CN103374151A - Rubber composition for sidewall/clinch of tire and pneumatic tire - Google Patents
Rubber composition for sidewall/clinch of tire and pneumatic tire Download PDFInfo
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- CN103374151A CN103374151A CN2013100322496A CN201310032249A CN103374151A CN 103374151 A CN103374151 A CN 103374151A CN 2013100322496 A CN2013100322496 A CN 2013100322496A CN 201310032249 A CN201310032249 A CN 201310032249A CN 103374151 A CN103374151 A CN 103374151A
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Abstract
The invention provides a rubber composition for the sidewall/clinch of a tire and a pneumatic tire formed through utilizing the rubber composition, wherein the properties of low heat, anti-crack growth resistance and discoloration resistance are further improved in a balanced manner at a low manufacturing cost. Taking the content of a rubber component as 100 parts by mass, the rubber composition for the sidewall/clinch of a tire comprises more than 2 parts of wet silica with the BET thereof to be 70 -250 m2/g; 20-40 parts of carbon black with the BET thereof to b 27-125 m2/g; and 2.0 -7.0 parts of at least one selected from cyclohexane diamine antioxidant and quinoline antioxidant.
Description
Technical field
The present invention relates to a kind of rubber combination for sidewall or clinch, and comprise the sidewall that formed by this rubber combination and/or the pneumatic tyre of clinch.
Background technology
The assembly that is used for doughnut is required to have various performances such as sidewall and clinch, such as rolling resistance, cracking growth resistance and weather resistance, and wishes simultaneously to suppress variable color such as the brown variable color on the parts surface.For example, in order to improve the performance of the aspects such as rolling resistance, weather resistance, there is following known method: reduce the weight of reinforcing filler, perhaps use the modification divinyl rubber, contain 1, the divinyl rubber of 2-syndiotactic polybutadiene crystal or hybrid cross-linked dose.
In addition, the reduction assembly causes alleviating of tire weight such as the thickness of sidewall section, thereby is conducive to reduce rolling resistance.Yet, because antioxidant is easy to volatilization or loss between sulfuration or usage period, so the situation when having common thickness with assembly is compared, need to mix more substantial antioxidant this moment.Therefore, be difficult to guarantee anti-discoloration.In addition, also should be taken into account, a certain amount of antioxidant sneaked into carcass with in the rubber combination or air retaining wall or in conjunction with glue with in the rubber combination, so that antioxidant little by little shifts in sidewall during use.Yet at the mileage initial stage, antioxidant causes lip-deep frostization via thermal fatigue and flexural fatigue and homogenize at whole sidewall rubber.So, be difficult to obtain sufficient anti-discoloration.
Patent documentation 1 proposes the method that a kind of divinyl rubber, natural rubber that comprises 1,2-syndiotactic polybutadiene crystal by use etc. improves fuel economy, cracking growth resistance etc.On the performance of improving the aspects such as rolling resistance (low heat generation), cracking growth resistance and anti-discoloration with balance mode, the method still has improved space.
Reference listing
Patent documentation
Patent documentation 1:JP-A2006-63143.
Summary of the invention
Technical problem
The object of the invention is to address the above problem and be provided for the rubber combination of sidewall or clinch, this rubber combination is lower with performance and its manufacturing cost that balance mode improves low heat generation, cracking growth resistance and anti-discoloration aspect, and the present invention also provides a kind of pneumatic tyre that is formed by this rubber combination.
The scheme of dealing with problems
The present invention relates to a kind of rubber combination for sidewall or clinch, with respect to the rubber components of per 100 mass parts, it comprises the above BET specific surface area of 2 mass parts is 70-250m
2The wet silicon-dioxide of/g; At least 20 mass parts but be 27-125m less than the BET specific surface area of 40 mass parts
2The carbon black of/g; And the 2.0-7.0 mass parts be selected from least a in phenylenediamine antioxidant and the quinoline antioxidant.
The BET specific surface area of preferred carbon black is 27-50m
2/ g.
Take the rubber components of 100 quality % as benchmark, the preferred rubber component comprises the isoprene rubber of 25-70 quality %, the divinyl rubber of 30-75 quality %, and the styrene-butadiene rubber(SBR) of 0-20 quality %.
In addition, the preferred rubber composition comprises at least a in quinoline antioxidant and the bisphenol antioxidant.
The rubber combination that is preferred for sidewall or clinch does not comprise silane coupling agent.
The invention still further relates to and comprise each the freely sidewall that forms of this rubber combination and at least a pneumatic tyre in the clinch.
Excellent technique effect of the present invention
With respect to per 100 mass parts rubber components, the BET specific surface area that the rubber combination for sidewall or clinch according to the present invention comprises more than 2 mass parts is 70-250m
2The wet silicon-dioxide of/g; At least 20 mass parts but be 27-125m less than the BET specific surface area of 40 mass parts
2The carbon black of/g; And the 2.0-7.0 mass parts be selected from least a in phenylenediamine antioxidant and the quinoline antioxidant.So this rubber combination can improve the performance of hanging down heat generation, cracking growth resistance and anti-discoloration aspect by balance mode.In addition, thus this rubber combination and use the cost manufacturing that its pneumatic tyre can be lower to realize cost.
Description of drawings
Fig. 1 is the synoptic diagram of the part of the cross section of demonstration tire according to the embodiment of the present invention.
Embodiment
With respect to per 100 mass parts rubber components, the BET specific surface area that the rubber combination for sidewall or clinch of the present invention comprises more than 2 mass parts is 70-250m
2The wet silicon-dioxide of/g; At least 20 mass parts but be 27-125m less than the BET specific surface area of 40 mass parts
2The carbon black of/g; And the 2.0-7.0 mass parts be selected from least a in phenylenediamine antioxidant and the quinoline antioxidant.
Have particular B ET specific surface area and from the teeth outwards in the situation of wet silicon-dioxide as the part of reinforcing filler with hydroxyl in interpolation, thereby silicon-dioxide will be attracted in order to suppress antioxidant excessive frostization on the surface of sidewall or clinch by the polar group in phenylenediamine or the quinoline antioxidant.So the variable color of assembly surface (for example, the brown variable color) can be suppressed, and simultaneously, can also increase the amount of antioxidant to improve cracking growth resistance.In addition, because that the content with carbon black of particular B ET specific surface area is adjusted to is less, so can also reduce rolling resistance.Therefore, the present invention can provide sidewall or the clinch that the performance of the aspects such as its low heat generation, cracking growth resistance and anti-discoloration can balance mode be enhanced.
The example that can be used as the material of rubber components comprises natural rubber (NR), epoxy natural rubber (ENR), synthetic polyisoprene (IR), divinyl rubber (BR), styrene-butadiene rubber(SBR) (SBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene-elastoprene (EPDM), chloroprene rubber (CR), paracril (NBR), isoprene-isobutylene rubber (IIR) etc.Wherein, consider cracking growth resistance, low heat generation etc., it is preferably that isoprene rubber is used in combination with BR, and can additionally add SBR according to estimated performance.These elastomeric materials can use separately or two or more being used in combination.
The example of isoprene rubber comprises NR, IR, modified natural rubber etc.The example of NR comprises DPNR (DPNR), and the example of modified natural rubber comprises epoxy natural rubber (ENR), purifying natural rubber (purifying NR) etc.Wherein, NR and IR are preferred, and NR is preferred.
As for NR, can use to be generally used in the rubber industry those, such as SIR20, RSS#3, TSR20 etc.In addition, IR is not particularly limited, and can use to be generally used in the rubber industry those.
Take the rubber components of 100 quality % as benchmark, the content of isoprene rubber is preferably more than the 25 quality %, more preferably more than the 30 quality %.If its content is lower than 25 quality %, extension at break may be insufficient so.In addition, below the preferred 70 quality % of the content of isoprene rubber, more preferably below the 60 quality %, more preferably below the 50 quality %.If its content surpasses 70 quality %, cracking growth resistance may be insufficient so.
The example of BR comprises high-cis 1，4-polybutadiene rubber (high-cis BR), contains the divinyl rubber (BR that contains SPB) of 1,2-syndiotactic polybutadiene crystal, modification divinyl rubber (modification BR), use the BR of rare earth catalyst etc.These BR can use separately or two or more being used in combination.
For example, consider wear resistance, the high-cis BR with the above cis of 90 quality %-Isosorbide-5-Nitrae content is disclosed as preferred BR.
The BR that preferably contains SPB, wherein 1,2-syndiotactic polybutadiene crystal (SPB) is allowed to and then the BR chemistry links and disperse, rather than simply is dispersed among the BR.When moulding of tyres, arrange in the rubber combination in the flash hole (spew hole) 1,2-syndiotactic polybutadiene crystal helps to improve hardness or the intensity of rubber combination, the appearance of this flash (broken spew) that can establishment break during the tire demoulding.
The fusing point of 1,2-syndiotactic polybutadiene crystal is preferably 180 ° more than the C, more preferably 190 ° more than the C.If its fusing point is lower than 180 ° of C, hardness is tending towards reducing so, and this is because this crystal melts between the tire pressurization curing time.In addition, its fusing point is preferably 220 ° below the C, more preferably 210 ° below the C.If its fusing point surpasses 220 ° of C, the molecular weight of BR is tending towards increasing so, thereby deteriorated its dispersiveness in rubber combination causes the relatively poor processibility of extruding thus.
The content that contains the insolubles in the normal hexane of boiling of BR of SPB is preferably more than the 2.5 quality %, more preferably more than the 8 quality %.If its content is lower than 2.5 quality %, can not obtain so the sufficient hardness of rubber combination.In addition, the content of the insolubles in the normal hexane of boiling is preferably below the 22 quality %, more preferably below the 20 quality %, more preferably below the 18 quality %.If its content surpasses 22 quality %, the viscosity of BR itself is tending towards higher so, so BR and the reinforcing filler dispersiveness in rubber combination is tending towards deteriorated.In addition, " insolubles in the normal hexane of boiling " refers to contain 1 among the BR of SPB, 2-syndiotactic polybutadiene.
Contain 1 among the BR of SPB, the content of 2-syndiotactic polybutadiene crystal is preferably more than the 2.5 quality %, more preferably more than the 10 quality %.If its content is lower than 2.5 quality %, rubber hardness is tending towards insufficient so.In addition, the content of 1,2-syndiotactic polybutadiene crystal is preferably below the 20 quality %, more preferably below the 18 quality %.If its content surpasses 20 quality %, BR is tending towards being difficult to disperse in rubber combination so, so it is deteriorated that processibility is tending towards.
In the situation that the BR that contains SPB is used, take the rubber components of 100 quality % as benchmark, the content that contains the BR of SPB is preferably more than the 15 quality %, more preferably more than the 25 quality %.If its content is lower than 15 quality %, rubber hardness is tending towards insufficient so.In addition, the content that contains the BR of SPB is preferably below the 50 quality %, more preferably below the 45 quality %, more preferably below the 35 quality %.If its content surpasses 50 quality %, processibility is tending towards deteriorated so.
The example of modification BR is tin modification BR, and it is by using lithium initiator polymerization 1,3-butadiene, then making to its interpolation tin compound.Tin modification BR is preferably the tin modification BR of its molecule take tin-carbon bond as terminal.
The example of lithium initiator comprises lithium compound such as lithium alkylide, lithium aryl, vinyl lithium, organotin lithium, and the organonitrogen lithium compound, and the lithium metal.Lithium initiator can prepare as the use of the initiator that is used for modification BR and has than high-vinyl-content with than the modification BR of low cis content.
The example of tin compound comprises tin tetrachloride, trichlorine butyl tin, dichloro dibutyl tin, dichloro dioctyl tin, tributyltin chloride, triphenyltin chloride, phenylbenzene dibutyl tin, oxyethyl group triphenyltin, phenylbenzene tin methide, xylyl chloride base tin, two sad tin diphenyls, divinyl tin ethide, tin tetraphenyl, distearyl acid dibutyl tin, tetra allylic tin, and vinylbenzene is to tributyl tin.
Tin atom content among the tin modification BR is preferably more than the 50ppm, more preferably more than the 60ppm.If tin atom content is lower than 50ppm, accelerate so the effect that carbon black disperses and be tending towards less in modification BR, and the value of tan δ is tending towards increasing.In addition, tin atom content is preferably below the 3000ppm, more preferably below the 2500ppm, more preferably below the 250ppm.If tin atom content surpasses 3000ppm, extrude so processibility and be tending towards deteriorated, thereby this is may demonstrate relatively poor cohesiveness formation Roughen Edges because mediate mixture.
The molecular weight distribution of tin modification BR (Mw/Mn) is preferably below 2, more preferably below 1.5.If Mw/Mn surpasses 2, the dispersiveness of carbon black is tending towards value deteriorated and tan δ and is tending towards increase so.Should be noted that the Mw that uses among the present invention and Mn are the values of measuring and proofreading and correct with polystyrene standard by gel permeation chromatography (GPC).
Vinyl binding capacity among the tin modification BR is preferably more than the 5 quality %, more preferably more than the 7 quality %.If its vinyl binding capacity is lower than 5 quality %, the polymerization of modification BR (preparation) is tending towards difficulty so.In addition, its vinyl binding capacity is preferably below the 50 quality %, more preferably below the 20 quality %.If its content surpasses 50 quality %, the dispersiveness of carbon black is tending towards value deteriorated and tan δ and is tending towards increase so.
In the situation that tin modification BR is used, take 100 quality % rubber components as benchmark, the content of tin modification BR is preferably more than the 15 quality %, more preferably more than 25 quality.In addition, below the preferred 55 quality % of the content of tin modification BR, more preferably below the 45 quality %, more preferably below the 35 quality %.Being combined with of tin modification BR helps improve low heat generation, so balance has been improved this performance and cracking growth resistance.
Rare earth BR is the divinyl rubber that uses rare earth catalyst synthetic, and its take have than high-cis content and than low vinyl content as feature.The example of rare earth BR comprises those during being generally used for tire makes.
As for the rare earth catalyst for the synthesis of rare earth BR, can use known those in the association area, and its example comprises lanthanide series rare-earth elements compound, organo-aluminium compound, aikyiaiurnirsoxan beta or halogen contained compound, have alternatively Lewis base.Wherein, the Nd catalyzer is particularly preferred, its comprise contain neodymium (Nd) compound as the lanthanide series rare-earth elements compound.
The example of lanthanide series rare-earth elements compound comprises that atomicity is halogenide, carboxylate salt, alcoholate, sulfo-alcoholate and the amide of the rare earth metal of 57-71.Wherein, consider to obtain to have than high-cis content and than the BR of low vinyl content that above-mentioned Nd catalyzer is preferred.
The example of organo-aluminium compound comprises uses general formula AlR
aR
bR
cThe compound of expression (R wherein
a, R
bAnd R
cBe same to each other or different to each other, and represent separately hydrogen or have the alkyl of 1-8 carbon atom).The example of aikyiaiurnirsoxan beta comprises non-annularity aikyiaiurnirsoxan beta and ring-type aikyiaiurnirsoxan beta.The example that contains the compound of halogen comprises uses general formula AlX
kR
d 3-k(wherein X is halogen to the aluminum halide of expression, R
dBe C1-20 alkyl, aryl or aralkyl, and k is 1,1.5,2 or 3); The halogenation strontium is such as Me
3SrCl, Me
2SrCl
2, MeSrHCl
2And MeSrCl
3And metal halide is such as silicon tetrachloride, tin tetrachloride and titanium tetrachloride.Lewis base is used to compound lanthanide series rare-earth elements compound, and its suitable example comprises methyl ethyl diketone, ketone and alcohol.
Rare earth catalyst can be when the polymerization divinyl be used with the solution in the organic solvent (such as normal hexane, hexanaphthene, normal heptane, toluene, dimethylbenzene, benzene etc.) or the form that is loaded on suitable carrier (for example silicon-dioxide, magnesium oxide and magnesium chloride).As for polymerizing condition, polymerization can be solution polymerization or mass polymerization, and polymerization temperature is preferably-30 to 150 ° of C, and polymerization pressure is selected suitably according to other conditions.
The mooney viscosity ML of rare earth BR
1+4(100 ° of C) is preferably more than 35, more preferably more than 40.If its mooney viscosity is lower than 35, the viscosity of unvulcanized rubber composition is tending towards lower so, and after sulfuration, is tending towards keeping suitable thickness.Its mooney viscosity is preferably below 55, more preferably below 50.If its mooney viscosity surpasses 55, unvulcanized rubber composition is tending towards becoming too hard so, thereby is not easy to extrude to form the extrudate with smooth edges.Herein, mooney viscosity is measured according to ISO289 or JIS K6300.
Rare earth BR preferably has more than 1.2, the more preferably ratio (Mw/Mn) of the molecular-weight average more than 1.5 (Mw) and number-average molecular weight (Mn).If this ratio is less than 1.2, processibility is tending towards obviously relatively poor so.Mw/Mn is preferably below 5, more preferably below 4.If this ratio surpasses 5, the performance of heat generation aspect is tending towards relatively poor so.
The Mw of rare earth BR is preferably more than 300,000, more preferably more than 320,000.In addition, its Mw is preferably 1,500, below 000, and more preferably 1,300, below 000.In addition, the Mn of rare earth BR is preferably more than 100,000, and more preferably more than 150,000, and its Mn is preferably 1,000, below 000, more preferably below 800,000.If Mw or Mn are lower than lower limit, the performance of heat generation or extension at break aspect is tending towards relatively poor so.On the contrary, if Mw or Mn surpass the upper limit, processibility is deteriorated so.Herein, Mw and Mn are the values of measuring and proofreading and correct with polystyrene standard by gel permeation chromatography (GPC).
The cis of rare earth BR-Isosorbide-5-Nitrae content is preferably more than the 90 quality %, more preferably more than the 93 quality %, more preferably more than the 95 quality %.If its cis-Isosorbide-5-Nitrae content is lower than 90 quality %, extension at break or wear resistance are tending towards relatively poor so.
The contents of ethylene of rare earth BR is preferably below the 1.8 quality %, more preferably below the 1.0 quality %, more preferably below the 0.5 quality %, particularly preferably below the 0.3 quality %.If its contents of ethylene surpasses 1.8 quality %, extension at break or wear resistance are tending towards relatively poor so.Herein, the contents of ethylene among high-cis BR, modification BR and the rare earth BR (1，2-butadiene unit content) and cis-Isosorbide-5-Nitrae content can be determined by infrared absorption spectrum.
In the situation that rare earth BR is used, take the rubber components of 100 quality % as benchmark, the content of rare earth BR is preferably more than the 15 quality %, more preferably more than the 25 quality %.In addition, the content of rare earth BR is preferably below the 70 quality %, more preferably below the 60 quality %, more preferably below the 40 quality %.Being combined with of rare earth BR helps improve rubbery intensity, thereby improves Performance Ratio such as cracking growth resistance and wear resistance.
In above-mentioned BR, tin modification BR is because of its low febrifacient advantage but particularly preferred, and the BR that contains SPB because of its in the advantage of rubbery intensity and cracking growth resistance but preferred.So, preferably these BR use that is combined, this is because above-mentioned effect of the present invention can fully be obtained.In addition, rare earth BR because of its in the advantage of extension at break and wear resistance but preferred; And it is preferred using the synthetic BR of Nd catalyzer, and the high-cis BR that uses the Nd catalyzer to synthesize is more preferably.
In rubber combination of the present invention, in the rubber components with 100 quality %, the content of BR is preferably more than the 30 quality %, more preferably more than the 40 quality %, more preferably more than the 50 quality %.If its content is lower than 30 quality %, cracking growth resistance is tending towards relatively poor so, so the weather resistance of the sidewall that makes or clinch is tending towards insufficient.In addition, the content of BR is preferably below the 75 quality %, more preferably below the 65 quality %.If its content surpasses 75 quality %, EB and processibility are tending towards deteriorated so.
Take 100 quality % rubber components as benchmark, the total content of isoprene rubber and BR is preferably more than the 80 quality %, more preferably more than the 90 quality %, more preferably more than the 95 quality %.Its total content can be 100 quality %.If its total content is lower than 80 quality %, can not obtain so abundant effect of the present invention.
The example of SBR includes but not limited to the SBR of solution polymerization, the SBR of letex polymerization and the modification SBR that derives thus.The example of modification SBR comprises those (for example 3-TSL 8330, APTES, 3-aminopropyl dimethyl methyl TMOS, 3-aminopropyl methyl dimethoxysilane, 2-dimethyl aminoethyl Trimethoxy silane, 3-diethylamino propyl trimethoxy silicane and 3-dimethylaminopropyl Trimethoxy silanes) that the compound described by modification JP-A2010-111753 is modified.
In the combined situation of SBR, take 100 quality % rubber components as benchmark, the content of SBR is preferably below the 20 quality %, more preferably below the 15 quality %, more preferably below the 10 quality %.If its content surpasses 20 quality %, total content relative reduce of isoprene rubber and BR so is so can not obtain abundant effect of the present invention.The lower limit of its content is not particularly limited.
Rubber combination of the present invention comprises that the BET specific surface area is that the wet silicon-dioxide of particular value is as reinforcing filler.The excessive frostization of antioxidant is by the OH group on the silica sphere and the attraction effect between the polar group in the antioxidant and suppressed, so can suppress the brown variable color.Simultaneously, cracking growth resistance also can be enhanced by the amount that increases antioxidant.In addition, the combination of silicon-dioxide causes sufficient extension at break.In addition, the cost of the carbon black of petroleum increases day by day and the cost of silicon-dioxide becomes relatively lower day by day with respect to carbon black owing to be derived from, so can also reduce manufacturing cost.
The BET specific surface area of wet silicon-dioxide is 70-250m
2/ g is preferably 80-230m
2/ g, more preferably 100-200m
2/ g.If its BET specific surface area is lower than 70m
2/ g can not suppress the brown variable color so, and extension at break and wear resistance are tending towards relatively poor.If its BET specific surface area surpasses 250m
2/ g, the performance of heat generation or processibility aspect is tending towards relatively poor so.
In per 100 mass parts rubber components, the content of specific wet silicon-dioxide is more than 2 quality are divided, and is preferably more than 3 mass parts, more preferably more than 5 mass parts.If its content is lower than 2 mass parts, can not suppress fully the brown variable color so, and the effect that is difficult for obtaining sufficient cost effect and strengthens EB.Its upper limit is not particularly limited, but is preferably below 15 mass parts, more preferably below 12 mass parts, more preferably below 10 mass parts.If its content surpasses 15 mass parts, so wet silicon-dioxide is tending towards before sulfuration again subclustering, and rubber combination is tending towards shrinking when extruding.In addition, for the again subclustering that prevents wet silicon-dioxide to improve tan δ, may need to add silane coupling agent.This is tending towards increasing manufacturing cost.
In addition, the content of wet silicon-dioxide be preferably be contained in below 1/3 of total content of the reinforcing filler in the rubber combination of the present invention, more preferably below 1/4.Its content surpass 1/3 and the content of silicon-dioxide surpass in the situation of 15 quality %, for the again subclustering that prevents wet silicon-dioxide to improve tan δ, may need to add silane coupling agent.This is tending towards increasing manufacturing cost.
Rubber combination of the present invention comprises that specific carbon black is as reinforcing filler.The combination of wet silicon-dioxide and specific carbon black predetermined amount can improve the performance of hanging down heat generation, cracking growth resistance and anti-discoloration aspect by balance mode.
The BET specific surface area of specific carbon black is 27-125m
2/ g is preferably 27-85m
2/ g considers heat generation, and more preferably its BET specific surface area is 27-50m
2/ g.If its BET specific surface area is lower than 27m
2/ g, electroconductibility or extension at break are tending towards relatively poor so.In addition, if its BET specific surface area surpasses 125m
2/ g, heat generation, shrinking percentage and the performance of extruding the processibility aspect are tending towards insufficient so.
In the rubber components of per 100 mass parts, the content of specific carbon black is at least 20 mass parts but be lower than 40 mass parts, preferred 25-38 mass parts, more preferably 27-38 mass parts.If its content is lower than 20 mass parts, cracking growth resistance can reduce so.In addition, curb abradability (curb abrasion), electroconductibility, shrinking percentage and the performance of extruding the processibility aspect are tending towards relatively poor.If its content is more than 40 mass parts, the performance of heat generation aspect is tending towards relatively poor so.
Except specific wet silicon-dioxide and carbon black, rubber combination of the present invention can comprise any reinforcing filler that is generally used in the tire manufacturing, such as calcium carbonate, talcum and sericite.Yet carbon black and silicon-dioxide are preferably mainly comprised as reinforcing filler because of the advantage at aspects such as cracking growth resistance.
In the situation that reinforcing filler outside specific wet silicon-dioxide and specific carbon black is added, in per 100 mass parts rubber components, its content is preferably below 10 mass parts, more preferably below 3 mass parts.If its content surpasses 10 mass parts, wear resistance is tending towards relatively poor so.
Rubber combination of the present invention can not comprise any silane coupling agent.In this case, can reduce manufacturing cost.In addition, even being set as above-mentioned specified quantitative, the content of silicon-dioxide allow rubber combination when not comprising silane coupling agent, also to have sufficient rubber performance and processibility.The example of silane coupling agent comprises that the sulfuration silane coupling agent is such as two (3-triethoxysilylpropyltetrasulfide) disulphide etc.
In the present invention, phenylenediamine antioxidant and/or quinoline antioxidant are mixed.So, consider ozone resistants, anti-oxidant deterioration and uvioresistant deterioration, can use suitably them.Especially, consider ozone resistants and oxidation-resistance, preferably their uses that is combined.
The example of phenylenediamine antioxidant comprises N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D, N-sec.-propyl-N '-phenyl-Ursol D, N, N '-phenylbenzene-Ursol D, N, N '-two-2-naphthyl-Ursol D, N-cyclohexyl-N '-phenyl-Ursol D, N, N '-two (1-methylheptyl)-Ursol D, N, N '-two (1,4-dimethyl amyl group)-Ursol D, N, N '-two (1-ethyl-3-methyl amyl)-Ursol D, N-4-methyl-2-amyl group-N '-phenyl-Ursol D, N, N '-diaryl-Ursol D, diaryl-Ursol D is obstructed, benzene hexyl-Ursol D, benzene octyl group-Ursol D, and N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-Ursol D.Wherein, N-(1,3-dimethylbutyl)-N '-phenyl-Ursol D is preferred.
The example of quinoline antioxidant comprises 2,2,4 trimethyl 1,2 dihydroquinoline polymer, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihydroquinoline, 6-phenylamino-2,2,4-trimethylammonium-1,2-dihydroquinoline, and gather-2,2,4-trimethylammonium-1,2-dihydroquinoline.
In per 100 mass parts rubber components, the total content of phenylenediamine antioxidant and quinoline antioxidant is more than 2.0 mass parts, more than preferred 3.0 mass parts, more preferably more than 4.0 mass parts.If its total content is lower than 2.0 mass parts, can not obtain so sufficient cracking growth resistance.In addition, in per 100 mass parts rubber components, its total content is below 7.0 mass parts, below preferred 6.0 mass parts, more preferably below 5.0 mass parts.If its total content surpasses 7.0 mass parts, the performance of so variable color (brown variable color) or tan δ aspect is tending towards deteriorated.
In addition, in phenylenediamine antioxidant and quinoline antioxidant were combined situation about using, the proportioning of phenylenediamine antioxidant and quinoline antioxidant (amine type/quinoline type (mass ratio)) was preferably 50/50 to 95/5, and more preferably 60/40 to 80/20.
Except phenylenediamine antioxidant and/or quinoline antioxidant, rubber combination of the present invention can comprise another antioxidant.The example of other antioxidants comprises quinone antioxidant, phenolic antioxidant (single phenol, bis-phenol, triphenol and poly-phenol), thiobisphenol antioxidant, naphthylamines antioxidant, pentanoic antioxidant, benzoglyoxaline antioxidant, thiocarbamide antioxidant, phosphoric acid antioxidant, and organic thioic acid sulfoacid antioxidant.
The example of quinone antioxidant comprises benzoquinones, quinhydrones, catechol, quinondiimine, quinone methane, and quinone bismethane antioxidant.Wherein, the quinondiimine antioxidant is preferred.The object lesson of quinondiimine antioxidant comprises N-sec.-propyl-N '-phenyl-p-quinone diimine, N-(1, the 3-dimethylbutyl)-N '-phenyl-quinondiimine, N, N '-phenylbenzene-p-quinone diimine, N-cyclohexyl-N '-phenyl-p-quinone diimine, N-n-hexyl-N '-phenyl-p-quinone diimine, and N, N '-dioctyl-p-quinone diimine.Wherein, N-(1,3-dimethylbutyl)-N '-phenyl-quinondiimine (6QDI) is preferred.Further, other examples of quinone antioxidant comprise 2,5-diamyl quinhydrones and 2,5 di tert butylhydroquinone.
As for phenolic antioxidant, the object lesson of single phenolic antioxidant comprises 2,6-di-t-butyl-4-sylvan, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-tert-butylphenol, 1-oxygen base-3-methyl-4-isopropyl benzene, 2-methyl-4,6-two [(octylsulfo) methyl] phenol, butyl hydroxyanisole, 2,4-dimethyl-6-tert-butyl phenol, n-octyl decyl 3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-propionic ester, SP styrenated phenol, and the derivative of phenol.The object lesson of bis-phenol, triphenol or poly-phenolic antioxidant comprises 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2,2 '-methylene radical-two (4-ethyl-6-tert-butyl phenol), 4,4 '-butylidene-two (3-methyl-6-tert butyl phenol), 1,1 '-two (4-hydroxy phenyl) hexanaphthene, and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl)-propionic ester] methane.
The example of thiobisphenol antioxidant comprises 4,4 '-sulfo-two (the 6-tertiary butyl-3-sylvan) and 2,2 '-sulfo-two (the 6-tertiary butyl-4-sylvan).
The example of naphthylamines antioxidant comprises phenyl-a-naphthylamine, Phenyl beta naphthylamine, and aldol-α-trimethylammonium-1, the 2-naphthylamines.
The example of pentanoic antioxidant comprises p-isopropoxy pentanoic, p-(p-tolylsulfonyl ammonia) pentanoic, N, N-diphenylacetylene diamines, and octylated diphenylamine.
The example of benzoglyoxaline antioxidant comprises 2 mercaptomethyl benzimidazole and 2-mercaptobenzimidazole.The example of thiocarbamide antioxidant comprises tributyl thiourea.The example of phosphoric acid antioxidant comprises three (nonyl phenyl) phosphite.The example of organic thioic acid sulfoacid antioxidant comprises the dilauryl thiodipropionate.
In per 100 mass parts rubber components, the total content that is contained in the antioxidant of all kinds in the rubber combination of the present invention is preferably more than 2.0 mass parts, more preferably more than 3.0 mass parts, more preferably more than 4.0 mass parts.If its total content is lower than 2.0 mass parts, can not obtain sufficient cracking growth resistance so.In addition, in per 100 mass parts rubber components, its total content is preferably below 10.0 mass parts, more preferably below 7.0 mass parts, more preferably below 6.0 mass parts.If its total content surpasses 10.0 mass parts, the performance of so variable color (brown variable color) or tan δ aspect is tending towards deteriorated.
In the present invention, C5 petroleum resin, C9 petroleum resin, process oil, vegetables oil, coumarone-indene resin etc. can be used as tenderizer.In these tenderizers, for example, preferably use C5 petroleum resin, process oil and coumarone-indene resin.
The C5 petroleum resin are by polymerization C5(carbonatoms: 5) petroleum hydrocarbon obtains.Herein, the C5 petroleum hydrocarbon refers to the C5 fraction (carbonatoms is 5 fraction) by the acquisition of thermolysis petroleum naphtha, its object lesson comprises for example isoprene, 1 of diolefine, 3-pentadiene, Dicyclopentadiene (DCPD), piperylene etc., and monoolefine such as 2-methyl-1-butene alkene, 2-methyl-2-butene, cyclopentenes etc.Herein, in per 100 mass parts rubber components, the content of C5 petroleum resin is preferably the 1-5 mass parts, more preferably the 1-3 mass parts.
As for process oil, for example, can use paraffin process oil, aromatics process oil, and the cycloalkanes process oil.Herein, in per 100 mass parts rubber components, the content of process oil is preferably below 10 mass parts, more preferably the 2-5 mass parts.
Coumarone-indene resin is to contain cumarone and indenes as the resin of the monomeric unit of the skeleton (main chain) that forms resin.Except cumarone and indenes, the example that is contained in the monomer in this skeleton comprises vinylbenzene, alpha-methyl styrene, methyl indenes, and Vinyl toluene.Herein, the softening temperature of coumarone-indene resin is preferably-20 to 45 ° of C, more preferably-10 to 40 ° of C.Ball fell the temperature at place when the softening temperature of coumarone-indene resin referred in ring and ball softening point determinator mensuration JISK6220-1:2001 defined softening temperature.Herein, in per 100 mass parts rubber components, the content of coumarone-indene resin is preferably the 0.5-10 mass parts, more preferably the 2-7 mass parts.
Preferred rubber combination of the present invention comprises linking agent such as sulphur, alkylphenol-sulfur subchloride condenses etc.Sulphur is not particularly limited, can use to be generally used in the tire industry those, for example, sulphur powder, precipitated sulfur, sulfidal, insoluble sulfur, and polymolecularity sulphur.Especially, preferably use insoluble sulfur.
Owing to can obtain good E*, good tan δ and the good adhesion strength to adjacent groups compound (such as carcass, tyre surface etc.), so in per 100 mass parts rubber components, the content of sulphur is preferably more than 0.7 mass parts, more preferably more than 1.2 mass parts.Since can obtain good aging after extension at break, so the content of sulphur be preferably below 2.5 mass parts, more preferably below 2.2 mass parts.
Should be noted that at insoluble sulfur to be used as in the situation of sulphur that the content of sulphur refers to the content of the bright sulfur except oil.
By mixed alkylphenol-sulfur subchloride condenses, improved significantly fuel economy and weather resistance thereby can form on the calorifics than common sulfur-crosslinked more stable crosslinking structure, and improved simultaneously operational stability.Alkylphenol-sulfur subchloride condenses is preferably with the alkylphenol of following general formula (1) expression-sulfur subchloride condenses:
Wherein R is same to each other or different to each other, and represents separately C5-15 alkyl or amyl group; X and y are same to each other or different to each other, and represent separately 1 to 4 integer; And m is 0 to 300 integer.
Consider the alkylphenol-good dispersion of sulfur subchloride condenses in rubber components, m is 0 to 300 integer, is preferably 3 to 100 integer.Considering provides high rigidity (being anti-reversion) effectively, and respectively do for oneself 1 to 4 integer of x and y preferably is 2.Consider the alkylphenol-good dispersion of sulfur subchloride condenses in rubber components, R is C5-15 alkyl or amyl group, is preferably the C8-15 alkyl.
Alkylphenol-sulfur subchloride condenses can prepare by currently known methods, and the example of the method includes but not limited to the method that wherein alkylphenol and sulfur subchloride react with the mol ratio of for example 1:0.9-1.25.
The commercial goods of alkylphenol-sulfur subchloride condenses comprises Tackirol V200(in general formula (1), R=C
8H
17, x=2, y=2, and m is 0 to 100 integer (mean value: 33)), and TS3101(is in general formula (1), R=C
12H
25, x=2, y=2, and m is 170 to 210 integer), these two kinds of materials are made by Taoka Chemical Industries Co. Ltd..
In per 100 mass parts rubber components, the content of alkylphenol-sulfur subchloride condenses is preferably more than 0.2 mass parts, more preferably more than 0.5 mass parts.If its content is lower than 0.2 mass parts, can not obtain so the abundant effect of low tan δ aspect.In per 100 mass parts rubber components, its content is preferably below 5.0 mass parts, more preferably below 2.0 mass parts.If its content surpasses 5.0 mass parts, can obviously reduce extension at break, wear resistance and weather resistance so.
Except said components, rubber combination of the present invention can suitably comprise the gradation composition that is used for traditionally rubber industry, such as zinc oxide, stearic acid, and various vulcanization accelerator.
Rubber combination of the present invention can have electroconductibility (conductive rubber composition that is used for sidewall or clinch).In this case, conductive rubber composition preferably has 1 * 10
8Ω cm is following, more preferably 1 * 10
6The volume specific resistance that Ω cm is following.If its volume specific resistance surpasses 1 * 10
8Ω cm, thus static is tending towards in automobile accumulation causes problem (such as lighting, the people gets an electric shock etc.) during adding fuel so.Herein, by further providing conductive layer with outstanding electroconductibility or by guaranteeing with the sticking adhesive layer pathway in the situation of electroconductibility that with cord body cost increases.In addition, because the mixed main stuffing as conductive layer or cord body usefulness sticking adhesive layer of carbon black, so the performance of heat generation aspect is tending towards deteriorated.Simultaneously, the lower limit of volume specific resistance is not particularly limited.
That sidewall or clinch are with in the situation of conductive rubber composition at rubber combination of the present invention, preferred it comprises conductive carbon black, the dibutyl phthalate oil absorbed dose (DBP) of this carbon black is more than the 300mL/100g, more than the preferred 400mL/100g, more preferably more than the 450mL/100g.This can obtain the superperformance of static resistance (preventing accumulation of static electricity) and rolling resistance aspect.In addition, below the preferred 1000mL/100g of its DBP, more preferably below the 500mL/100g.Herein, the DBP of carbon black measures according to JIS K6217-4:2001.
In the rubber components of per 100 mass parts, more than preferred 0.5 mass parts of the content of conductive carbon black, more preferably more than 3 mass parts.If its content is lower than 0.5 mass parts, can not obtain so sufficient electroconductibility.In per 100 mass parts rubber components, below preferred 10 mass parts of the content of conductive carbon black, more preferably below 8 mass parts.If its content surpasses 10 mass parts, so dispersed can be deteriorated, fuel economy or weather resistance can be deteriorated, and the resistance that makes tire can significantly increase in time.
Rubber combination of the present invention can be used for passenger vehicle with radial, all steel radials (radial with steel band and steel carcass) and industrial automobile with sidewall and clinch in the all-purpose tire, and be particularly useful for fuel economy tire sidewall.
The rubber combination that is used for sidewall or clinch among the present invention can prepare by usual method.Especially, for example, this rubber combination can prepare by the following method: using appts is such as Banbury, kneader or to drive the roller machine kneaded together with above-mentioned rubber components and other gradation compositions optionally, then vulcanizes this mixture.
Pneumatic tyre of the present invention can pass through usual method or winding method manufacturing.Especially, unvulcanized rubber composition is extruded the sidewall that is processed into tire or the shape of clinch, then in the tire molding machine, in common mode itself and other tyre assembly is fitted together to form not vulcanized tyre.Alternatively, the string rubber as belt is wound to form not vulcanized tyre in the tire molding machine.The not vulcanized tyre that obtains by above-mentioned either method experiences heating and pressurizing in vulcanizer, can obtain according to tire of the present invention thus.
With reference to accompanying drawing 1, airtyred example of the present invention is described.Fig. 1 represents the partial cross-sectional view of tire according to the embodiment of the present invention, but the invention is not restricted to this embodiment.
Pneumatic tyre shown in Figure 1 comprises: fetus face 1; Sidewall 4; Clinch 5; Bead part 6; Radially extend internally, then center on the cord body 3 that bead part 6 arranges from fetus face 1 via sidewall 4 along tire; And be arranged on buffer layer 2 between fetus face 1 and the cord body 3.Two ends of cord body 3 are turned back and are centered on pair of bead core 7 closures that are arranged in the bead part 6, and chafer fabric 8 is arranged in the zone that contacts with wheel rim R in the cord body 3.In addition, wheel rim R directly contacts with clinch 5, and clinch 5 is connected with sidewall section with cord body 3 and is connected.
Discharge path as for the earthed surface of the fetus face from wheel rim R to tire 1 shown in Figure 1, exemplary main discharge path comprises successively " the cord body path " via clinch 5, cord body 3, buffer layer 2 and fetus face 1, and successively via " the sidewall path " of clinch 5, sidewall 4, buffer layer 2 and fetus face 1.If cord body belt higher with the resistivity of overlay glue or that have a relatively low conductivity is arranged between cord body and the buffer layer, be difficult to so to cause the electroconductibility via " cord body path ".For this reason, the electroconductibility by improving sidewall or clinch can improve the tire electric conductivity to guarantee the electric conductivity in " sidewall path " when reducing cost.In addition, in the inadequate situation of the electric conductivity of fetus face 1, base pen (the base pen) 10 that formed by the rubber combination with outstanding electric conductivity can be set to guarantee the electric conductivity of tire between buffer layer 2 and earthed surface.
When the base pen is not set up, that is to say that when tyre surface had electric conductivity, the resistivity of tyre surface was preferably 1 * 10
8Below the Ω cm, more preferably 1 * 10
6Below the Ω cm.On the other hand, when the base pen was set up, the resistivity of base pen was preferably 1 * 10
8Below the Ω cm, more preferably 1 * 10
6Below the Ω cm.
Embodiment
Based on embodiment the present invention is described more specifically, but the invention is not restricted to this embodiment.
The various chemical that are used for embodiment and reference examples are summarized as follows.
NR：TSR20
IR：IR2200
BR1250H(tin modification BR): the BR1250H(that Zeon company makes is by using lithium initiator polymerization, vinyl binding capacity: 10-13 quality %, Mw/Mn:1.5, tin atom content: 250ppm)
Nd-BR(CB25): the BUNA-CB25(that Lanxess company makes is by using the synthetic BR of Nd catalyzer, cis-content: 96mol%)
VCR617(contains the BR of SPB): the VCR617(SPB content that Ube Industries, Ltd makes: 17 quality %, the fusing point of SPB: 200 ° of C, the insolubles content in the normal hexane of boiling: 15-18 quality %)
HPR340(modification SBR): the HPR340(modification S-SBR that JSR company makes)
The SHOBLACK N220(N220 that N220:Cabot Japan company makes, BET:114m
2/ g)
The SHOBLACK N330(N330 that N330:Cabot Japan company makes, BET:78m
2/ g)
The SHOBLACK N550(N550 that N550:Cabot Japan company makes, BET:40m
2/ g)
The carbon black N660(N660 that N660:Jiangxi Black Cat Carbon Black company makes, BET:32m
2/ g)
The PRINTEX XE2B(BET:1000m that XE2B:Degussa company makes
2/ g, DBP:420mL/100g)
The ULTRASIL U9000Gr(BET:230m that U9000Gr:Evonik company makes
2/ g)
The ULTRASIL VN3(BET:175m that VN3:Evonik company makes
2/ g)
The ULTRASIL VN2(BET:125m that VN2:Evonik company makes
2/ g)
The Z1085Gr(BET:80m that Z1085Gr:Rhodia company makes
2/ g)
The ULTRASIL U360(BET:50m that U360:Evonik company makes
2/ g)
Silane coupling agent: Si75(two (3-triethoxysilylpropyltetrasulfide) disulphide that Evonik company makes)
C5 resin: Marukarez resin (C5 petroleum resin, softening temperature: 100 ° of C) that Maruzen Petrochemical Co., Ltd. makes
TDAE oil: H﹠amp; The VIVATEC 400(TDAE oil that R company makes)
C10 resin: the NOVARES C10(liquid coumarone-indene resin that Rutgers Chemicals company makes, softening temperature: 5-15 ° C)
Zinc oxide: No. 1, the zinc oxide that Mitsu Mining ﹠ Smelting Co., Ltd makes
Stearic acid: the stearic acid that NOF Corp makes
Wax: the Ozoace 355 that Japanese smart wax Co., Ltd. makes
Antioxidant RD: the ANTAGE RD(2 that chemical industry Co., Ltd. of Kawaguchi makes, 2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance)
The Vulkanox 4030(N that antioxidant 77PD:LANXESS company makes, N '-two (1, the 4-3,5-dimethylphenyl)-and Ursol D) antioxidant W-500: the ANTAGE W-500(2 that chemical industry Co., Ltd. of Kawaguchi makes, 2 '-methylene radical-two (4-ethyl-6-tert-butyl phenol))
The insoluble sulfur that comprises 10% oil: the Japanese universe SEIMI sulphur (insolubles content in the dithiocarbonic anhydride: more than 60%, comprise the insoluble sulfur of 10 quality % oil) that industry Co., Ltd. makes of sneaking away during work hours
V200: the Tackirol V200 that Taoka Chemical Industries Co. Ltd. makes
Vulcanization accelerator TBBS: the Nocceler NS(N-tertiary butyl that the emerging chemical industry of imperial palace Co., Ltd. makes-2-[4-morpholinodithio sulphenamide)
Embodiment and reference examples
The chemical (except linking agent and vulcanization accelerator) of table shown in the 1-3 stands basic mixing step (the outflow temperature place at 150 ° of C continues 4 minutes) and the step of regrinding (at the outflow temperature place of 130 ° of C lasting 3 minutes) to obtain mixing thing in Banbury.Then, in the mixing thing that obtains, add linking agent and vulcanization accelerator, and make them in driving the roller machine, stand final mixing step (the outflow temperature place at 100 ° of C continues 2 minutes) to obtain unvulcanized rubber composition.
With the unvulcanized rubber composition that obtains the temperature place of 170 ° of C press vulcanization 12 minutes with the preparation vulcanizate compositions.
Individually, the unvulcanized rubber composition that obtains is extruded the shape that is processed as sidewall, then itself and other tyre assembly is fitted together to form not vulcanized tyre.With vulcanized tyre not the temperature place of 170 ° of C press vulcanization 12 minutes with preparation test tire (radial that is used for passenger vehicle, size: 205/65R15).
Unvulcanized rubber composition, vulcanizate compositions and the test tire that makes carried out following test.Table 1-3 has shown test-results.
＜brown discoloration test 〉
Outdoor brown variable color assessment
The test tire is placed on 6 months (from winter to the summer) of outside on ground at the sunshine of Japan Kobe.Use colour-difference meter, measure a* and b*.Based on the value that obtains, tire is assessed for 5 other standards of level according to following.Numerical value is larger, and the brown variable color is fewer.Herein, the target value of this performance be 3+(-20＜-(a
*+ b
*) * 10≤-15).
(standard)
1：-(a
*+b
*)×10≤-30
2：-30<-(a
*+b
*)×10≤-20
3：-20<-(a
*+b
*)×10≤-10
4：-10<-(a
*+b
*)×10≤0
5：-(a
*+b
*)×10>0
＜crack test 〉
(open air) carries out the pavement test of about 1 year (comprising winter) to the test tire in the Kobe.Formation degree according to following criterion evaluation crackle.Numerical value is larger, and cracking resistance (cracking growth resistance) is better.Herein, the target value of this performance be 3+(observe be lower than 1mm than crackle).
(standard)
Above crackle or the fracture of 1:3mm is observed.
2: 1mm but be lower than being observed than deep torn grain of 3mm at least.
3: the darker and relatively large crackle that is lower than 1mm is observed.
4: naked eyes almost do not observe crackle or fracture.
5: naked eyes can not be observed crackle or fracture, but with magnifying glass (magnification: * 10) can be observed.
＜test for viscoelastic 〉
The complex elastic modulus E of vulcanizate compositions
*(MPa) and losstangenttanδ use Co., Ltd. of this makings of visco-elasticity spectrometer VES(rock institute to make) mensuration under the following conditions: 70 ° of C of temperature, frequency 10Hz, initial strain 10%, and dynamic strain 2%.E
*Value larger, operational stability is better.The value of tan δ is less, the performance of rolling resistance aspect better (or rolling resistance is lower).Herein, the target value of these performances is as follows: E
*Value be 3.0-5.0, the value of tan δ is lower than 0.13.
＜tension test 〉
According to JIS K6251 2010 " determining of vulcanized rubber or thermoplastic elastomer-tensile stress-strain property ", No. 3 dumbbell-shaped test pieces that made by each vulcanizate compositions at room temperature stand tension test.The fracture stretching EB(% of test piece) determined.The value of EB is larger, and weather resistance is better.The target value of this performance is to surpass 480%.
＜flash breaks 〉
To the break flash (broken spew) of at least 100 tires calculating on each experimental wheel fetus in fetu sidewall of the demoulding or the quantity of short flash (short spew) (owing to the rubber that sticks in the molded flash hole produces).As observed, its length is defined as short flash unlike about one medium-sized flash of the length in no problem zone herein.Then, break flash or the short flash of each prescription are represented as index based on following formula.Index value is larger, and the possibility of the flash that breaks is less.The target value of this performance is to surpass 90 value.
(flash rupture index)=(quantity of break flash or short flash in the reference examples 1)/(quantity of break flash or short flash in each prescription) * 100
In the embodiment of the specific wet silicon-dioxide that uses predetermined amount and carbon black, the performance of rolling resistance and cracking resistance aspect is outstanding, and the brown variable color is also suppressed.In addition, even when not specific use silane coupling agent, also can obtain estimated performance, therefore can obtain the chromatic effect that of cost.
The label symbol tabulation
1 fetus face
2 buffer layers
3 cord bodies
4 sidewall
5 clinch
6 bead part
7 bead cores
8 chafer fabrics
10 base pens
The R wheel rim
Claims (6)
1. be used for the rubber combination of sidewall or clinch, with respect to per 100 mass parts rubber components, described rubber combination comprises:
The above BET specific surface area of 2 mass parts is 70-250m
2The wet silicon-dioxide of/g;
At least 20 mass parts but be 27-125m less than the BET specific surface area of 40 mass parts
2The carbon black of/g; And
2.0-7.0 being selected from by phenylenediamine antioxidant and quinoline antioxidant, mass parts consists of at least a in the group.
2. the rubber combination for sidewall or clinch as claimed in claim 1 is characterized in that, the BET specific surface area of described carbon black is 27-50m
2/ g.
3. the rubber combination for sidewall or clinch as claimed in claim 1, it is characterized in that, take the rubber components of 100 quality % as benchmark, described rubber components comprises the isoprene rubber of 25-70 quality %, the divinyl rubber of 30-75 quality %, and the styrene-butadiene rubber(SBR) of 0-20 quality %.
4. the rubber combination for sidewall or clinch as claimed in claim 1 is characterized in that, described rubber combination comprises at least a in quinoline antioxidant and the bisphenol antioxidant.
5. the rubber combination for sidewall or clinch as claimed in claim 1 is characterized in that, described rubber combination does not comprise silane coupling agent.
6. pneumatic tyre, it comprises at least a in sidewall that each rubber combination freely as claimed in claim 1 forms and the clinch.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012092302A JP5647170B2 (en) | 2012-04-13 | 2012-04-13 | Rubber composition for sidewall or clinch, and pneumatic tire |
| JP2012-092302 | 2012-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103374151A true CN103374151A (en) | 2013-10-30 |
Family
ID=49460027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100322496A Pending CN103374151A (en) | 2012-04-13 | 2013-01-28 | Rubber composition for sidewall/clinch of tire and pneumatic tire |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5647170B2 (en) |
| CN (1) | CN103374151A (en) |
| BR (1) | BR102013009025A2 (en) |
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| CN105315512A (en) * | 2014-08-01 | 2016-02-10 | 东洋橡胶工业株式会社 | Run flat tire |
| US9834043B2 (en) | 2014-07-14 | 2017-12-05 | Toyo Tire & Rubber Co., Ltd. | Run flat tire |
| US9914330B2 (en) | 2014-05-30 | 2018-03-13 | Toyo Tire & Rubber Co., Ltd. | Run flat tire and method for producing same |
| US9931896B2 (en) | 2014-06-10 | 2018-04-03 | Toyo Tire & Runner Co., Ltd. | Run flat tire |
| US10214058B2 (en) | 2014-04-24 | 2019-02-26 | Toyo Tire Corporation | Run flat tire |
| CN111183049A (en) * | 2017-10-06 | 2020-05-19 | 株式会社普利司通 | Tire bead member, tire, and method for manufacturing tire bead member |
| CN115838498A (en) * | 2022-10-31 | 2023-03-24 | 合肥万力轮胎有限公司 | Sidewall rubber composition for improving appearance of tire, preparation method of sidewall rubber composition and tire |
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| EP3196244B1 (en) * | 2014-10-06 | 2021-02-24 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
| JP6045553B2 (en) * | 2014-11-14 | 2016-12-14 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN107074015B (en) | 2014-10-06 | 2019-12-06 | 住友橡胶工业株式会社 | Rubber composition for tire, pneumatic tire, and non-pneumatic tire |
| JP6228335B1 (en) * | 2017-04-13 | 2017-11-08 | 住友ゴム工業株式会社 | Cap tread rubber composition for studless tires |
| US11059958B2 (en) * | 2017-05-12 | 2021-07-13 | Hankook Tire Co., Ltd. | Rubber composition for protecting sidewall of tire from ozone and tire manufactured using the same |
| KR102555990B1 (en) * | 2018-12-17 | 2023-07-17 | 주식회사 엘지화학 | Rubber compostion and rubber molded articles produced by the same |
| JP6819027B1 (en) * | 2020-08-04 | 2021-01-27 | 住友ゴム工業株式会社 | Pneumatic tires for passenger cars |
| JP6819026B1 (en) * | 2020-08-04 | 2021-01-27 | 住友ゴム工業株式会社 | Pneumatic tires |
| KR20220070616A (en) * | 2020-11-23 | 2022-05-31 | 현대자동차주식회사 | Natural rubber composition and a molded article manufactured using the same |
| WO2023079949A1 (en) * | 2021-11-05 | 2023-05-11 | 株式会社ブリヂストン | Rubber composition for tire, rubber member for tire, and tire |
| JP7287437B2 (en) | 2021-11-05 | 2023-06-06 | 横浜ゴム株式会社 | Rubber composition and tire using the same |
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| JP2011132472A (en) * | 2009-12-25 | 2011-07-07 | Toyo Tire & Rubber Co Ltd | Rubber composition, method for producing the same, and pneumatic tire |
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- 2013-04-12 BR BR102013009025A patent/BR102013009025A2/en not_active Application Discontinuation
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| CN101643004A (en) * | 2008-08-07 | 2010-02-10 | 住友橡胶工业株式会社 | Tire |
| JP2011063718A (en) * | 2009-09-17 | 2011-03-31 | Toyo Tire & Rubber Co Ltd | Rubber composition, process for producing the same and pneumatic tire |
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| US10214058B2 (en) | 2014-04-24 | 2019-02-26 | Toyo Tire Corporation | Run flat tire |
| US9914330B2 (en) | 2014-05-30 | 2018-03-13 | Toyo Tire & Rubber Co., Ltd. | Run flat tire and method for producing same |
| US9931896B2 (en) | 2014-06-10 | 2018-04-03 | Toyo Tire & Runner Co., Ltd. | Run flat tire |
| US9834043B2 (en) | 2014-07-14 | 2017-12-05 | Toyo Tire & Rubber Co., Ltd. | Run flat tire |
| CN105315512A (en) * | 2014-08-01 | 2016-02-10 | 东洋橡胶工业株式会社 | Run flat tire |
| US9849735B2 (en) | 2014-08-01 | 2017-12-26 | Toyo Tire & Rubber Co., Ltd. | Run flat tire |
| CN105315512B (en) * | 2014-08-01 | 2018-04-20 | 东洋橡胶工业株式会社 | Runflat tire |
| CN111183049A (en) * | 2017-10-06 | 2020-05-19 | 株式会社普利司通 | Tire bead member, tire, and method for manufacturing tire bead member |
| CN111183049B (en) * | 2017-10-06 | 2022-03-11 | 株式会社普利司通 | Tire bead member, tire, and method for manufacturing tire bead member |
| CN115838498A (en) * | 2022-10-31 | 2023-03-24 | 合肥万力轮胎有限公司 | Sidewall rubber composition for improving appearance of tire, preparation method of sidewall rubber composition and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013221052A (en) | 2013-10-28 |
| JP5647170B2 (en) | 2014-12-24 |
| BR102013009025A2 (en) | 2015-01-06 |
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Application publication date: 20131030 |