CN104487506A - Rubber composition for tread, and pneumatic tire - Google Patents

Rubber composition for tread, and pneumatic tire Download PDF

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Publication number
CN104487506A
CN104487506A CN201380038132.7A CN201380038132A CN104487506A CN 104487506 A CN104487506 A CN 104487506A CN 201380038132 A CN201380038132 A CN 201380038132A CN 104487506 A CN104487506 A CN 104487506A
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rubber
quality
resin
unbranched
silicon
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CN104487506B (en
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宫崎达也
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Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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    • C08L15/00—Compositions of rubber derivatives
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
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    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
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  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided are: a rubber composition for a tread, which has excellent abrasion resistance and good wet grip performance and can have good fuel efficiency and good elongation at break; and a pneumatic tire (particularly a tire for a passenger car or a tire for a versatile sports car) which is produced using the rubber composition. The present invention relates to a rubber composition for a tread, in which the content of a modified butadiene rubber for silica which has a cis content of 50 mass% or less is 8 to 40 mass% and the content of a styrene-butadiene rubber is 25 to 75 mass% both relative to 100 mass% of rubber components, and silica having a nitrogen adsorption specific surface area of 160 to 270 m2/g is contained in an amount of 40 to 120 parts by mass relative to 100 parts by mass of the rubber components.

Description

Rubber composition for tire tread and pneumatic tyre
Technical field
The pneumatic tyre that the present invention relates to a kind of rubber composition for tire tread and formed by this rubber combination.
Background technology
The contact force of the tire unit surface of passenger car and SUV (Sport Utility Vehicle) is low, and the tread portion contacted with road surface needs to possess good wear resistance simultaneously, wet earth-catching property and fuel economy, especially good wear resistance.
As the example improving wearing-resistance method, introduce and use the technique means of silicon-dioxide (fine particle silica) that N2 adsorption specific surface area is large or the large carbon black (micro mist carbon black) of N2 adsorption specific surface area to improve wet earth-catching property, fuel economy and wear resistance.(see, such as, patent documentation 1).
Unfortunately, fine particle silica and micro mist carbon black have stronger being polymerized and are inclined to, and are therefore difficult to disperse equably.About this point, the manufacturerss of the silicon-dioxide surfactivity and size distribution of attempting by adjusting silicon-dioxide improves its dispersiveness in rubber combination.Such as, but containing in the preparation process of polymer-modified rubber combination, these polymer-modified starting stages mediating can suppress the dispersion of silicon-dioxide with silica bound.Therefore, fine particle silica or micro mist carbon black are difficult to disperse equably, and the use of fine particle silica or carbon black is more prone to reduce elongation at break.
The method of the improvement wear resistance that another kind is known is the linking agent using sulfur-bearing, such as, 1, two (the N of 6-, N '-phenylbenzene thiocarbamoyl dithio) hexane, two (3-triethoxysilylpropyl) tetrasulfide or poly-3,6-dioxaoctane tetrasulfides, and the use reducing ring-type sulphur (S8).Regrettably, these containing sulfur crosslinking agent expensive and also can only improve about 10% wear resistance.Other method known is the masterbatch of the polymkeric substance of preparation containing silicon-dioxide (or carbon black) and partial amount, and interpolation can improve the dispersiveness of silicon-dioxide with the interactional modified group of silicon-dioxide on the end of the chain or main chain of styrene-butadiene rubber(SBR).But similarly, these methods all can only improve the wear resistance of about 10%, therefore need to improve wear resistance further.
The technology of the another kind of improvement wear resistance known is also had to be in every 100 quality % rubber components, add about 10-35 quality % use the cis-rich polybutadiene rubber of Nd catalyzer synthesis thus the characteristic utilizing polybutadiene rubber self.Unfortunately, this technique means can reduce the wet earth-catching property of passenger vehicle tyre and SUV (Sport Utility Vehicle) tire tread (in these tires, the electric shock pressure on per unit area and road surface is low) significantly.Based on this reason, in every 100 quality % rubber components, the content of polybutadiene rubber is strictly restricted to about 35 quality %.
As mentioned above, we need to provide a kind of rubber composition for tire tread, and it can provide good fuel economy and good elongation at break while possessing good wear resistance and wet earth-catching property.
Reference listing
Patent documentation
Patent documentation 1:JP 2011-132307A
Summary of the invention
Technical problem
Target of the present invention is to solve the problem, namely rubber composition for tire tread is provided, it can provide good fuel economy and elongation at break while possessing outstanding wear resistance and wet earth-catching property, provides a kind of pneumatic tyre (especially for passenger car and SUV (Sport Utility Vehicle)) obtained by this rubber combination simultaneously.
The technical scheme of dealing with problems
The present invention relates to a kind of rubber composition for tire tread, with 100 quality % rubber components for benchmark, it comprises, and the cis-content of 8-40 quality % is the modified polybutadiene rubber for silicon-dioxide of below 50 quality % and the styrene-butadiene rubber(SBR) of 25-55 quality %; And relative to the rubber components of 100 mass parts, it comprises further, and 40-120 mass parts N2 adsorption specific surface area is 160-270m 2the silicon-dioxide of/g.
Modified polybutadiene rubber for silicon-dioxide is preferably selected from least one in the group be made up of following compound: by polybutadiene rubber compound modified following formula (1) Suo Shi, by the polybutadiene rubber of low-molecular weight compound modification comprising Racemic glycidol amino in molecule, and the polybutadiene rubber of the mixture modification to be made up of dipolymer or the high-order oligopolymer of the low-molecular weight compound and this low-molecular weight compound that comprise Racemic glycidol amino in molecule
Wherein R 1, R 2and R 3be same to each other or different to each other, represent alkyl separately, alkoxyl group, siloxy-, acetal radical, carboxyl, the derivative of sulfydryl or above-mentioned group; R 4and R 5be same to each other or different to each other, represent hydrogen atom or alkyl separately, R 4and R 5can be bonded to each other and form ring structure together with nitrogen-atoms, and n is integer.
The compound that the low-molecular weight compound comprising Racemic glycidol amino in molecule is preferably shown below:
Wherein, R 11and R 12be same to each other or different to each other, eachly represent C1-10 alkyl, this alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 13and R 14be same to each other or different to each other, eachly represent hydrogen atom or C1-20 alkyl, this alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 15represent C1-20 alkyl, this alkyl comprises alternatively and is selected from by ether, tertiary amine groups, epoxy group(ing), at least one in the group that carbonyl and halogen group are formed, and m is the integer of 1-6.
Styrene-butadiene rubber(SBR) preferably includes the modified styrene butadiene rubber for silicon-dioxide.
In addition, relative to the silicon-dioxide of 100 mass parts, this rubber composition for tire tread preferably comprises at least one silane coupling agent be selected from the group be made up of following compound of 1-15 mass parts: following compound shown in formula I:
Wherein, R 101to R 103separately for having side chain or unbranched C1-12 alkyl, there are side chain or unbranched C1-12 alkoxyl group, or-O-(R 111-O) z-R 112, wherein z R 111respective representative has side chain or unbranched C1-30 bivalent hydrocarbon radical and z R 111be same to each other or different to each other, R 112representative has side chain or unbranched C1-30 alkyl, have side chain or unbranched C2-30 alkenyl, C6-30 aromatic base or C7-30 aralkyl, and z represents the integer of 1-30, R 101to R 103mutually the same or different; And R 104representative has side chain or unbranched C1-6 alkylene;
Comprise such as formula the connector element A shown in (II) and the compound such as formula the connector element B shown in (III):
Wherein, R 201represent hydrogen, halogen, have side chain or unbranched C1-30 alkyl, have side chain or unbranched C2-30 alkenyl, have the alkyl that side chain or unbranched C2-30 alkynyl or its end hydrogen are substituted by hydroxyl or carboxyl; R 202representative has side chain or unbranched C1-30 alkylene, has side chain or unbranched C2-30 alkylene group or has side chain or unbranched C2-30 alkynylene, R 201and R 202ring structure can be formed together; And
The compound be shown below:
In addition, with 100 quality % rubber components for benchmark, the amount preferably using the polybutadiene rubber of rare earth catalyst synthesis is below 40 quality %.
This rubber composition for tire tread preferably comprises the liquid resin that softening temperature is-20 ~ 45 DEG C, and this liquid resin is at least one in liquid coumarone-indene resin and liquid terpene resin.
This rubber composition for tire tread preferably comprises that to be selected from by softening temperature be the terpine resin of 46 ~ 160 DEG C, softening temperature is the Gum Rosin of 46 ~ 140 DEG C, at least one resin in the C5 petroleum resin that softening temperature is 46 ~ 140 DEG C and the group that the anine that softening temperature is 46 ~ 140 DEG C is formed.
The present invention relates to the pneumatic tyre obtained by above-mentioned rubber combination.
This pneumatic tyre is preferably used for passenger car or SUV (Sport Utility Vehicle) SUV.
Beneficial effect of the present invention
The invention provides rubber composition for tire tread, with 100 quality % rubber components for benchmark, it comprises, the modified polybutadiene rubber for silicon-dioxide of 8-40 quality %, and its cis-content is below 50 quality %, and the styrene-butadiene rubber(SBR) of 25-75 quality %; Relative to 100 mass parts rubber components, its N2 adsorption specific surface area comprising 40-120 mass parts is further 160-270m 2the silicon-dioxide of/g.Therefore, due to dispersed in polybutadiene rubber region and styrene-butadiene rubber(SBR) region of silicon-dioxide in this kind of rubber combination, when this rubber combination is used for tire tread, pneumatic tyre can be made to possess outstanding wear resistance and good wet earth-catching property, good fuel economy and good elongation at break (weather resistance) are provided simultaneously.
Embodiment
Rubber composition for tire tread according to the present invention comprises the modified polybutadiene rubber for silicon-dioxide (BR) of specified quantitative, its cis-content is below 50 quality %, namely for modification low cis BR, the styrene-butadiene rubber(SBR) (SBR) of silicon-dioxide, and N2 adsorption specific surface area is 160-270m 2the silicon-dioxide (fine particle silica) of/g.Therefore, this rubber combination, it can provide good fuel economy and elongation at break while possessing good wear resistance and wet earth-catching property.
Fine particle silica has stronger polymerization tendency and is usually difficult to disperse equably.The modification low cis BR for silicon-dioxide of specified quantitative and the use of SBR in this rubber combination (being preferred for silica modified), fine particle silica is allowed to disperse equably, allow to provide good wear resistance simultaneously, wet earth-catching property, fuel economy and elongation at break.Therefore, the balance between these characteristics can be increased significantly.
Rubber components in rubber combination of the present invention comprises the modification low cis BR for silicon-dioxide.This use allows fine particle silica high dispersing, improves fuel economy and wet earth-catching property thus especially, causes the balance on improved performance.In addition, this modification low cis BR being used for silicon-dioxide comprises the vinyl of reactive behavior in molecule, thus is even also easy to when using the silane coupling agent such as Si266 of low reactivity form coupling, therefore, it is possible to effectively realize effect of the present invention.
This is used for the not special restriction of the modification low cis BR (for silicon-dioxide by can the compound modified modification BR that have compared with low cis content interactional with silicon-dioxide) of silicon-dioxide, as long as it involvedly can have BR (preferred function group comprise be selected from by nitrogen, at least one atom in the group that oxygen and silicon are formed) compared with low cis content with the interactional functional group of silicon-dioxide compound modified.Its example comprises the low cis BR of chain end modification, and it obtains by carrying out modification with the compound containing functional group (properties-correcting agent) at least one chain end in BR; The low cis BR of backbone modification, its main chain has this functional group; And the low cis BR of main chain and chain end modification, all there is functional group (such as, its main chain have functional group and have at least one main chain of chain end with modifier modification and the low cis BR of chain end modification) on its main chain and on its chain end.Wherein, the low cis BR of chain end modification is preferred.
The example of this functional group comprises: amino, acid amides, alkoxysilyl, isocyanic ester, imino-; imidazoles, urea, ether, carbonyl, containing oxygen carbonyl; sulfide, disulphide, alkylsulfonyl, sulfinyl; thiocarbonyl, ammonium, imide, hydrazo; azo, diazo, carboxyl, itrile group; pyridyl, alkoxyl group, hydroxyl, containing oxygen base and epoxy group(ing).These functional groups can be replaced.Especially, this functional group is preferably primary amino, secondary amino group or tertiary amino (especially Racemic glycidol is amino), epoxy group(ing), hydroxyl and alkoxyl group (preferably there is the alkoxyl group of 1-6 carbon atom), or alkoxysilyl (preferably having the alkoxysilyl of 1-6 carbon atom), because it is efficient in lifting fuel economy and wet earth-catching property.
The low cis BR of chain end modification is preferably the modified polybutadiene rubber (low cis BR of S-modification) had compared with low cis content carrying out modification with the compound shown in following formula (1).
In formula (1), R 1, R 2and R 3be same to each other or different to each other, represent alkyl separately, alkoxyl group, siloxy-, acetal radical, carboxyl (-COOH), the derivative of sulfydryl (-SH) or above-mentioned group; R 4and R 5be same to each other or different to each other, represent hydrogen atom or alkyl separately, R 4and R 5can be combined with each other and form ring structure together with nitrogen-atoms; And n is integer.
The example of S-modification BR comprises those that describe in JP 2010-111753A and other patent documentation.
In formula (1), R 1, R 2and R 3be alkoxyl group (preferably there is the alkoxyl group of 1-8 carbon atom, more preferably 1-4 carbon atom) suitably separately, this is because it can obtain outstanding fuel economy and resistance to fracture.R 4and R 5be alkyl (preferably there is the alkyl of 1-3 carbon atom) separately suitably.Symbol n is preferably the integer of 1-5, is more preferably the integer of 2-4, is also more preferably 3.In addition, at R 4and R 5be combined with each other and form in the situation of ring structure together with nitrogen-atoms, this ring structure is preferably 4-8 ring.It should be noted that alkoxyl group comprises cycloalkyloxy (such as: cyclohexyloxy) and fragrant oxygen base (such as: phenoxy group and benzyloxy).When this preferred compound is used, effect of the present invention can be implemented well.
The object lesson of the compound representated by formula (1) comprises 2-dimethyl aminoethyl Trimethoxy silane, 3-dimethylaminopropyl Trimethoxy silane, 2-dimethyl aminoethyl triethoxyl silane, 3-dimethylaminopropyl triethoxyl silane, 2-diethyllaminoethyl Trimethoxy silane, 3-diethylin propyl trimethoxy silicane, 2-diethyllaminoethyl triethoxyl silane, and 3-diethylin propyl-triethoxysilicane, in these, preferred 3-dimethylaminopropyl Trimethoxy silane, 3-dimethylaminopropyl triethoxyl silane, and 3-diethylin propyl trimethoxy silicane, this is because they allow above-mentioned performance to be improved better.Above-claimed cpd may be used singly or two or more in combination.
Polybutadiene rubber can carry out modification with the compound shown in formula (1) by known method, such as JP H06-53768B, JP H06-57767 B and those methods described in other patent documentation.Such as, polybutadiene rubber can carry out modification by contacting with this compound.Specifically, a kind of noticeable method is, after obtaining polybutadiene rubber by anionoid polymerization, the compound of predetermined content is added in rubber solutions to make the polymerizable end (reactive terminal) of compound and polybutadiene rubber react.
The low cis BR of chain end modification is also preferably by the modified polybutadiene rubber with low cis content of the low-molecular weight compound modification comprising Racemic glycidol amino in molecule.Such as, the low cis BR of chain end modification may suitably be by the modified polybutadiene rubber with low cis content of the low-molecular weight compound modification shown in following formula:
Wherein, R 11and R 12mutually the same or different, eachly represent a C1-10 alkyl, this alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 13and R 14mutually the same or different, eachly represent hydrogen atom or C1-20 alkyl, this alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 15represent C1-20 alkyl, this alkyl comprises alternatively and is selected from by ether, tertiary amine groups, epoxy group(ing), at least one in the group that carbonyl and halogen group are formed; And m is the integer of 1-6.
R 11and R 12the alkylene of each C1-10 of being preferably (being preferably C1-3).R 13and R 14each preferably hydrogen atom.R 15can be C3-20 (be preferably C6-10, be more preferably C8) alkyl and the cycloalkyl be preferably shown below or cycloalkenyl group, be more preferably cycloalkenyl group.
M is preferably 2 or 3.The above-mentioned suitable example such as formula shown compound comprises four glycidyl group-m-xylene diamine, four Racemic glycidol aminodiphenylmethanes, four glycidyl group-Ursol D, 2-glycidyl aminomethyl cyclohexane and the two aminomethyl cyclohexane of four glycidyl group-1,3-.
The above-mentioned modified polybutadiene rubber (low cis BR of A-modification) with low cis content being more preferably the mixture modification be made up of the dipolymer of the low-molecular weight compound and this low-molecular weight compound that comprise Racemic glycidol amino in molecule or high-order oligopolymer by the modified polybutadiene rubber with low cis content comprising the low-molecular weight compound modification of Racemic glycidol amino in molecule.The example of the low cis BR of A-modification comprises those that describe in JP 2009-275178 A and other patent documentation.
Oligopolymer is preferably dipolymer to ten polymers of this low-molecular weight compound.In addition, this low-molecular weight compound refers to that molecular weight is the organic compound of less than 1000, and it can suitably for as shown in the formula the compound shown in (2):
Wherein, R represents bivalent hydrocarbon radical or comprises the divalent organic group of at least one polar group, and this polar group is selected from by containing oxygen polar group such as ether, epoxy group(ing), and ketone group; Sulfur-bearing polar group such as thioether and thioketones base; And in the combination that nitrogenous polar group such as uncle is amino and imino-is formed.Above-mentioned bivalent hydrocarbon radical can be saturated or undersaturated, and can be straight chain, have side chain or ring-type.The example of this bivalent hydrocarbon radical comprises alkylene, alkylene group and phenylene.Its object lesson comprises methylene radical, ethene, butylene, cyclohexylene, and 1, two (methylene radical) hexanaphthene of 3-, two (vinyl) hexanaphthene of 1,3-, adjacent phenylene, metaphenylene, to phenylene, m-xylene, p-Xylol and two (phenylene) methane.
The object lesson of the low-molecular weight compound shown in above-mentioned formula (2) comprises: four glycidyl group-1, the two aminomethyl cyclohexane of 3-, N, N, N ', N '-four glycidyl group-m-xylene diamine, 4, 4-methylene radical-bis-(N, N-diglycidylaniline), 1, two (the N of 4-, N-2-glycidyl is amino) hexanaphthene, N, N, N ', N '-four glycidyl group-Ursol D, 4, 4 '-bis-(2-glycidyl is amino) benzophenone, 4-(4-glycidyl piperazinyl)-(N, N-diglycidyl) aniline, and 2-[2-(N, N-diglycidyl is amino) ethyl]-1-glycidyl tetramethyleneimine.In these, the preferred two aminomethyl cyclohexane of four Racemic glycidols-1,3-.
The suitable example of above-mentioned oligopolymer component comprises the trimer shown in the dipolymer shown in following formula (3) and following formula (4):
When using the mixture of low-molecular weight compound and oligopolymer to carry out modification, with the mixture of 100 quality % for benchmark, properties-correcting agent (mixture) preferably comprises, the low-molecular weight compound of 75-95 quality % and the oligopolymer of 25-5 quality %.
In properties-correcting agent, the ratio of low-molecular weight compound and oligopolymer can pass through gel permeation chromatography (GPC) and measures.
Specifically, allow to be selected the pillar analyzed to the sample of oligopolymer component from low-molecular weight compound and in order to analyze them.By the peak value observed in analyzing, along be derived from low-molecular weight compound peak high molecular side on first flex point vertically draw a line to calculate the ratio between the area of lower-molecular-weight component and the area of high molecular weight component.This area ratio corresponds to the ratio between low-molecular weight compound and oligopolymer component.
It should be noted that and to be integrated from the peak on the high molecular side of oligopolymer component, until its molecular weight reaches the point of the molecular weight 10 times being no more than low-molecular weight compound (determining relative to polystyrene standard); Or under the following conditions until the peak of component reaches the point of 0: if reach the point of the molecular weight 10 times being no more than low-molecular weight compound at its molecular weight before, the peak of component reaches 0.
Properties-correcting agent is undertaken by making the reactive terminal of properties-correcting agent and polymkeric substance react with the reaction with the butadiene polymer of reactive terminal of being synthesized by anionoid polymerization (using polymerization starter such as lithium compound).Utilize the modification of the low-molecular weight compound comprising the sweet amino that shrinks in molecule or the polybutadiene rubber carried out in the mixture that its oligopolymer is formed by this compound to use to carry out according to the method for modification such as formula the compound (properties-correcting agent) shown in (1).
Cis-content for the modification low cis BR of silicon-dioxide is below 50 quality %, is preferably below 45 quality %, is more preferably below 40 quality %.If its cis-content is more than 50 quality %, then the per-cent owing to adding the silicon-dioxide-modified group in polymkeric substance reduces, and BR is tending towards being not easy to react to each other with silicon-dioxide.The lower limit of its cis-content is not particularly limited, and is preferably more than 10 quality %, is more preferably more than 20 quality %.If its cis-content is lower than 10 quality %, elongation at break EB and wear resistance may reduce.
Contents of ethylene for the modification low cis BR of silicon-dioxide is preferably below 35 quality %, is more preferably below 30 quality %.If its contents of ethylene is more than 35 quality %, so fuel economy and elongation at break EB may reduce.The lower limit of its contents of ethylene is not particularly limited, and is preferably more than 1 quality %, more preferably more than 10 quality %.If its contents of ethylene is lower than 1 quality %, so E* may reduce.
Weight-average molecular weight (Mw) for the modification low cis BR of silicon-dioxide is preferably 200, more than 000, is more preferably 400, more than 000.If Mw is less than 200,000, satisfied wear resistance and elongation at break cannot be obtained.Its Mw is preferably 900, and less than 000, be more preferably 700, less than 000.When the weight-average molecular weight Mw of BR is greater than 900, when 000, can processibility be reduced and cause poor dispersiveness, causing insufficient fuel economy, wear resistance and elongation at break.
Cis-content used herein (cis-Isosorbide-5-Nitrae-butadiene unit content) and contents of ethylene (1，2-butadiene unit content) can be measured by infrared absorption spectrum.Weight-average molecular weight (Mw) and number-average molecular weight (Mn) can utilize gel permeation chromatography (GPC) (the GPC-8000 series manufactured by TOSOH company, detector: differential refractometer, chromatographic column: the TSKGEL SUPERMULTIPORE HZ-M manufactured by TOSOH company) be that standard measures with polystyrene.
With 100 quality % rubber components for benchmark, the content for the modification low cis BR of silicon-dioxide is more than 8 quality %, is preferably more than 10 quality %, is more preferably more than 12 quality %.If this content is lower than 8 quality %, gratifying fuel economy and wear resistance cannot be obtained.Correspondingly, its content is below 40 quality %, is preferably below 30 quality %, is more preferably below 20 quality %.If this content is more than 40 quality %, then wear resistance and elongation at break are tending towards reducing.
The example of other BR includes but not limited to, is generally used for those of tire industry, comprises the BR1220 that high-cis BR manufactures as ZEON company and the BR150B manufactured by Ube Industries, Ltd; Comprise the BR (SPB) of 1,2-syndiotactic polybutadiene crystal, as VCR412 and VCR617 manufactured by Ube Industries, Ltd; With the polybutadiene rubber (BR of rare earth catalyst) using rare earth catalyst synthesis.Other example comprises modified polybutadiene rubber and such as carries out the tin modification polybutadiene rubber (tin modification BR (the modification BR for carbon black)) of modification (such as by tin compound, with the tin modification BR of lithium initiator polymerization, its vinyl binding capacity is 5-50 quality %, Mw/Mn is less than 2.0, and the content of tin atom is 50-3000ppm).Especially, the BR of rare earth catalyst is preferred.
It is high that BR due to rare earth catalyst has cis-content, contents of ethylene is low, the feature that weight-average molecular weight (Mw) is low with the ratio (Mw/Mn) of number-average molecular weight (Mn), therefore it not only possesses good wear resistance and can provide good fuel economy, elongation at break and cracking growth resistance simultaneously.But although itself and carbon black have very high consistency, the BR of rare earth catalyst and silicon-dioxide have lower consistency.In order to solve this problem, if combinationally used for the modification low cis BR of silicon-dioxide and the BR of rare earth catalyst, so because the BR of rare earth catalyst has close chemical constitution with the modification low cis BR for silicon-dioxide, therefore they can form a phase.Therefore, having with silicon-dioxide makes silicon-dioxide can be dispersed in well in BR phase compared with the modification low cis BR for silicon-dioxide of high-compatibility, has simultaneously compared with the BR of the rare earth catalyst of high-compatibility, carbon black can be dispersed in BR phase well with carbon black.Due to the combination of above-mentioned two kinds of BR, make silicon-dioxide and carbon black to disperse well and to be distributed in BR phase simultaneously, cause good wear resistance thus, fuel economy, wet earth-catching property and elongation at break, especially good wear resistance.
Next, will the polybutadiene rubber (BR of rare earth catalyst) using rare earth catalyst synthesis be described.
The BR of rare earth catalyst refers to the polybutadiene rubber using rare earth catalyst synthesis, and it is high that it possesses cis-content, the feature that contents of ethylene is low.As the BR of rare earth catalyst, the product of the usual object used in Tire production can be used.
Rare earth catalyst can be known one, and its example comprises the catalyzer containing lanthanide rare compound, organo-aluminium compound, aikyiaiurnirsoxan beta or halogen contained compound, and it has Lewis base alternatively.In these, particularly preferably containing the Nd catalyzer of neodymium (Nd) compound as lanthanide rare compound.
The example of lanthanide rare compound comprises halogenide, carboxylicesters, alkoxide, and thioalkoxide and ordination number are the acid amides of the rare earth metal of 57-71.As mentioned above, in these, preferred Nd catalyzer, because it allows the generation of the BR with high cis-contents and low vinyl content.
The example of organo-aluminium compound comprises as AlR ar br cshown compound, wherein R a, R band R cbe same to each other or different to each other, each alkyl representing hydrogen or there is 1-8 carbon atom.The example of aikyiaiurnirsoxan beta comprises Cyclic aluminoxane and non-annularity aikyiaiurnirsoxan beta.The example of halogen contained compound comprises as AlX kr d 3-kshown aluminum halide, wherein X represents halogen; R drepresent C1-20 alkyl, aryl or aralkyl; K represents 1,1.5,2 or 3; Halogenation strontium is as Me 3srCl, Me 2srCl 2, MeSrHCl 2and MeSrCl 3; And metal halide is as silicon tetrachloride, tin tetrachloride and titanium tetrachloride.Lewis base is used for complexing lanthanide rare compound, and its suitable example comprises methyl ethyl diketone, ketone and alcohol.
In polymerized butadiene, rare earth catalyst can at organic solvent (such as, normal hexane, hexanaphthene, normal heptane, toluene, dimethylbenzene and benzene) in solution form to use or with load at suitable carrier (such as, silicon-dioxide, magnesium oxide and magnesium chloride) on form use.About polymerizing condition, polymerization can be solution polymerization or mass polymerization, and polymerization temperature is preferably-30 ~ 150 DEG C, and polymerization pressure can be selected suitably according to other conditions.
The weight-average molecular weight (Mw) of the BR of rare earth catalyst is preferably more than 1.2 with the ratio (Mw/Mn) of number-average molecular weight (Mn), is more preferably more than 1.5.If this ratio is lower than 1.2, processibility is tending towards deterioration significantly.This ratio Mw/Mn is preferably less than 5, is more preferably less than 4, is also more preferably less than 3, is preferably less than 2 especially, most preferably is less than 1.9.If this ratio is more than 5, the effect so improving wear resistance is tending towards reducing.
The Mw of the BR of rare earth catalyst is preferably 200, and more than 000, be more preferably 250,000, but it is preferably 900, less than 000, is more preferably 600, less than 000.In addition, the Mn of the BR of rare earth catalyst is preferably 100, and more than 000, be more preferably 150, more than 000, but it is preferably 800, less than 000, is more preferably 700, less than 000.If Mw or Mn is less than above-mentioned lower value, wear resistance is tending towards reducing and fuel economy aggravates.If Mw or Mn exceedes the above-mentioned upper limit, processibility may be poor.
The cis-content of the BR of rare earth catalyst is preferably more than 90 quality %, is more preferably more than 93 quality %, is more preferably more than 95 quality %.If its cis-content is lower than 90 quality %, wear resistance can be lowered.
The contents of ethylene of the BR of rare earth catalyst is preferably below 1.8 quality %, is more preferably below 1.0 quality %, is more preferably below 0.5 quality %, is preferably below 0.3 quality % especially.If its contents of ethylene is more than 1.8 quality %, wear resistance can be lowered.
When rubber combination according to the present invention comprises the BR of rare earth catalyst, with the rubber components of 100 quality % for benchmark, the content of the BR of rare earth catalyst is preferably more than 5 quality %, is more preferably more than 10 quality %, is more preferably more than 12 quality %.If its content is lower than 5 quality %, satisfied wear resistance and elongation at break cannot be obtained.Its content is preferably below 40 quality %, is more preferably below 35 quality %, is more preferably below 30 quality %.If its content is more than 40 quality %, satisfied fuel economy and wear resistance cannot be obtained.
In rubber combination of the present invention, with 100 quality % rubber components for benchmark, the content of BR is more than 8 quality %, is preferably more than 10 quality %, is more preferably more than 15 quality %.If its content is lower than 8 quality %, wear resistance can reduce.BR content is preferably below 60 quality %, is more preferably below 55 quality %.If its content is more than 60 quality %, wet earth-catching property, processibility and elongation at break EB will deteriorations.
Styrene-butadiene rubber(SBR) (SBR) is comprised according to the rubber components in rubber combination of the present invention.It can provide good wet earth-catching property, fuel economy and antireversion.
SBR is not particularly limited, its example comprises the SBR (E-SBR) of letex polymerization, the SBR (S-SBR) of solution polymerization and the modified styrene butadiene rubber (the modification SBR for silicon-dioxide) (it has been used can be interactional compound modified with silicon-dioxide) for silicon-dioxide.Especially, E-SBR and the modification SBR for silicon-dioxide is preferred, and the combination of these SBR is preferred.E-SBR has a high proportion of high molecular weight component and can provide outstanding wear resistance and elongation at break.On the other hand, for the modification SBR of silicon-dioxide and silicon-dioxide Degree of interaction high, therefore allow dispersion that silicon-dioxide is good thus improve fuel economy and wear resistance.
Next, E-SBR is specifically described.
E-SBR is not particularly limited, can use be generally used in tire industry those.
When rubber combination according to the present invention comprises E-SBR, with 100 quality % rubber components for benchmark, the content of E-SBR is preferably more than 10 quality %, is more preferably more than 30 quality %.If its content is lower than 10 quality %, satisfied wear resistance cannot be obtained, elongation at break and processibility.The content of E-SBR is preferably below 70 quality %, is more preferably below 60 quality %.If its content is more than 70 quality %, fuel economy and wear resistance are tending towards reducing.
Next, will describe with carrying out the modified styrene butadiene rubber (the modification SBR for silicon-dioxide) being used for silicon-dioxide of modification with the interactional compound of silicon-dioxide.
Modification SBR for silicon-dioxide can be by replacing above-mentioned obtained for the skeleton structure in the modification BR of silicon-dioxide and polybutadiene rubber with styrene-butadiene rubber(SBR).Especially, modification SBR for silicon-dioxide is preferably with such as formula the compound modified divinyl rubber (S-modification SBR) shown in (1), and suitable solution polymerization styrene-butadiene rubber (S-SBR), the compound of its polymerizable end (reactive terminal) shown in formula (1) carries out modification (S-modification S-SBR (the modification SBR described in patent documentation JP2010-111753).
In the present invention, the styrene for the modification SBR of silicon-dioxide is preferably below 40 quality %, is more preferably below 35 quality %, is more preferably below 30 quality %.If styrene is more than 40 quality %, fuel economy can deterioration.Also be preferably more than 15 quality % for the styrene in the modification SBR of silicon-dioxide, be more preferably more than 23 quality %.If this styrene is lower than 15 quality %, wet earth-catching property is tending towards poor.
Styrene content passes through H 1-NMR method measures.
Rubber combination according to the present invention comprises in the situation for the modification SBR of silicon-dioxide, with 100 quality % rubber components for benchmark, content for the modification SBR of silicon-dioxide is preferably more than 8 quality %, is more preferably more than 15 quality %, is more preferably more than 20 quality %.If this content is lower than 8 quality %, satisfied wet earth-catching property and fuel economy cannot be obtained.This content is also preferably below 80 quality %, is more preferably below 75 quality %, is more preferably below 72 quality %, is preferably below 70 quality % especially.If this content is more than 80 quality %, wear resistance and fuel economy are tending towards reducing.
In rubber combination of the present invention, with 100 quality % rubber components for benchmark, the content of SBR is more than 25 quality %, is preferably more than 30 quality %, is more preferably more than 35 quality %.If this content is lower than 25 quality %, wet earth-catching property and antireversion can worsen.The content of SBR is also below 75 quality %, is preferably below 72 quality %, is more preferably below 70 quality %.If this content is more than 75 quality %, the content of NR and BR of mixing can reduce thus cannot obtain satisfied wear resistance and processibility (when NR).
Except BR and SBR, the example of other elastomeric material in rubber combination used in the present invention comprises polydiene as natural rubber (NR), epoxy natural rubber (ENR), polyisoprene rubber (IR), high-purity natural rubber (phosphorus content is the HPNR of below 200ppm), 3,4-polyisoprene rubber (3,4-IR), styrene isoprene butadiene rubber (SIBR) (SIBR), chloroprene rubber (CR), and paracril (NBR).Other elastomeric material (such as, ethylene propylene diene rubber (EPDM) and isoprene-isobutylene rubber (IIR)) except polydiene can be comprised in rubber components.These elastomeric materials may be used singly or two or more in combination.Preferred NR in these, because it can provide good elongation at break.
It is 160-270m that rubber combination according to the present invention comprises N2 adsorption specific surface area 2the silicon-dioxide of/g, i.e. fine particle silica.This fine particle silica can be used alone or is used in combination.
N2 adsorption specific surface area (the N of fine particle silica 2sA) 170m is preferably 2/ more than g, is more preferably 195m 2/ more than g, is more preferably 210m 2/ more than g.If this N2 adsorption specific surface area is less than 160m 2/ g, wet earth-catching property, elongation at break and wear resistance (particularly wear resistance) will be tending towards being enhanced fully, because the effect of such silicon-dioxide in enhancing polymeric matrix is poor, cause the formation of a small amount of filler gel, thus affect wear resistance and fracture tensile strength.Its N2 adsorption specific surface area is preferably 260m 2/ below g, is more preferably 250m 2/ below g.If its N2 adsorption specific surface area is more than 270m 2/ g, such silicon-dioxide itself has very strong tendency of certainly reuniting, thus is tending towards having poor dispersiveness, causes fuel economy, the reduction of elongation at break and wear resistance.
Herein, the N of silicon-dioxide 2sA value is measured by BET method according to ASTM D3037-81 standard.
Relative to 100 mass parts rubber components, the content of fine particle silica is more than 40 mass parts, is preferably more than 50 mass parts.If this content is lower than 40 mass parts, fuel economy, wet earth-catching property, the improvement effect of elongation at break and wear resistance can be insufficient.This content is below 120 mass parts, is preferably below 110 mass parts, is more preferably below 105 mass parts, is more preferably below 100 mass parts.If this content is more than 120 mass parts, the dispersiveness of fine particle silica is poor, can cause fuel economy, the reduction of elongation at break and wear resistance.
According in rubber combination of the present invention, preferred silane coupling agent and silica composition use.Especially, mercaptosilane coupling agents is preferred.Consider wear resistance, mercaptosilane coupling agents is preferred, because compare with traditional Si266 with Si69, even if applying frictional force on road surface, they also can keep the coupling between silicon-dioxide and polymkeric substance.When using the BR of rare earth catalyst, the own tight agglomeration of polymer molecule and there is lower bonding strength with Si266 or Si69, but they and mercaptosilane coupling agents form firm combination.
The suitable example comprising the silane coupling agent of sulfydryl (-SH) comprises the compound as shown in formula I and the compound containing the connector element A shown in formula II and the connector element B shown in formula III:
Wherein, R 101to R 103each representative has side chain or unbranched C1-12 alkyl, has the alkoxyl group of side chain or unbranched C1-12, or-O-(R 111-O) z-R 112, wherein z R 111respective representative has side chain or unbranched C1-30 bivalent hydrocarbon radical, z R 111can be same to each other or different to each other.R 112representative has side chain or unbranched C1-30 alkyl, have side chain or unbranched C2-30 alkenyl, C6-30 aryl or C7-30 aralkyl, and z represents the integer of 1-30, R 101to R 103can be same to each other or different to each other; R 104representative has side chain or unbranched C1-6 alkylene.
Wherein, R 201represent hydrogen, halogen, have side chain or unbranched C1-30 alkyl, have side chain or unbranched C2-30 alkenyl, have side chain or unbranched C2-30 alkynyl, or the alkyl that its end hydrogen is substituted by hydroxyl or carboxyl, R 202representative has side chain or unbranched C1-30 alkylene, has side chain or unbranched C2-30 alkenylene, or has side chain or unbranched C2-30 alkynylene, R 201and R 202ring structure can be formed together.
The example of the compound shown in formula I comprises 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto ethyl trimethoxy silane, 2-mercaptoethyltriethoxysilane, and the compound (Si363 manufactured by EVONIK-DEGUSSA) representated by following formula.Compound representated by following formula can use suitably.These compounds may be used singly or two or more in combination.
Next, the compound containing the connector element A shown in formula II and the connector element B shown in formula III will be described.In the silane coupling agent with this structure, consider the effect that enhancing prevents viscosity from increasing between processing period and prevent scorch time from reducing, the content of connector element A is preferably more than 30 % by mole, be more preferably more than 50 % by mole, also be preferably less than 99 % by mole simultaneously, be more preferably less than 90 % by mole.In addition, the content of connector element B is preferably more than 1 % by mole, is more preferably more than 5 % by mole, is more preferably more than 10 % by mole, is also preferably less than 70 % by mole simultaneously, is more preferably less than 65 % by mole, is more preferably less than 55 % by mole.In addition, the combined amount of connector element A and B is preferably more than 95 % by mole, is more preferably more than 98 % by mole, is preferably 100 % by mole especially.
It should be noted that the content of connector element A or B is the content comprising connector element A or B (if existence) being positioned at end of silane place.If connector element A or B is positioned at end of silane place, so their form is not particularly limited, as long as they are formed to correspond to represent the formula II of connector element A and B and the unit of (III) respectively.
For R 201the example of halogen comprise chlorine, bromine and fluorine.For R 201the example of side chain or unbranched C1-30 alkyl that has comprise methyl and ethyl.The carbonatoms of this alkyl is preferably 1-12.For R 201have side chain or unbranched C2-30 alkenyl comprise vinyl and 1-propenyl, the carbonatoms of this alkenyl is preferably 2-12.For R 201the example of side chain or unbranched C2-30 alkynyl that has comprise ethynyl and proyl.The carbonatoms of this alkynyl is preferably 2-12.For R 202the example of side chain or unbranched C1-30 alkylene that has comprise a vinyl and propenyl.The carbonatoms of this alkylene is preferably 1-12.For R 202the example of the alkenylene of side chain or unbranched C2-30 that has comprise vinylidene and 1-propenylidene.The carbonatoms of this alkenylene is preferably 2-12.For R 202the example of side chain or unbranched C2-30 alkynylene that has comprise ethynylene and sub-proyl, the carbonatoms of this alkynylene is preferably 2-12.
In the compound comprising the connector element B shown in the connector element A shown in formula II and formula III, total multiplicity (x+y) preferable range of the multiplicity y of the multiplicity x of the connector element A shown in formula II and the connector element B shown in formula III is 3-300.Gross weight is scolded when above-mentioned scope again, and the hydrosulphonyl silane of connector element B is connected the-C of unit A 7h 15part covered, its can guarantee with silicon-dioxide or rubber components sound response while prevent the minimizing of scorch time.
The example comprising the compound of the connector element A shown in formula II and the connector element B shown in formula III comprises NXT-Z30, NXT-Z45, and NXT-Z60 (manufacturing by MomentivePerformanceMaterials).These compounds may be used singly or in combination of two or more.
In addition, the compound representated by following formula can be used suitably:
Relative to the silicon-dioxide of 100 mass parts, silane coupled agent content is preferably more than 1 mass parts, is more preferably more than 3 mass parts.If this content is lower than 1 mass parts, wear resistance, elongation at break and viscosity (processibility) aggravate.The content of silane coupling agent is also preferably below 15 mass parts, is more preferably below 12 mass parts.If this content is more than 15 mass parts, being tending towards obtaining increases proportional effect with cost.
Preferably comprising N2 adsorption specific surface area according to rubber combination of the present invention is 100-250m 2the carbon black of/g, that is, micro mist carbon black.This micro mist carbon black can be used alone or be used in combination.
N2 adsorption specific surface area (the N of micro mist carbon black 2sA) 120m is preferably 2/ more than g, is more preferably 140m 2/ more than g.If its N 2sA is less than 100m 2/ g, is tending towards obtaining satisfied elongation at break and wear resistance.Its N 2sA is preferably 200m 2/ below g, is more preferably 180m 2/ below g.N 2sA is more than 250m 2the carbon black of/g is tending towards having poor dispersiveness, causes fuel economy, elongation at break and wear resistance to reduce.
The N of carbon black herein 2sA is according to JIS K 6217-2:2001 standard test.
Relative to 100 mass parts rubber components, the content of micro mist carbon black is preferably more than 1 mass parts, is more preferably more than 3 mass parts.If this content is lower than 1 mass parts, the interpolation of this carbon black does not have effect.In addition, it also cannot stop the UV degradation of rubber.This content is also preferably below 50 mass parts, is more preferably below 40 mass parts, is more preferably below 30 mass parts.If this content is more than 50 mass parts, satisfied fuel economy and elongation at break cannot be obtained.
Rubber combination of the present invention can comprise the mineral filler of aluminium system as aluminium hydroxide.Aluminium hydroxide is not particularly limited, and can be that it is that to be generally used in tire industry.The average primary particle diameter of aluminium hydroxide is preferably 0.3-10 μm, is more preferably 0.6-3 μm.
Rubber combination of the present invention preferably comprises sulphur.The example of sulphur comprises powder sulphur, precipitated sulfur, sulfoid, insoluble sulfur and polymolecularity sulphur.
Relative to the rubber components of 100 mass parts, the content of sulphur is preferably more than 0.5 mass parts, is more preferably more than 0.7 mass parts.The content of sulphur is also preferably below 2 mass parts, is more preferably below 1.7 mass parts.When the content of sulphur drops in above-mentioned scope, effect of the present invention can more suitably be implemented.
Be used in rubber combination of the present invention if softening temperature is the liquid resin of-20 ~ 45 DEG C, due to resin itself, there is good dispersiveness and elastoprene (BR can be lubricated suitably, SBR) polymer chain thus be polymer chain and the fine particle silica of elastoprene, or micro mist carbon black, or between sulphur, provide suitable oilness.Fine particle silica, micro mist carbon black and sulphur can be evenly dispersed in whole rubber combination in kneading step.In addition, because sulphur is uniformly dispersed, polymer molecule can be cross-linked to each other equably in vulcanisation step.
As mentioned above, when the liquid resin with specific softening temperature is used in rubber combination of the present invention, the dispersiveness of fine particle silica and micro mist carbon black is further improved, and meanwhile, polymer molecule is cross-linked to each other equably.Therefore, can obtain good elongation at break, therefore fuel economy, wet earth-catching property, the balance between elongation at break and wear resistance is improved and can be implemented.
Especially, when the liquid coumarone-indene resin with specific softening temperature is used as liquid resin, this resin and sulphur (being especially contained in the Sauerstoffatom in liquid coumarone-indene resin and sulphur) are attracted each other by Van der Waals force, make the surface of sulphur coated by this resin, thus there is the surface energy (reducing the tendency of reuniting) of reduction.So because the difference of the SP value between the surface of sulphur and elastoprene reduces, the dispersiveness of sulphur is improved significantly.In addition, due to resin itself, there is good dispersiveness and lubricate the polymer chain of elastoprene, therefore sulphur is more uniformly scattered in whole rubber combination in kneading step, and polymer molecule is more uniformly cross-linked to each other in vulcanisation step.Therefore, the effect improving above-mentioned performance can realize better.
As mentioned above, rubber combination of the present invention is preferably the liquid resin of-20 ~ 45 DEG C containing softening temperature.This liquid resin is preferred for substituting oil.
Liquid resinous softening temperature is more than-20 DEG C, is preferably more than-10 DEG C.If softening temperature is lower than-20 DEG C, the effect of can not be improved fully fuel economy and elongation at break.Softening temperature is also less than 45 DEG C, is preferably less than 40 DEG C, if softening temperature is higher than 45 DEG C, fuel economy, elongation at break and wear resistance can deteriorations.
Liquid resinous softening temperature refers to that in the softening point measurement specified in JIS K 6220-1:2001 standard by ring and ball softening point survey meter, ball falls the temperature at place.
Liquid resin is not particularly limited, and only has its softening temperature in above-mentioned scope.Liquid resinous example comprises the coumarone-indene resin that aromatic liquid resin (or having the anine of above-mentioned softening point range) such as particularly has above-mentioned softening point range; Liquid terpene resin (or there is the terpine resin of above-mentioned softening point range); And liquid Gum Rosin (or there is the Gum Rosin of above-mentioned softening point range).Especially, aromatic liquid resin such as particularly liquid coumarone-indene resin and liquid terpene resin are preferred, and liquid coumarone-indene resin is preferred, because they can make effect of the present invention more suitably realize.
Anine refers to the resin obtained by polymerization C8-10 fragrance cut, and it is usually fissioned by petroleum naphtha and obtains and comprise Vinyl toluene, indenes and methyl indenes as principal monomer.Here, other component in anine comprises vinylbenzene and its homologues as alpha-methyl styrene and Beta-methyl vinylbenzene.Anine also can comprise aliphatics olefin unit, phenol units and/or cresols unit.
The example of anine comprises coumarone-indene resin, indene resin, aromatic ethylene polymkeric substance (resin obtained by polymerization alpha-methyl styrene and/or vinylbenzene) and C9 hydrocarbon resin.In these, preferred coumarone-indene resin, because it can make effect of the present invention more suitably realize.That is, the coumarone-indene resin with above-mentioned softening point range is preferred.
Coumarone-indene resin refers to and comprises coumarone and indenes as the resin of monomeric unit of skeleton (main chain) forming this resin.Except coumarone and indenes, the example that can be comprised in the monomeric unit in its skeleton comprises vinylbenzene, alpha-methyl styrene, methyl indenes and Vinyl toluene.
The example of terpine resin comprises polyterpene resin and terpene phenol resin.Polyterpene resin is preferred.In other words, liquid terpene resin is preferably liquid terpene resin (having the polyterpene resin of above-mentioned softening point range).
Polyterpene resin comprises by the obtained resin of polymerization terpene compound and its hydrogenated products.Terpene compound comprises formula (C 5h 8) hydrocarbon representated by n and containing oxygen derivative thereof.Terpene compound has and is divided into monoterpene (C 10h 16), sesquiterpene (C 15h 24), di-terpene (C 20h 32) etc. the basic framework of terpenes.The example of terpene compound comprises α-sobrerone, β-sobrerone, limonene, limonene, myrcene, alloocimene, ocimene, α-phellandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-Terpane, Isosorbide-5-Nitrae-Terpane, α-terpinol, β-terpinol, and γ-terpinol.
The example of polyterpene resin comprises by the obtained terpine resin of above-mentioned any terpene compound such as α-sobrerone resin, β-sobrerone resin, limonene resin, limonene resin and β-sobrerone/limonene resin, and the hydrogenated terpene resin obtained by carrying out hydrogenation to terpine resin.In these, preferred limonene resin, because it can provide good wet earth-catching property.
The example of terpene phenol resin comprises the resin obtained by above-mentioned terpene compound and phenolic compound.Its object lesson comprises by terpene compound, and phenolic compound and formalin carry out condensation and obtained resin.The example of phenolic compound comprises phenol, dihydroxyphenyl propane, cresols and xylenol.
Relative to 100 mass parts rubber components, liquid resinous amount is preferably more than 0.5 mass parts, is more preferably more than 1 mass parts.If this content is lower than 0.5 mass parts, the effect of fuel economy, elongation at break and the wear resistance of cannot being improved fully.Liquid resinous content is also preferably below 20 mass parts, is more preferably below 10 mass parts, is more preferably below 5 mass parts.If this content is more than 20 mass parts, complex modulus (E*) and hardness can be lowered.
It is the terpine resin of 46 ~ 160 DEG C that rubber combination of the present invention preferably comprises that at least one is selected from by softening temperature, softening temperature is the Gum Rosin of 46 ~ 140 DEG C, the resin in softening temperature to be the C5 petroleum resin of 46 ~ 140 DEG C and softening temperature be combination that the anine of 46 ~ 140 DEG C forms.Although present invention uses the BR causing wet earth-catching property to reduce that content is relatively high, the use of these rubber provides good wet earth-catching property, and fuel economy, wet earth-catching property, elongation at break and wear resistance can more suitably be improved.This may be because these resins are distributed in rubber components with the spherical form of 100nm-1 μm, thus tire grab ground time provide physical property grab (such as, when road surface has comparatively high temps, produce anchoring effect or adherent zone effect by making resin melting).
At least one resin be selected from aforesaid combination is preferably terpine resin or anine.Terpine resin is efficient in the wet earth-catching property of improvement and fuel economy, and anine is efficient in the wet earth-catching property of improvement.
Relative to 100 mass parts rubber components, the combined content being selected from the resin in aforesaid combination is preferably more than 1 mass parts, is more preferably more than 3 mass parts, is more preferably more than 7 mass parts.Its combined content is also preferably below 20 mass parts, is more preferably below 15 mass parts, is more preferably below 12 mass parts.When its combined content drops in above-mentioned scope, fuel economy, wet earth-catching property, elongation at break and wear resistance can be improved suitably.
Softening temperature is that the liquid terpene resin of terpine resin only from above-mentioned in softening temperature of 46 ~ 160 DEG C is different.This terpine resin may suitably be polyterpene resin or terpene phenol resin, is more suitably terpene phenol resin.
Preferred polyterpene resin is limonene resin, because it can provide outstanding earth-catching property.In the present invention, except terpene compound, terpine resin (polyterpene resin, terpene phenol resin) can comprise other a small amount of monomers if alpha-methyl styrene is as monomeric unit.Such as, by terpene compound, phenolic compound and a small amount of alpha-methyl styrene are included in terpene phenol resin as the resin that monomer is obtained.
The softening temperature of terpine resin is preferably more than 46 DEG C, is more preferably more than 80 DEG C, is more preferably more than 100 DEG C.If its softening temperature is lower than 46 DEG C, the effect improving wet earth-catching property can be lowered.Its softening temperature is also preferably less than 160 DEG C, is more preferably less than 135 DEG C.If its softening temperature is more than 160 DEG C, such resin can have the dispersiveness of reduction, causes elongation at break and wear resistance to reduce.
Be used as in the situation of at least one resin be selected from aforesaid combination only having terpine resin, the preferred amounts of terpine resin is the combined content of the above-mentioned resin be selected from aforesaid combination.
Softening temperature is that the anine of 46 ~ 140 DEG C refers to that the softening temperature obtained by polymerization C8-C10 fragrance cut is the resin of 46 ~ 140 DEG C, and it is usually fissioned by petroleum naphtha and obtains and comprise Vinyl toluene, indenes and methyl indenes as principal monomer.Here, other components in fragrant cut comprise vinylbenzene and cinnamic homologue as alpha-methyl styrene and Beta-methyl vinylbenzene.Anine also can comprise coumarone unit.Anine also can comprise fatty olefin unit, phenol units and/or cresols unit.
The softening temperature of anine is more than 46 DEG C, is preferably more than 60 DEG C, is more preferably more than 70 DEG C, is more preferably 80 DEG C, and is preferably more than 90 DEG C especially.If its softening temperature is lower than 46 DEG C, the effect improving earth-catching property can be lowered.In addition, its softening temperature is less than 140 DEG C, is preferably less than 130 DEG C.If softening temperature is more than 140 DEG C, such resin can have the dispersiveness of reduction, causes elongation at break and wear resistance to reduce.
The example of anine comprises coumarone-indene resin, indene resin, aromatic ethylene polymkeric substance (resin obtained by polymerization alpha-methyl styrene and/or vinylbenzene), and C9 hydrocarbon resin.Especially, coumarone-indene resin, indene resin and aromatic ethylene polymkeric substance are preferred, and coumarone-indene resin and aromatic ethylene polymkeric substance are preferred, because they can improve fuel economy evenly, wet earth-catching property, elongation at break and wear resistance.Also preferred coumarone-indene resin and aromatic ethylene combination of polymers to be used.
The coumarone-indene resin of the above-mentioned example as anine is only different from previously mentioned liquid coumarone-indene resin in softening temperature.When only having coumarone-indene resin (anine) as at least one resin be selected from aforesaid combination, the preferred amounts of coumarone-indene resin is the combined content of the above-mentioned resin be selected from aforesaid combination.
Aromatic ethylene polymkeric substance is formed as aromatic vinyl monomers (unit) by vinylbenzene and/or alpha-methyl styrene.Aromatic ethylene polymkeric substance can be the homopolymer of each of these monomers, or the multipolymer of two kinds of monomers.Aromatic ethylene polymkeric substance is preferably alpha-methyl styrene or cinnamic homopolymer, or alpha-methyl styrene and cinnamic multipolymer, be more preferably alpha-methyl styrene and cinnamic multipolymer, because it is environmental protection and be easy to process, good wet earth-catching property can be provided.
As aromatic ethylene polymkeric substance, commercially available prod can be used suitably, the SYLVARES SA85 that such as Arizona chemical company manufactures, SA100, SA120 and SA140, the R2336 that Eastman Chemical Company produces.
The softening temperature of aromatic ethylene polymkeric substance is preferably more than 46 DEG C, is more preferably more than 60 DEG C, is more preferably more than 70 DEG C.If its softening temperature is lower than 46 DEG C, wet earth-catching property can reduce.This softening temperature is also preferably less than 140 DEG C, is more preferably less than 100 DEG C.If softening temperature is higher than 140 DEG C, fuel economy can worsen.
The softening temperature of terpine resin, Gum Rosin, C5 petroleum resin, anine and aromatic ethylene polymkeric substance refers to that in the softening point measurement specified in JIS K 6220-1:2001 standard by ring and ball softening point survey meter, ball falls the temperature at place separately.
When only having aromatic ethylene polymkeric substance as at least one resin be selected from aforesaid combination, the preferred amounts of aromatic ethylene polymkeric substance is the combined content of the above-mentioned resin be selected from aforesaid combination.
The combination of rubber combination of the present invention preferably containing softening temperature to be-20 ~ 45 DEG C of liquid coumarone-indene resins and softening temperature the be anine of 46 ~ 140 DEG C, because this allows effect of the present invention more suitably to realize.
In addition to the above components, rubber combination of the present invention can suitably comprise, and is generally used for the Synergist S-421 95 in rubber combination preparation, comprises, such as, processing aid as zinc oxide, stearic acid, and fatty acid metal salt, multiple antioxidant, wax, oil, vulcanizing agent and vulcanization accelerator.
From the angle of realizing effect of the present invention fully, relative to 100 mass parts rubber components, oil, liquid resin, and the combined content of at least one resin be selected from aforesaid combination is preferably 2-35 mass parts.From the angle of improving fuel economy and wear resistance, this combined content is more preferably 3-15 mass parts.
Rubber combination of the present invention is prepared by general method.Specifically, rubber combination is by such as following method preparation: use Banbury mixer, kneader, open roll mill etc. are mediated component, then carry out sulfuration to mixture.This rubber combination can suitably for tire tread.
More particularly, to rubber components, silicon-dioxide, carbon black, silane coupling agents etc. carry out mediating until outflow temperature reaches 120 ~ 180 DEG C (be preferably 130 ~ 175 DEG C (when silane coupling agent is Si266 for about 150 DEG C; Be about 170 DEG C when silane coupling agent is NXT; Be about 140 DEG C when silane coupling agent is NXTZ or Si363) (basic kneading step).Next, by vulcanizing agent as sulphur, vulcanization accelerators etc. add in mixture, then when kneader is cooled, start to mediate at the temperature of about 50 DEG C, when kneader is used continuously, start to mediate at the temperature of about 80 DEG C, then continue to carry out until final outflow temperature reaches about 110 ~ 120 DEG C (final kneading steps).Then sulfuration is carried out to kneaded mixture, rubber combination of the present invention can be obtained thus.Preferably, basic kneading step is above in two steps performs.Further, in each step in basic kneading step, silicon-dioxide and the preferred portion-wise addition of silane coupling agent are also mediated.More preferably, rubber components, carbon black, first part of silica and the first step of part silane coupling agent in basic kneading step are mediated, and remaining chemical reagent is added in subsequent steps and mediates.Such as, when basic kneading step is made up of two steps, the silicon-dioxide of the rubber components of whole amount and carbon black and half amount and the silane coupling agent of half amount can be added in a first step and mediate, and the silicon-dioxide of residual content and silane coupling agent and other chemical reagent can be added in the kneaded mixture obtained in a first step and to mediate in second step.By this way, the dispersiveness of silicon-dioxide can further improve.
Pneumatic tyre of the present invention can use above-mentioned rubber combination to be manufactured by general method.
Specifically, comprise the rubber combination of said components, before sulfuration, be extruded according to the shape of tyre assembly as tyre surface and process, then on Tire production machine, by normal method shaping thus obtained unvulcanized tire together with other tyre assembly.This unvulcanized tire is heated and pressurized thus forms tire in vulcanizer.
Pneumatic tyre of the present invention can be used as the tire of passenger car, the tire for truck and motorbus, for the tire of SUV (Sport Utility Vehicle) (SUVs), racing-car tyres etc., particularly suitable acts on the tire of passenger car and the tire for SUV (Sport Utility Vehicle).
Embodiment
The present invention more specifically will be described by embodiment, but the invention is not restricted to these embodiments.
(preparation of chain end properties-correcting agent)
Under nitrogen protection; 20.8g 3-(N is loaded in 250ml measuring bottle; N '-dimethylamino) propyl trimethoxy silicane (AZmax Co., Ltd.) and anhydrous hexane (Kanto Kagaku K. K.) make its total amount reach 250ml, obtained chain end properties-correcting agent thus.
(multipolymer prepares 1)
18L hexanaphthene (Kanto Kagaku K. K.) is loaded in the pressure-resistant vessel fully purified through nitrogen (30L), 2000g divinyl (high thousand fringe business Co., Ltd.), the diethyl ether (Kanto Kagaku K. K.) of 53mmol, rises to 60 DEG C by temperature.Next, the butyllithium (commercial firm of Kanto Kagaku K. K.) of 16.6ml is added in mixture, then stir 3 hours.Then add 12ml 0.4mol/L silicon tetrachloride/hexane solution, then stir 30 minutes.Then add 13ml chain end properties-correcting agent, then stir 30 minutes.Be dissolved with 0.2g 2 adding 2ml, after the methyl alcohol (Kanto Kagaku K. K.) of 6-Butylated Hydroxytoluene (Japanese God Light chemical company), reaction soln is transferred in the stainless steel vessel that 18L methyl alcohol is housed, and collects obtained aggregate.By aggregate drying under reduced pressure 24 hours with obtained modification BR.The Mw of this modification BR is 420,000 and contents of ethylene is 13 quality %.
(multipolymer prepares 2)
In the pressure-resistant vessel fully purified through nitrogen (30L), load 18L normal hexane, 540g vinylbenzene (Kanto Kagaku K. K.), the Tetramethyl Ethylene Diamine of 1460g divinyl and 17mmol, rises to 40 DEG C by temperature.Next, the silicon tetrachloride/hexane solution of 3.5ml0.4mol/L is added in mixture, then stir 30 minutes.Then the butyllithium of 10.5ml is joined in mixture, then temperature is risen to 50 DEG C, then stir 3 hours.Then add 30ml chain end properties-correcting agent, then stir 30 minutes.Add after 2ml is dissolved with the methyl alcohol (Kanto Kagaku K. K.) of 0.2g 2,6-Butylated Hydroxytoluene (Japanese God Light chemical company), reaction soln is transferred in the stainless steel vessel that 18L methyl alcohol is housed, and collects obtained aggregate.By aggregate drying under reduced pressure 24 hours with obtained modification SBR.Styrene in this modification SBR is that 27 quality %, Mw are 400,000 and contents of ethylene is 53mol%.
(multipolymer prepares 3)
In the pressure-resistant vessel fully purified through nitrogen (30L), load 18L normal hexane, 740g vinylbenzene (Kanto Kagaku K. K.), the Tetramethyl Ethylene Diamine of 1260g divinyl and 17mmol, rises to 40 DEG C by temperature.Next, the silicon tetrachloride/hexane solution of 3.5ml0.4mol/L is added in mixture, then stir 30 minutes.Then the butyllithium of 10.5ml is joined in mixture, then temperature is risen to 50 DEG C, then stir 3 hours.Then add 30ml chain end properties-correcting agent, then stir 30 minutes.Add after 2ml is dissolved with the methyl alcohol (Kanto Kagaku K. K.) of 0.2g 2,6-Butylated Hydroxytoluene (Japanese God Light chemical company), reaction soln is transferred in the stainless steel vessel that 18L methyl alcohol is housed, and collects obtained aggregate.By aggregate drying under reduced pressure 24 hours with obtained modification SBR.Styrene in this modification SBR is that 37 quality %, Mw are 410,000 and contents of ethylene is 54mol%.
(multipolymer prepares 4)
In the pressure-resistant vessel fully purified through nitrogen (30L), load 18L normal hexane, 520g vinylbenzene (Kanto Kagaku K. K.), the Tetramethyl Ethylene Diamine of 1480g divinyl and 17mmol, rises to 40 DEG C by temperature.Next, the silicon tetrachloride/hexane solution of 3.5ml0.4mol/L is added in mixture, then stir 30 minutes.Then the butyllithium of 10.5ml is joined in mixture, then temperature is risen to 50 DEG C, then stir 3 hours.Then add 30ml chain end properties-correcting agent, then stir 30 minutes.Add after 2ml is dissolved with the methyl alcohol (Kanto Kagaku K. K.) of 0.2g 2,6-Butylated Hydroxytoluene (Japanese God Light chemical company), reaction soln is transferred in the stainless steel vessel that 18L methyl alcohol is housed, and collects obtained aggregate.By aggregate drying under reduced pressure 24 hours with obtained modification SBR.Styrene in this modification SBR is that 26 quality %, Mw are 430,000 and contents of ethylene is 56mol%.
Hereinafter, the chemical reagent used in embodiment and reference examples is summarized.
NR：TSR20
ENR:ENR25 (epoxy natural rubber, Kumpulan Guthrie Berhad company manufactures, the western industry in Malaysia; Epoxy rate: 25mol%)
BR1:CB25, Lanxess company manufactures (with the BR (BR of Nd catalysis) of Nd catalyzer synthesis, cis-content: 97 quality %, contents of ethylene: 0.7 quality %, Mw/Mn:1.78, Mw:500,000, Mn:280,000) BR2:BR150B, Ube Industries, Ltd manufactures (with the BR (BR of Co catalysis) of Co catalyzer synthesis, cis-content: 96 quality %, contents of ethylene: 2.1 quality %, Mw/Mn:2.30, Mw:440,000, Mn:190,000)
Modification BR1 for silicon-dioxide: multipolymer prepares modification BR (contents of ethylene: 13 quality %, cis-content: 38 quality %, trans content: 50 quality %, Mw/Mn:1.19, Mw:420,000) obtained in 1
Modification BR2 for silicon-dioxide: modified polybutadiene rubber (S-modification BR), Sumitomo Chemical Co manufactures.(contents of ethylene 15 quality %; R 1, R 2, R 3=-OCH 3, R 4, R 5=-CH 2cH 3, n=3)
For the modification BR:BR1250H of CB, ZERO company manufactures (with the tin modification BR (the modification BR for carbon black) of lithium initiator polymerization, contents of ethylene: 10 quality %, cis-content: 40 quality %, trans content: 50 quality %, Mw/Mn:1.40, Mw:460,000, Mn:330,000, tin atom content: 250ppm)
Modification SBR1 for silicon-dioxide: multipolymer prepares modification SBR (styrene: 27 quality %) obtained in 2
Modification SBR2 for silicon-dioxide: multipolymer prepares modification SBR (styrene: 37 quality %) obtained in 3
Modification SBR3 for silicon-dioxide: multipolymer prepares modification SBR (styrene: 26 quality %) obtained in 4
E-SBR:SBR1723, JSR Corp. manufactures (styrene: 23.5%)
Carbon black: HP160, Columbia Carbon company manufactures (N 2sA:165m 2/ g)
Silica 1: Zeosil 1085Gr, Phodia company manufactures (N 2sA:90m 2/ g)
Silicon-dioxide 2:Zeosil 1115Gr, Phodia company manufactures (N 2sA:115m 2/ g)
Silicon-dioxide 3:Zeosil 1165MP, Phodia company manufactures (N 2sA:165m 2/ g)
Silicon-dioxide 4:ULTRASIL VN3, Evonik Degussa company manufactures (N 2sA:175m 2/ g)
Silicon-dioxide 5:Zeosil Premium 200MP, Phodia company manufactures (N 2sA:215m 2/ g)
Silicon-dioxide 6:U9000Gr, Evonik Degussa company manufactures (N 2sA:235m 2/ g)
Silicon-dioxide 7:prototype, Tokuyama Co., Ltd manufactures (N 2sA:260m 2/ g)
Silicon-dioxide 8:prototype, Tokuyama Co., Ltd manufactures (N 2sA:280m 2/ g)
Silane coupling agent 1:Si75, Evonik Degussa company manufactures (two (3-triethoxysilylpropyltetrasulfide) disulphide)
Silane coupling agent 2:NXT-Z45, MomentivePerformanceMaterials manufactures
Silane coupling agent 3:NXT, MomentivePerformanceMaterials manufactures
Silane coupling agent 4:Si363, Evonik Degussa company manufactures
Coumarone-indene resin: NOVARES C10, Rutgers chemistry manufactures (liquid coumarone-indene resin, softening temperature: 5-15 DEG C)
Aromatic ethylene polymkeric substance: Sylvares SA85, Arizona chemistry manufactures (alpha-methyl styrene and cinnamic multipolymer, softening temperature: 85 DEG C, Mw:1000)
Terpene phenol resin: Sylvares TP115, Arizona chemistry manufactures (terpene phenol resin, softening temperature: 115 DEG C, hydroxyl value: 50KOH mg/g)
TDAE:VIVATEC 500, H & R manufactures
Wax: Ozoace 0355, Japanese Jing La Co., Ltd. manufactures
Antioxidant: Antigene 6C, Sumitomo Chemical Co manufactures (N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine)
TMQ:NOCRAC 224, Ouchi Shinko Chemical Ind Co., Ltd. manufactures
Stearic acid: stearic acid " Tsubaki ", Japan Oil Co manufactures
Zinc oxide: Ginrei R, Dong Bangxin industry Co., Ltd. manufactures
Powder sulphur containing 5% oil: HK-200-5, Hosoi chemical company manufactures
TBBS:NOCCELER NS-G, Ouchi Shinko Chemical Ind Co., Ltd. manufactures (the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine)
DPG:NOCCELER D, Ouchi Shinko Chemical Ind Co., Ltd. manufactures (vulkacit D)
(embodiment and reference examples)
Each formula according to table 1 and 2, by rubber components, the silicon-dioxide of half amount, the carbon black of whole amount and the silane coupling agent of half amount use 1.7L Banbury mixer to mediate until mediate temperature to reach 150 DEG C, to prepare kneaded mixture 1.Next, by the kneaded mixture 1 obtained, the silicon-dioxide of residual content and silane coupling agent, the residue chemical reagent outside sulphur removal and vulcanization accelerator joins in 1.7L Banbury mixer to be mediated until mediate temperature to reach 150 DEG C, to prepare kneaded mixture 2.Then, sulphur and vulcanization accelerator are joined in obtained kneaded mixture 2, then use open roll mill to carry out mediating until mediate temperature to reach 105 DEG C, to prepare unvulcanized rubber composition.
At obtained unvulcanized rubber composition is placed in 170 DEG C, press vulcanization 12 minutes is to prepare vulcanizate compositions.
Respectively, obtained unvulcanized rubber composition is shaped to the shape of tyre surface, on Tire production machine and other tyre assembly fit together, be then placed in 170 DEG C of press vulcanizations 12 minutes to prepare testing tire.(tire size: 245/40R18).
Vulcanizate compositions obtained thus and testing tire are according to assessing as follows, and test result is shown in table 1 and 2.
(visco-elasticity test)
Use the visco-elasticity spectrometer VES manufactured by Iwamoto Seisakusho Co., Ltd., the complex modulus E* (MPa) of vulcanizate compositions and losstangenttanδ are measured, condition determination is 30 DEG C of temperature, 10Hz frequency, 10% initial strain and 2% dynamic strain.E* value larger expression rigidity is higher, so operational stability is better.Tan δ value is less, and heat generation is lower, so fuel economy is higher.This tan δ value is also expressed as the index relative to reference examples 1 (=100).This index higher expression fuel economy is higher.
(wet earth-catching property)
Often organize on automobile that testing tire is all arranged on the front engine rear wheel drive (FR) that Japan manufactures (displacement: 2000cc), and this automobile travels on the test road of moist 10 times than bituminous pavement.Then the control stiffness of test drive person to the period that drives a car is evaluated.Result is expressed as the index relative to reference examples 1 (=100).The higher then wet earth-catching property of this index is better.
(wear resistance)
Often organize on automobile that testing tire is all arranged on the front engine rear wheel drive (FR) that Japan manufactures (displacement: 2000cc), and this automobile travels on the test road with dried asphalt road.Then the residue groove depth (initial depth: 8.0mm) of tire tread rubber is measured to assess wear resistance.Residue groove depth is larger, and wear resistance is better.Residue groove depth is expressed as the index relative to reference examples 1 (=100).This index is higher, and wear resistance is better.
(Elongation test)
No. 3 dumbbell shape samples obtained by this vulcanizate compositions, according to JIS K 6251 " mensuration of vulcanized rubber or thermoplastic elastomer-tensile stress-deformation nature ", at room temperature carry out Elongation test, to measure elongation at break EB (%).The larger expression elongation at break of EB value (weather resistance) is better.
[table 1]
Table 1 and 2 displays, embodiment shows outstanding wear resistance and good fuel economy, wet earth-catching property and elongation at break (weather resistance), it is 160-270m that embodiment employs the modification low cis BR for silicon-dioxide of predetermined content and SBR and N2 adsorption specific surface area 2the silicon-dioxide of/g.

Claims (10)

1. a rubber composition for tire tread,
With 100 quality % rubber components for benchmark, described rubber combination comprises: the cis-content of 8-40 quality % is the modified polybutadiene rubber for silicon-dioxide of below 50 quality %, and 25-75 quality % styrene-butadiene rubber(SBR); And
Relative to 100 mass parts rubber components, the N2 adsorption specific surface area that described rubber combination comprises 40-120 mass parts is further 160-270m 2the silicon-dioxide of/g.
2. rubber composition for tire tread as claimed in claim 1,
Wherein, for the modified polybutadiene rubber of silicon-dioxide for being selected from least one in the group that is made up of following polybutadiene rubber: by the compound modified polybutadiene rubber shown in following formula (1), by the polybutadiene rubber of low-molecular weight compound modification comprising Racemic glycidol amino in molecule, with the polybutadiene rubber by mixture modification, described mixture is included in molecule containing the low-molecular weight compound of Racemic glycidol amino and the dipolymer of described low-molecular weight compound or high-order oligopolymer
Wherein R 1, R 2and R 3be same to each other or different to each other, and represent alkyl, alkoxyl group, siloxy-, acetal radical, carboxyl separately, sulfydryl or their derivative; R 4and R 5be same to each other or different to each other, and represent hydrogen atom or alkyl separately, R 4and R 5can be bonded to each other and form ring structure together with nitrogen-atoms; And n is integer.
3. rubber composition for tire tread as claimed in claim 2,
Wherein, the low-molecular weight compound of Racemic glycidol amino is comprised in described molecule for the compound shown in following formula:
Wherein, R 11and R 12be same to each other or different to each other, and represent C1-10 alkyl separately, described C1-10 alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 13and R 14be same to each other or different to each other, and represent hydrogen atom or C1-20 alkyl separately, described C1-20 alkyl comprises at least one in the group being selected from and being made up of ether and tertiary amine groups alternatively; R 15represent C1-20 alkyl, described C1-20 alkyl comprises at least one in the group being selected from and being made up of ether, tertiary amine groups, epoxy group(ing), carbonyl and halogen group alternatively; And m is the integer of 1-6.
4. the rubber composition for tire tread according to any one of claim 1-3,
Wherein, described styrene-butadiene rubber(SBR) comprises the modified styrene butadiene rubber for silicon-dioxide.
5. the rubber composition for tire tread according to any one of claim 1-4,
Wherein, relative to the silicon-dioxide of 100 mass parts, described rubber combination comprises at least one silane coupling agent be selected from the group be made up of following compound of 1-15 mass parts:
Compound such as formula shown in (I):
Wherein, R 101to R 103respective representative has side chain or unbranched C1-12 alkyl, has side chain or unbranched C1-12 alkoxyl group, or-O-(R 111-O) z-R 112, wherein z R 111respective representative has side chain or unbranched C1-30 bivalent hydrocarbon radical, z R 111be same to each other or different to each other, R 112representative has side chain or unbranched C1-30 alkyl, has side chain or unbranched C2-30 alkenyl, C6-30 aryl or C7-30 aralkyl, and z represents the integer of 1-30, R 101to R 103be same to each other or different to each other; And R 104representative has side chain or unbranched C1-6 alkylidene group,
Comprise the compound of the connector element A as shown in formula II and the connector element B as shown in formula III:
Wherein, R 201represent hydrogen, halogen, have side chain or unbranched C1-30 alkyl, have side chain or unbranched C2-30 alkenyl, have side chain or unbranched C2-30 alkynyl or end hydrogen by the alkyl of hydroxyl or carboxyl substituted, R 202representative has side chain or unbranched C1-30 alkylidene group, has side chain or unbranched C2-30 alkenylene or have side chain or unbranched C2-30 alkynylene, R 201and R 202ring structure can be formed together, and
The compound be shown below:
6. the rubber composition for tire tread according to any one of claim 1-5,
Wherein, with 100 quality % rubber components for benchmark, the amount using the polybutadiene rubber of rare earth catalyst synthesis is below 40 quality %.
7. the rubber composition for tire tread according to any one of claim 1-6, wherein,
Described rubber combination comprises the liquid resin that softening temperature is-20 ~ 45 DEG C,
Described liquid resin is at least one in liquid coumarone-indene resin and liquid terpene resin.
8. the rubber composition for tire tread according to any one of claim 1-7, wherein,
Described rubber combination comprises terpine resin, softening temperature that to be selected from by softening temperature be 46 ~ 160 DEG C to be Gum Rosin, the softening temperature of 46 ~ 140 DEG C the be C5 petroleum resin of 46 ~ 140 DEG C and softening temperature are at least one resin in the group that forms of the anine of 46 ~ 140 DEG C.
9. a pneumatic tyre, it is obtained by the rubber combination such as according to any one of claim 1-8.
10. pneumatic tyre as claimed in claim 9, it is for passenger car or SUV (Sport Utility Vehicle).
CN201380038132.7A 2012-08-03 2013-06-13 Rubber composition for tire tread and pneumatic tire Expired - Fee Related CN104487506B (en)

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CN107429006A (en) * 2014-12-22 2017-12-01 亚利桑那化学品有限责任公司 additive for rubber composition
CN109195810B (en) * 2016-06-07 2021-02-02 倍耐力轮胎股份公司 Tyre for vehicle wheels
CN109195810A (en) * 2016-06-07 2019-01-11 倍耐力轮胎股份公司 Tire for wheel
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CN110520470A (en) * 2017-04-14 2019-11-29 住友橡胶工业株式会社 Pneumatic tire
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