at the phenol position in the wherein said resin (A) is the p-tert-butylphenol structure.
15. rubber combination according to claim 2, wherein said resin (B) comprises terpenes-phenol copolymer resin at least, and the hydroxyl value of described terpenes-phenol copolymer resin is not less than 170.
16. rubber combination according to claim 2, wherein said resin (A) have softening temperature and are not less than 120 ℃.
17. rubber combination according to claim 2, wherein said rubber components comprise the butadiene type multipolymer that is not less than 70 quality %, the vinyl bonds content of described butadiene type multipolymer in the divinyl part is not less than 10%.
18. rubber combination according to claim 17, wherein said butadiene type multipolymer comprises styrene-butadiene copolymer.
19. rubber combination according to claim 18, wherein said styrene-butadiene copolymer have styrene content 20-70 quality %.
20. rubber combination according to claim 1, it is also take with respect to the amount compounding carbon black of per 100 mass parts rubber components as the 60-200 mass parts.
21. a pneumatic tyre is characterized in that right to use requires each described rubber combination of 1-20 in tread rubber.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP003502/2007 | 2007-01-11 | ||
| JP2007003502A JP5265115B2 (en) | 2007-01-11 | 2007-01-11 | Rubber composition and pneumatic tire using the same |
| JP003415/2007 | 2007-01-11 | ||
| JP003451/2007 | 2007-01-11 | ||
| JP2007003415A JP5265114B2 (en) | 2007-01-11 | 2007-01-11 | Rubber composition and pneumatic tire using the same |
| JP2007003451A JP5497254B2 (en) | 2007-01-11 | 2007-01-11 | Rubber composition and pneumatic tire using the same |
| JP010637/2007 | 2007-01-19 | ||
| JP2007010637A JP5265118B2 (en) | 2007-01-19 | 2007-01-19 | Rubber composition and pneumatic tire using the same |
| JP047712/2007 | 2007-02-27 | ||
| JP2007047712A JP5334234B2 (en) | 2007-02-27 | 2007-02-27 | Rubber composition and pneumatic tire using the same |
| PCT/JP2008/050299 WO2008084860A1 (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
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| CN101589100B true CN101589100B (en) | 2013-03-20 |
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| CN200880002192.2A Expired - Fee Related CN101589100B (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
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| JP5503159B2 (en) * | 2008-02-15 | 2014-05-28 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| JP5351244B2 (en) * | 2011-04-22 | 2013-11-27 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| JP5913188B2 (en) * | 2013-04-30 | 2016-04-27 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| KR101716764B1 (en) | 2013-12-06 | 2017-03-15 | 요코하마 고무 가부시키가이샤 | Tire rubber composition |
| JP5868443B2 (en) * | 2014-02-24 | 2016-02-24 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| CN104045767B (en) * | 2014-05-22 | 2016-06-01 | 宁波职业技术学院 | The preparation method of a kind of indenes modification �� pinene resin |
| CN106414585A (en) * | 2014-05-29 | 2017-02-15 | 株式会社普利司通 | Rubber tire-tread composition and passenger-vehicle pneumatic tire using same |
| EP3150661B1 (en) * | 2014-05-29 | 2018-07-04 | Bridgestone Corporation | Rubber tire-tread composition and passenger-vehicle pneumatic tire using same |
| US20170037225A1 (en) * | 2015-08-05 | 2017-02-09 | The Goodyear Tire & Rubber Company | Pneumatic tire |
| JP6627466B2 (en) * | 2015-12-04 | 2020-01-08 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| JP6733223B2 (en) * | 2016-03-07 | 2020-07-29 | 住友ゴム工業株式会社 | High performance tires |
| JP2019533738A (en) * | 2016-10-14 | 2019-11-21 | クレイトン・ケミカル・エル・エル・シー | Rubber composition containing improved tread enhancing additive and use thereof |
| JP6870978B2 (en) * | 2016-12-15 | 2021-05-12 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tires and pneumatic tires using it |
| KR102063713B1 (en) * | 2018-05-21 | 2020-01-08 | 한국타이어앤테크놀로지 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
| US11434352B2 (en) | 2019-04-25 | 2022-09-06 | Toyo Tire Corporation | Rubber composition and pneumatic tire |
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| JPH0912784A (en) * | 1995-06-29 | 1997-01-14 | Toyo Tire & Rubber Co Ltd | Rubber composition |
| JP3714750B2 (en) * | 1997-01-10 | 2005-11-09 | 横浜ゴム株式会社 | Tire tread rubber composition for competition |
| JPH10195242A (en) * | 1997-01-14 | 1998-07-28 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| US6221953B1 (en) * | 1999-08-10 | 2001-04-24 | The Goodyear Tire & Rubber Company | Tire with tread which contains spatially-defined resins |
| JP4036578B2 (en) * | 1999-08-11 | 2008-01-23 | 横浜ゴム株式会社 | Pneumatic bias racing tire |
| US6265478B1 (en) * | 1999-08-18 | 2001-07-24 | The Goodyear Tire & Rubber Company | Polymeric resinous material derived from limonene dicyclopentadiene indene and alpha-methyl styrene |
| EP1514901B1 (en) * | 2002-06-19 | 2011-06-01 | Bridgestone Corporation | Rubber composition for tire and tire made therefrom |
| JP4955191B2 (en) * | 2002-08-21 | 2012-06-20 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
| JP2005350535A (en) * | 2004-06-09 | 2005-12-22 | Sumitomo Rubber Ind Ltd | Rubber composition for tire |
| JP4602716B2 (en) * | 2004-08-24 | 2010-12-22 | 住友ゴム工業株式会社 | Rubber composition for tread |
| JP2006249230A (en) * | 2005-03-10 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and pneumatic tire using the same |
| JP2007321046A (en) * | 2006-05-31 | 2007-12-13 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire |
| JP2008163129A (en) * | 2006-12-27 | 2008-07-17 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
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- 2008-01-11 CN CN200880002192.2A patent/CN101589100B/en not_active Expired - Fee Related
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| JP5265114B2 (en) | 2013-08-14 |
| JP2008169295A (en) | 2008-07-24 |
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