WO2011010665A1 - 空気入りタイヤ - Google Patents
空気入りタイヤ Download PDFInfo
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- WO2011010665A1 WO2011010665A1 PCT/JP2010/062249 JP2010062249W WO2011010665A1 WO 2011010665 A1 WO2011010665 A1 WO 2011010665A1 JP 2010062249 W JP2010062249 W JP 2010062249W WO 2011010665 A1 WO2011010665 A1 WO 2011010665A1
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- pneumatic tire
- silicic acid
- aromatic vinyl
- rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Definitions
- the present invention relates to a low heat-generating tire, and more specifically, a rubber composition excellent in low heat-generating property, wear resistance and processability using a low molecular weight synthetic rubber as a rubber component and hydrous silicic acid having a specific structure as a reinforcing filler.
- the present invention relates to tires using objects.
- carbon black is often used as a reinforcing filler because it can impart high abrasion resistance to rubber compositions.
- carbon black is used. It is known that the amount of the filler is reduced, or a large particle size is used, and in any case, it is inevitable that the reinforcement, wear resistance, and grip performance on wet road surfaces are lowered.
- silica is known as a filler to improve low heat build-up (for example, Patent Documents 1 to 4), but silica tends to aggregate particles due to hydrogen bonding of silanol groups that are surface functional groups.
- the silanol group has a hydrophilicity —OH group, so that the wettability with the rubber molecule is not good, and the silica is not well dispersed in the rubber. In order to improve this, it is necessary to lengthen the kneading time. Further, since the silica is not sufficiently dispersed in the rubber, the rubber composition has a high Mooney viscosity, and has disadvantages such as inferior processability such as extrusion. Furthermore, since the surface of the silica particles is acidic, when the rubber composition is vulcanized, a basic substance used as a vulcanization accelerator is adsorbed, vulcanization is not sufficiently performed, and the elastic modulus does not increase. It also had the disadvantage of.
- Patent Document 1 discloses the use of hydrophobic precipitated silicic acid.
- silicic acid precipitated after complete hydrophobization is used, there is a surface silanol group that reacts with the silane coupling agent. As a result, there was a drawback that the rubber could not be sufficiently reinforced.
- Patent Document 6 discloses the use of silica having a special shape, but the low heat buildup and wear resistance of the rubber composition is not sufficient.
- Patent Document 7 As a method for improving the rubber component, many technical developments of modified rubbers that interact with fillers such as carbon black and silica have been made (Patent Document 7), but in a rubber composition containing silica and carbon black. A sufficient modification effect is not always obtained.
- Patent Documents 8 and 9 liquid styrene-butadiene rubber having a low molecular weight is used (Patent Documents 8 and 9).
- JP-A-6-248116 Japanese Patent Laid-Open No. 7-70369 JP-A-8-245838 JP-A-3-252431 JP-A-6-157825 JP 2006-37046 A Japanese Patent Publication No. 6-57767 Japanese Patent Laid-Open No. 1-197541 JP 2005-298804 A
- the present inventors can obtain low exothermic property and good workability even when a low molecular weight polymer is used as a rubber component and a hydrous silicic acid having a specific structure is used as silica.
- the inventors have found that the wear resistance of the rubber composition is improved by using both at the same time, thereby completing the present invention. It is an object of the present invention to provide a tire using such a rubber composition as a member and having a low rolling resistance and a low heat build-up and excellent wear resistance.
- the rubber composition used in the tire of the present invention comprises a natural rubber and / or a diene synthetic rubber (A), a low molecular weight aromatic vinyl compound-diene compound copolymer (B), a structural hydrous silicic acid, and a specific structure.
- the low molecular weight aromatic vinyl compound-diene compound copolymer (B) used in the present invention comprises an aromatic vinyl compound having a weight average molecular weight of 4,000 to 250,000 and 0 to 80% by mass.
- the difference in the content of the aromatic vinyl compound between the rubber component (A) and the copolymer (B) is 30.
- the compatibility of a rubber component (A) and a copolymer (B) can be improved.
- the hydrous silicic acid used in the present invention is characterized by having a structure (primary aggregation) that can be expressed by the following index. That is, cetyl trimethyl ammonium bromide adsorption specific surface area (CTAB) (m 2 / g ) and the mode A ac and the following formula of the diameter of the primary aggregates determined by an acoustic particle size distribution analyzer (nm) (I) A ac ⁇ ⁇ 0.76 ⁇ (CTAB) +274 (I) Further, the loss on ignition (mass loss% when heated at 750 ° C. for 3 hours) and the weight loss on heating (mass loss% when heated at 105 ° C.
- CTAB cetyl trimethyl ammonium bromide adsorption specific surface area
- the hydrous silicic acid used in the present invention is a method for precipitating and precipitating hydrous silicic acid by neutralizing an aqueous alkali silicate salt solution such as sodium silicate with a mineral acid such as sulfuric acid, so-called precipitation method producing hydrous silicic acid. It is obtained by a method according to the method.
- a rubber composition excellent in low heat buildup and processability is obtained, and when this is used as a tire member, both the low heat buildup and wear resistance, both of which have been a trade-off in the past, are excellent, and the fuel consumption is low. It can greatly contribute to energy saving.
- the rubber composition used in the tire of the present invention is a low molecular weight aromatic vinyl compound-diene compound copolymer (B) of 5 to 60 masses per 100 mass parts of natural rubber and / or diene synthetic rubber (A).
- a rubber composition obtained by blending and kneading a part and a structural hydrous silicic acid, a silane coupling agent having a specific structure, and carbon black.
- the rubber component (A) is composed of at least one of natural rubber and synthetic diene rubber. Various types are applicable, but those by emulsion polymerization or solution polymerization are preferred.
- Synthetic diene rubbers include cis-1,4-polyisoprene, styrene-butadiene copolymer (SBR), low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, and ethylene-propylene-diene copolymer.
- SBR styrene-butadiene copolymer
- Polymers, chloroprene rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber and the like can be exemplified, and natural rubber and synthetic diene rubber can be used alone or in combination.
- Preferred rubber component (A) is natural rubber, cis-1,4-polyisoprene, SBR, and polybutadiene.
- the rubber component (A) contains 10 parts by mass or more of SBR or polybutadiene, it is preferable in that the improvement effect by the combination of the predetermined copolymer (B) becomes clear.
- the rubber component (A) contains 30 parts by mass or more of a styrene-butadiene copolymer or polybutadiene having a weight average molecular weight of 300,000 to 1,500,000.
- the styrene-butadiene copolymer or polybutadiene is composed of 0 to 60% by mass of styrene, and the amount of vinyl bonds in the diene compound portion is preferably 0 to 80% by mass. More specifically, the styrene-butadiene copolymer or polybutadiene is an emulsion polymerization or solution polymerization styrene-butadiene copolymer or polybutadiene composed of 0% by mass or more of styrene.
- the difference in the content of the aromatic vinyl compound in the styrene-butadiene copolymer and the copolymer (B) is 30% by mass or less. When the difference in the content of the aromatic vinyl compound exceeds 30% by mass, the compatibility is likely to be lowered, and sufficient fracture strength may not be obtained.
- the low molecular weight aromatic vinyl compound-diene compound copolymer (B) is a compound obtained by copolymerizing a monomeric aromatic vinyl compound and a diene compound. It has a weight average molecular weight of 4,000 to 250,000 (polystyrene conversion by gel permeation chromatography).
- the copolymer (B) is composed of 0 to 80% by mass of an aromatic vinyl compound, and the amount of vinyl bonds in the diene compound part is composed of 0 to 80% by mass. In both cases, if it exceeds 80% by mass, the workability deteriorates.
- it is composed of an aromatic vinyl compound in an amount of 0 to 60% by mass, and is composed of an aromatic vinyl compound in which the vinyl bond content of the diene compound is 0 to 80% by mass, more preferably 0 to 50% by mass.
- the copolymer (B) preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 30,000 to 150,000, and still more preferably 50,000 to 150,000.
- weight average molecular weight is 200,000 or more, workability is lowered.
- molecular weight distribution is preferably narrow, and Mw / Mn is preferably 5.0 or less. If it is wide, it tends to be inferior to tan ⁇ , which is an indicator of low heat generation.
- a copolymer composed of an aromatic vinyl compound exceeding 80% by mass and a diene compound having a vinyl bond amount exceeding 80% by mass is insufficient in improving workability, low heat build-up and wear resistance.
- the vinyl bond amount specified here indicates the amount of vinyl bond in the structural unit derived from the diene compound, and the vinyl bond occupies the amount of all bonds including other bonds represented by cis bond and trans bond. Indicates percentage of quantity.
- aromatic vinyl compound examples include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, chloromethylstyrene, vinyltoluene and the like.
- styrene, p-methylstyrene, and ⁇ -methylstyrene are used.
- styrene is preferable.
- butadiene isoprene, pentadiene, 2,3-dimethylbutadiene or the like is used, and butadiene is particularly preferable.
- the copolymer (B) can be obtained by various production methods as long as a predetermined molecular structure is given.
- various liquid or low molecular weight polymers or rubbers can be applied, and preferably produced by solution polymerization of styrene and butadiene.
- the copolymer (B) is a solution polymerized styrene-butadiene copolymer rubber.
- An example of an industrial method is a method in which a predetermined monomer is copolymerized in a hydrocarbon solvent using an organolithium compound as an initiator.
- the copolymer (B) can be obtained using 1,3-butadiene in a tank-type or column-type reactor using an organic lithium compound initiator in a hydrocarbon solvent in the presence of ether or a tertiary amine.
- Such a diene compound and an aromatic vinyl compound can be obtained by copolymerization, but the production method is not limited thereto.
- the low molecular weight aromatic vinyl compound-diene compound copolymer (B) is contained in an amount of 5 to 60 parts by mass with respect to 100 parts by mass of the rubber component (A). If it is less than 5 parts by mass, the effect is not exhibited, and if it exceeds 60 parts by mass, the fracture characteristics are deteriorated.
- the structural hydrous silicic acid used in the present invention can be confirmed by the fact that the characteristic values measured by a method generally measured with silica or carbon black satisfy the following relationship. That is, the cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) and the diameter A ac (nm) of the mode of the number of primary aggregates determined by acoustic particle size distribution measurement are represented by the following formula (I) A ac ⁇ ⁇ 0.76 ⁇ (CTAB) +274 (I)
- CTAB cetyltrimethylammonium bromide adsorption specific surface area
- a ac (nm) of the mode of the number of primary aggregates determined by acoustic particle size distribution measurement are represented by the following formula (I) A ac ⁇ ⁇ 0.76 ⁇ (CTAB) +274
- the loss on ignition mass loss% when heated at 750 ° C. for 3 hours
- the weight loss on heating mass loss% when heated
- Cetyltrimethylammonium bromide adsorption specific surface area is the specific surface area (m 2 / g) of hydrous silicic acid calculated from the amount of cetyltrimethylammonium bromide adsorbed on the hydrous silicic acid surface.
- CTAB can be measured according to the method described in ASTM D3765-92. Since the method described in ASTM D3765-92 is a method for measuring CTAB of carbon black, it is slightly modified.
- CE-TRAB cetyltrimethylammonium bromide
- hydrous silicate sodium di-2-ethylhexylsulfosuccinate
- the hydrous silicic acid used in the present invention desirably has a CTAB of 50 to 250 m 2 / g, preferably 100 to 200 m 2 / g.
- CTAB a CTAB of 50 to 250 m 2 / g, preferably 100 to 200 m 2 / g.
- the CTAB is less than 50 m 2 / g, the storage elastic modulus of the rubber composition is remarkably lowered, and when it is more than 250 m 2 / g, the viscosity of the rubber composition when unvulcanized may be increased.
- the diameter (acoustic particle size distribution diameter) measured by an acoustic particle size distribution measuring device is an index of the development of the structure.
- the hydrous silicic acid particles include those in which finely sized particles are primary aggregated and those that are slightly secondary aggregated.
- the measurement with an acoustic particle size distribution measuring apparatus is carried out by dispersing a hydrous silicic acid 0.01 M KCl aqueous solution with ultrasonic waves for 5 minutes to remove bubbles and destroying secondary aggregates. The distribution of the particle size and the number of particles of hydrous silicic acid primary aggregates is obtained. Of these, the most frequently occurring particle diameter is A ac (nm).
- CTAB low heat build-up and the wear resistance of the rubber composition
- Aac is preferably 1 ⁇ m or less.
- hydrous silicic acid becomes a fracture nucleus, and the mechanical properties of the rubber composition may be impaired.
- the difference between the decrease in mass when the hydrous silicic acid used in the present invention is heated (%) and the decrease in mass when heated (%) is, (Loss on ignition)-(Lose on heating) ⁇ 3 (II)
- the loss on heating and the loss on ignition are carried out in accordance with the test method of the compounding agent for JIS K6220-1 rubber.
- the loss on heating is usually the decrease in mass when heated at 105 ⁇ 2 ° C. for 2 hours, and the loss on ignition is usually 750 ⁇ 25. It is the% decrease in mass when ignited at 3 ° C. for 3 hours.
- the amount of hydrous silicic acid used in the present invention is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component (A). If it is less than 10 parts by mass, the reinforcement is not sufficient, and if it exceeds 150 parts by mass, the workability is deteriorated.
- the hydrous silicic acid used in the present invention is produced according to the method for producing hydrous silicic acid by precipitation method.
- sodium silicate and sulfuric acid are placed in a reaction vessel preliminarily filled with a certain amount of warm water while controlling pH and temperature, and added for a certain period of time to obtain a hydrous silicate slurry.
- the hydrated silicate slurry is filtered and washed by a filter capable of cake washing such as a filter press to remove the by-product electrolyte, and then the obtained hydrated silicate cake is slurried, and a spray dryer or the like It is dried and manufactured using a dryer.
- silane coupling agent reacts with the silanol group remaining on the surface of the hydrous silicic acid and the rubber component polymer, and acts as a bonding bridge between the hydrous silicic acid and the rubber to form a reinforcing phase.
- the silane coupling agent used in the present invention is preferably at least one selected from the group consisting of compounds represented by the following general formula.
- A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom
- B is an alkyl group having 1 to 3 carbon atoms
- m is an integer of 1 to 3
- a is 1
- An integer of ⁇ 9 and b may be an integer of 1 or more and have a distribution.
- two B may be the same or different
- two or three A may be the same or different.
- A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom
- B is an alkyl group having 1 to 3 carbon atoms
- Y is a mercapto group, a vinyl group, an amino group, A glycidoxy group or an epoxy group
- m is an integer of 1 to 3
- c is an integer of 0 to 9.
- two B may be the same or different, and when m is 2 or 3, two or three A may be the same or different.
- A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom
- B is an alkyl group having 1 to 3 carbon atoms
- Z is a benzothiazolyl group, N, N-dimethylthio It is a carbamoyl group or a methacryloyl group
- m is an integer of 1 to 3
- a is an integer of 1 to 9
- b is an integer of 1 or more and may have a distribution.
- two B may be the same or different
- two or three A may be the same or different.
- the silane coupling agent represented by the general formula (III) includes bis- (3-triethoxysilylpropyl) tetrasulfide, bis- (3-trimethoxysilylpropyl) tetrasulfide, bis- ( 3-methyldimethoxysilylpropyl) tetrasulfide, bis- (3-triethoxysilylethyl) tetrasulfide, bis- (3-triethoxysilylpropyl) disulfide, bis- (3-trimethoxysilylpropyl) disulfide, bis- ( 3-triethoxysilylpropyl) trisulfide,
- silane coupling agent represented by the general formula (IV) examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane,
- silane coupling agent represented by the general formula (V) examples include 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-trimethoxy And silylpropylmethacryloyl monosulfide.
- the amount of the silane coupling agent used is preferably 1 to 20% by mass relative to the amount of hydrous silicic acid. If the amount used is less than 1% by mass, a sufficient coupling effect may not be obtained, and if it exceeds 20% by mass, gelation of the polymer may be caused.
- carbon black can be used as a reinforcing filler together with hydrous silicic acid.
- the wear resistance of the rubber composition can be improved.
- carbon black carbon black of various grades, such as SAF, HAF, ISAF, HAF, FEF, GPF, can be used, for example.
- the amount of carbon black used is preferably 80 parts by mass or less with respect to 100 parts by mass of the rubber component (A), and the total amount of carbon black and hydrous silicic acid combined is preferably 120 parts by mass or less. By setting the total blending amount to 120 parts by mass or less with respect to 100 parts by mass of the rubber component, low heat buildup and wear resistance can be sufficiently improved.
- various chemicals usually used in the rubber industry for example, other reinforcing fillers, vulcanizing agents, vulcanization accelerators, as long as the object of the present invention is not impaired.
- a softener, an antioxidant, a scorch inhibitor, zinc white, stearic acid, and the like can be appropriately blended.
- At least one kind of process oil for example, paraffinic, naphthenic, aromatic, etc.
- aromatics are used for applications that emphasize fracture characteristics and wear resistance.
- a naphthene type or paraffin type is preferable for applications in which exothermic properties and low temperature characteristics are important.
- Examples of the vulcanizing agent include sulfur and the like.
- the amount of these used is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the rubber component (A). 0.0 part by mass. If the amount is less than 0.1 parts by mass, the fracture characteristics and wear resistance of the vulcanized rubber are deteriorated.
- the rubber composition of the present invention is obtained by kneading using an open kneader such as a roll or a closed kneader such as a Banbury mixer, and is vulcanized after molding to provide a vibration-proof rubber, belt, hose. It can also be used for other industrial products. In particular, it is suitably used as tire rubber, and can be applied to all tire members such as tread rubber (including cap rubber and base rubber), side rubber, side reinforcing rubber, and inner liner rubber.
- the tire of the present invention is characterized by applying the above rubber composition to a member.
- a tire using the rubber composition as a tread member has low rolling resistance and excellent wear resistance because the rubber composition has low heat generation.
- As the gas filled in the tire of the present invention normal or air having a changed oxygen partial pressure, or an inert gas such as nitrogen can be used.
- silicate OT sodium di-2-ethylhexylsulfosuccinate
- Abrasion resistance The amount of wear with a slip rate of 60% at room temperature was measured according to JIS K6264 using a Ramborn type wear tester, and the reciprocal of the amount of wear was expressed as an index with Comparative Example 1 being 100. The larger this value, the better the wear resistance.
- the breaking strength (TB) is measured according to JIS K6301-1995.
- the comparative example 1 is indexed as 100 and evaluated. The larger the index, the better the durability.
- the liquid aromatic vinyl compound-diene compound copolymer (B-1) having a weight average molecular weight of 80,000 can be produced as follows. In an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of butadiene (16%) and a cyclohexane solution of styrene (21%) become 37.5 g of butadiene monomer and 12.5 g of styrene monomer.
- the weight average molecular weights are 4,000, 9,000, 12,000, 25,000, 40,000, 60,000, 120,000, 180,000 and 220,000, and 25% by mass of styrene.
- Aromatic vinyl compound-diene compound copolymers B-2 to B-10 having a vinyl bond amount of 65% by mass were prepared.
- the neutralization reaction was performed while maintaining the Na 2 O concentration in the reaction solution in the range of 0.00 to 0.01 mol / L. From the middle of the reaction, white turbidity started, and the viscosity increased at 47 minutes to form a gel solution. Further addition was continued and the reaction was stopped in 90 minutes. After stopping the reaction, the reaction solution temperature was maintained at 96 ° C. for 30 minutes. The silica concentration in the resulting solution was 55 g / L. Subsequently, sulfuric acid having the above-described concentration was added until the pH of the solution reached 3, to obtain a silicic acid slurry. The obtained silicic acid slurry was filtered with a filter press and washed with water to obtain a wet cake. Next, the wet cake was made into a slurry using an emulsifier and dried with a spray dryer to obtain a wet method hydrous silicate A.
- Production example B Using the same container and raw materials as in Production Example A, 93 L of water and 0.6 L of an aqueous sodium silicate solution were added and heated to 90 ° C. The Na 2 O concentration in the obtained solution was 0.005 mol / L. While maintaining the temperature of this solution at 90 ° C., the same sodium silicate aqueous solution as described above was simultaneously added dropwise at a flow rate of 540 ml / min and sulfuric acid (18 mol / L) at a flow rate of 24 ml / min. While adjusting the flow rate, the neutralization reaction was performed while maintaining the Na 2 O concentration in the reaction solution in the range of 0.00 to 0.01 mol / L.
- Production Example C Using the same container and raw material as in Production Example A, 93 L of water and 0.6 L of sodium silicate aqueous solution were added and heated to 65 ° C. The Na 2 O concentration in the obtained solution was 0.005 mol / L. While maintaining the temperature of this solution at 65 ° C., the same sodium silicate aqueous solution as described above was simultaneously added dropwise at a flow rate of 540 ml / min and sulfuric acid (18 mol / L) at a flow rate of 24 ml / min. While adjusting the flow rate, the neutralization reaction was performed while maintaining the Na 2 O concentration in the reaction solution in the range of 0.00 to 0.01 mol / L.
- reaction solution began to become cloudy, and the viscosity increased to a gel solution at 50 minutes. Further addition was continued and the reaction was stopped in 90 minutes. After stopping the reaction, the reaction solution temperature was maintained at 65 ° C. for 60 minutes. The silica concentration in the resulting solution was 55 g / L. Subsequently, sulfuric acid having the above-described concentration was added until the pH of the solution reached 3, to obtain a silicic acid slurry. Thereafter, wet method hydrous silicic acid C was obtained in the same manner as in Production Example A.
- Production Example D Using the same container and raw material as in Production Example A, 86 L of water and 0.5 L of an aqueous sodium silicate solution were added and heated to 96 ° C. The Na 2 O concentration in the obtained solution was 0.005 mol / L. While maintaining the temperature of this solution at 96 ° C., the same aqueous sodium silicate solution as described above was simultaneously added dropwise at a flow rate of 615 ml / min and sulfuric acid (18 mol / L) at a flow rate of 27 ml / min. While adjusting the flow rate, the neutralization reaction was performed while maintaining the Na 2 O concentration in the reaction solution in the range of 0.00 to 0.01 mol / L.
- reaction solution started to become cloudy, and the viscosity increased to a gel solution at 40 minutes. Further addition was continued and the reaction was stopped in 90 minutes. After stopping the reaction, the reaction solution temperature was maintained at 96 ° C. for 30 minutes. The silica concentration in the resulting solution was 62 g / L. Subsequently, sulfuric acid having the above-described concentration was added until the pH of the solution reached 3, to obtain a silicic acid slurry. Thereafter, wet method hydrous silicic acid D was obtained in the same manner as in Production Example A.
- Examples 1 to 13 and Comparative Examples 1 to 5 As an example, a rubber composition using low molecular weight aromatic vinyl compound-diene compound copolymers B-1 to B-10 and hydrous silicic acids A to D obtained in Production Examples A to D, as a comparative example Do not use low molecular weight aromatic vinyl compound-diene compound copolymer, or use B-1 and use hydrous silicic acid C or D as silica, or Nipsil AQ manufactured by Tosoh Silica or ULTRASIL VN2 manufactured by Degussa Then, based on the formulation shown in Tables 1 and 2, the components of the tread formulation and the side formulation were kneaded by a conventional method to prepare rubber compositions.
- the rubber composition was vulcanized at 160 ° C. for 15 minutes, and the processability, low heat build-up, wear resistance or durability of the vulcanized rubber was evaluated.
- the results are shown in Tables 3 and 4 together with the properties of the hydrous silicic acid used.
- Acoustic particle size distribution diameter A ac of precipitated silica A ⁇ D is used in Table 3 and 4 embodiment, wherein: with respect to greater than the value determined by -0.76 ⁇ (CTAB) +274, Comparative Example It can be seen that the commercially available silica used in A has a small Aac . Further, from Tables 3 and 4, the hydrous silicic acids A to D satisfy the above formula (II) in the difference between the loss on ignition and the loss on heating.
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Abstract
Description
従来、ゴムの低発熱化技術としては、低ロス化剤の添加やポリマー変性による補強充填剤として添加するカーボンブラックの分散性の向上や充填剤にシリカを使用するなどが数多く検討されている。
また、特許文献5には、疎水性沈降ケイ酸を用いることが開示されているが、完全疎水化処理した沈降ケイ酸を用いているので、シランカップリング剤が反応する表面シラノール基が存在しなくなるため、ゴムの補強が十分にとれないという欠点があった。さらに、低発熱性を高めるため、シリカを大粒径化することが行われているが、大粒径化することでシリカの比表面積が低下し、補強性が悪くなる。特許文献6には、特殊形状のシリカを用いることが開示されているが、ゴム組成物の低発熱性、耐摩耗性が十分ではない。
本発明で用いる低分子量の芳香族ビニル化合物-ジエン化合物共重合体(B)は、重量平均分子量4千~25万で、0~80質量%の芳香族ビニル化合物からなり、ジエン化合物の部分のビニル結合量が0~80質量%である共重合体である。さらに、ゴム成分(A)として分子量の大きいに芳香族ビニル化合物-ジエン化合物共重合体を使用する場合、ゴム成分(A)と共重合体(B)の芳香族ビニル化合物の含量の差が30質量%以下とすることによって、ゴム成分(A)と共重合体(B)の相溶性を高めることができる。
即ち、セチルトリメチルアンモニウムブロミド吸着比表面積(CTAB)(m2/g)と音響式粒度分布測定によって求められる一次凝集体の直径(nm)の最頻値Aacとが下記式(I)
Aac≧-0.76×(CTAB)+274・・・(I)
を満たし、さらに灼熱減量(750℃で3時間加熱した時の質量減少%)と加熱減量(105℃で2時間加熱した時の質量減少%)とが下記式(II)
(灼熱減量)-(加熱減量)≦3・・・(II)
を満たすことが好ましく、このような含水ケイ酸を含有するゴム組成物は、低発熱性と耐摩耗性が両立でき、加工性にも優れる。
ゴム成分(A)は、天然ゴム及び合成ジエン系ゴムのうち少なくとも1方のゴムからなる。各種のものが適用可能であるが、乳化重合又は溶液重合によるものが好ましい。
好ましくは、ゴム成分(A)は、30万~150万の重量平均分子量のスチレン-ブタジエン共重合体もしくはポリブタジエンを30質量部以上含有する。このスチレン-ブタジエン共重合体もしくはポリブタジエンは、0~60質量%のスチレンからなり、ジエン化合物の部分のビニル結合量が0~80質量%であることが好ましい。より具体的には、このスチレン-ブタジエン共重合体もしくはポリブタジエンは、0質量%以上のスチレンからなる乳化重合または溶液重合スチレン-ブタジエン共重合体もしくはポリブタジエンである。また、好ましくは、このスチレン-ブタジエン共重合体と共重合体(B)中の芳香族ビニル化合物の含量の差は30質量%以下である。芳香族ビニル化合物の含量の差が30質量%を超えると、相溶性が低下し易く、十分な破壊強度が得られない可能性がある。
即ち、セチルトリメチルアンモニウムブロミド吸着比表面積(CTAB)(m2/g)と音響式粒度分布測定によって求められる一次凝集体の数の最頻値の直径Aac(nm)とが下記式(I)
Aac≧-0.76×(CTAB)+274・・・(I)
を満たし、好ましくは灼熱減量(750℃で3時間加熱した時の質量減少%)と加熱減量(105℃で2時間加熱した時の質量減少%)とが下記式(II)
(灼熱減量)-(加熱減量)≦3・・・(II)
を満たす含水ケイ酸である。
CTABの測定は、ASTM D3765-92記載の方法に準拠して行うことができる。ASTM D3765-92記載の方法は、カーボンブラックのCTABを測定する方法であるので、若干の修正を加える。即ち、カーボンブラックの標準品を使用せず、セチルトリメチルアンムニウムブロミド(以下、CE-TRABと略記する)標準液を調製し、これによって含水ケイ酸OT(ジ-2-エチルヘキシルスルホコハク酸ナトリウム)溶液の標定を行い、含水ケイ酸表面に対するCE-TRAB1分子当たりの吸着断面積を0.35nm2としてCE-TRABの吸着量から、比表面積を算出する。
音響式粒度分布測定装置による測定は、含水ケイ酸の0.01M KCl水溶液を超音波で5分間分散処理し、泡を除去して二次凝集体を破壊した後、測定する。含水ケイ酸の一次凝集体の粒径と粒子数の分布が得られ、このうち、最も頻度が多く現われた粒子の直径をAac(nm)とすると、
Aac≧-0.76×(CTAB)+274・・・(I)
を満足するとき、ゴム組成物の低発熱性と耐摩耗性が共に改善される。Aacが、この条件を満たさない時、低発熱性と耐摩耗性のどちらか又は両方が低下する。さらに、Aacは、1μm以下であることが好ましい。1μmより大きいと含水ケイ酸が破壊核となり、ゴム組成物の力学的特性が損なわれる虞がある。
(灼熱減量)-(加熱減量)≦3・・・(II)
であることが好ましい。
加熱減量及び灼熱減量は、JIS K6220-1ゴム用配合剤の試験方法に準じて行い、加熱減量は通常105±2℃で2時間加熱した時の質量の減少%、灼熱減量は通常750±25℃で3時間強熱した時の質量の減少%である。
続いて、該含水ケイ酸スラリーをフィルタープレス等のケーキ洗浄が可能なろ過機により濾別、洗浄して副生電解質を除去した後、得られた含水ケイ酸ケーキをスラリー化し、噴霧乾燥機等の乾燥機を用いて乾燥し製造される。
本発明で用いられるシランカップリング剤は、好ましくは下記一般式で表される化合物よりなる群から選ばれた少なくとも一種である。
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、mは1~3の整数、aは1~9の整数、bは1以上の整数で分布を有していてもよい。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、Yはメルカプト基、ビニル基、アミノ基、グリシドキシ基又はエポキシ基であり、mは1~3の整数、cは0~9の整数である。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、Zはベンゾチアゾリル基、N,N-ジメチルチオカルバモイル基又はメタクリロイル基であり、mは1~3の整数、aは1~9の整数、bは1以上の整数で分布を有していてもよい。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]
カーボンブラックの使用量は、好ましくはゴム成分(A)100質量部に対して80質量部以下で、カーボンブラックと含水ケイ酸を合わせた総配合量が120質量部以下であることが好ましい。総配合量をゴム成分100質量部に対して120質量部以下とすることで、低発熱性及び耐摩耗性を十分に向上させることができる。
以下の実施例、比較例において、各種測定、評価は、下記の方法に従って行なった。
(1)重量平均分子量(Mw)の測定
ゲルパーミエーションクロマトグラフィー(GPC)(東ソー社製、HLC-8220GPC)を用いて、ポリスチレン換算で求めた。
(2)スチレン量(ポリマー中の質量%)
270MHz 1H-NMRによって求めた。
(3)ビニル量(ジエン化合物部分全体に対する質量%)
270MHz 1H-NMRによって求めた。
(1)音響式粒度分布径の測定
各含水ケイ酸の0.01M KCl水溶液を超音波で5分間分散処理し、泡を除去した後、超音波式粒度分布測定装置DT1200(Dispertion Technology社製)を用いて、含水ケイ酸の1次凝集体の直径の最頻値Aac(nm)を測定した。
ASTM D3765-92記載の方法に準拠して実施した。ASTM D3765-92記載の方法は、カーボンブラックのCTABを測定する方法であるので、若干の修正を加えた。すなわち、カーボンブラックの標準品であるIRB#3(83.0m2/g)を使用せず、別途セチルトリメチルアンムニウムブロミド(以下、CE-TRABと略記する)標準液を調製し、これによって含水ケイ酸OT(ジ-2-エチルヘキシルスルホコハク酸ナトリウム)溶液の標定を行い、含水ケイ酸表面に対するCE-TRAB1分子当たりの吸着断面積を0.35nm2としてCE-TRABの吸着量から、比表面積(m2/g)を算出した。これは、カーボンブラックと含水ケイ酸とでは表面が異なるので、同一表面積でもCE-TRABの吸着量に違いがあると考えられるからである。
含水ケイ酸サンプルを秤量し、加熱減量の場合は105±2℃でサンプルを2時間加熱し、灼熱減量の場合は750±25℃でサンプルを3時間加熱した後、質量を測定し、加熱前のサンプル質量との差を加熱前の質量に対して%で表した。
JIS K6300-1994に従い、Lローターを使用して、予熱1分、ローター作動時間4分、温度130℃の条件でムーニー粘度(ML1+4、130℃)を測定し、比較例1を100として指数で表示した。この数値が大きい程、加工性が悪い。
粘弾性スペクトロメーター(東洋精機株式会社製)を使用し、温度60℃、歪1%、周波数50Hzでtanδ(動的損失)を測定した。(比較例1のtanδ/実施例のtanδ)×100として指数で表示した。この数値が小さい程、低発熱性に優れる。
ランボーン型摩耗試験機を用い、JIS K6264に従い、室温におけるスリップ率60%の摩耗量を測定し、摩耗量の逆数を比較例1を100として指数で表示した。この数値が大きい程、耐摩耗性が良好である。
破壊強度(TB)を、JIS K6301-1995に従って測定する。比較例1を100として指数化し評価する。指数が大きいほど耐久性が良好である。
重量平均分子量8万の液状芳香族ビニル化合物-ジエン化合物共重合体(B-1)は、以下のように製造することができる。
乾燥し、窒素置換された800mLの耐圧ガラス容器に、ブタジエンのシクロヘキサン溶液(16%)、スチレンのシクロヘキサン溶液(21%)をブタジエン単量体37.5g、スチレン単量体12.5gとなるように注入し、2,2-ジテトラヒドロフリルプロパン0.66ミリモルを注入し、これに、n-ブチルリチウム(BuLi)1.32ミリモルを加えた後、50℃の温水浴中で1.5時間重合する。重合転化率はほぼ100%である。
この後、重合系に、更に、2,6-ジ-t-ブチル-p-クレゾール(BHT)のイソプロパノール5重量%溶液0.5mLを添加し、反応を停止させる。その後、常法に従い乾燥することにより、重合体を得る。
得られた共重合体は、重量平均分子量8万、25質量%のスチレンからなり、ブタジエンの部分のビニル結合量は65質量%である。
製造例A
攪拌機を備えた容量180Lのジャケット付ステンレス製反応槽に、水93Lとケイ酸ナトリウム水溶液(SiO2 160g/L、SiO2/Na2Oモル比3.3)0.6Lを入れ96℃に加熱した。得られた溶液中のNa2O濃度は、0.005mol/Lであった。
この溶液の温度を96℃に維持しながら、上記と同じケイ酸ナトリウム水溶液を540ml/分、硫酸(18mol/L)を24ml/分の流量で同時に滴下した。流量を調整しながら、反応溶液中のNa2O濃度を0.00~0.01mol/Lの範囲に維持して中和反応を行なった。反応途中から白濁をはじめ、47分目に粘度が上昇してゲル状溶液となった。さらに添加を続けて90分で反応を停止した。反応停止後、反応液温度を96℃に30分間維持した。生じた溶液中のシリカ濃度は55g/Lであった。引き続いて、上記濃度の硫酸を溶液のpHが3になるまで添加してケイ酸スラリーを得た。得られたケイ酸スラリーをフィルタープレスで濾過、水洗を行なって湿潤ケーキを得た。次いで、湿潤ケーキを乳化装置を用いてスラリーとして、噴霧式乾燥機で乾燥して湿式法含水ケイ酸Aを得た。
製造例Aと同じ容器および原料を使用し、水93Lとケイ酸ナトリウム水溶液0.6Lを入れ、90℃に加熱した。得られた溶液中のNa2O濃度は0.005mol/Lであった。
この溶液の温度を90℃に維持しながら、上記と同じケイ酸ナトリウム水溶液を540ml/分、硫酸(18mol/L)を24ml/分の流量で同時に滴下した。流量を調整しながら、反応溶液中のNa2O濃度を0.00~0.01mol/Lの範囲に維持して中和反応を行なった。反応途中から白濁をはじめ、47分目に粘度が上昇してゲル状溶液となった。さらに添加を続けて90分で反応を停止した。反応停止後、反応液温度を90℃に30分間維持した。生じた溶液中のシリカ濃度は55g/Lであった。引き続いて、上記濃度の硫酸を溶液のpHが3になるまで添加してケイ酸スラリーを得た。以下製造例Aと同様な方法で湿式法含水ケイ酸Bを得た。
製造例Aと同じ容器および原料を使用し、水93Lとケイ酸ナトリウム水溶液0.6Lを入れ、65℃に加熱した。得られた溶液中のNa2O濃度は0.005mol/Lであった。
この溶液の温度を65℃に維持しながら、上記と同じケイ酸ナトリウム水溶液を540ml/分、硫酸(18mol/L)を24ml/分の流量で同時に滴下した。流量を調整しながら、反応溶液中のNa2O濃度を0.00~0.01mol/Lの範囲に維持して中和反応を行なった。反応途中から反応溶液は白濁をはじめ、50分目に粘度が上昇してゲル状溶液となった。さらに添加を続けて90分で反応を停止した。反応停止後、反応液温度を65℃に60分間維持した。生じた溶液中のシリカ濃度は55g/Lであった。引き続いて、上記濃度の硫酸を溶液のpHが3になるまで添加してケイ酸スラリーを得た。以下製造例Aと同様な方法で湿式法含水ケイ酸Cを得た。
製造例Aと同じ容器および原料を使用し、水86Lとケイ酸ナトリウム水溶液0.5Lを入れ、96℃に加熱した。得られた溶液中のNa2O濃度は0.005mol/Lであった。
この溶液の温度を96℃に維持しながら、上記と同じケイ酸ナトリウム水溶液を615ml/分、硫酸(18mol/L)を27ml/分の流量で同時に滴下した。流量を調整しながら、反応溶液中のNa2O濃度を0.00~0.01mol/Lの範囲に維持して中和反応を行なった。反応途中から反応溶液は白濁をはじめ、40分目に粘度が上昇してゲル状溶液となった。さらに添加を続けて90分で反応を停止した。反応停止後、反応液温度を96℃に30分間維持した。生じた溶液中のシリカ濃度は62g/Lであった。引き続いて、上記濃度の硫酸を溶液のpHが3になるまで添加してケイ酸スラリーを得た。以下製造例Aと同様な方法で湿式法含水ケイ酸Dを得た。
実施例として、低分子量の芳香族ビニル化合物-ジエン化合物共重合体B-1~B-10と製造例A~Dで得られた含水ケイ酸A~Dを用いたゴム組成物、比較例として低分子量の芳香族ビニル化合物-ジエン化合物共重合体を用いないか、又はB-1を用い、シリカとして含水ケイ酸C又はD、あるいは東ソー・シリカ社製Nipsil AQ又はDegussa社製ULTRASIL VN2を用いて、第1、2表に示す配合処方に基づきトレッド配合及びサイド配合の各成分を常法により混練りし、ゴム組成物を調製した。
注
1)SBR#1500〔JSR社製〕
2)BR150L〔宇部興産社製〕
3)低分子量芳香族ビニル化合物-ジエン化合物共重合体B-1~B-10
4)シーストKH(N339)〔東海カーボン社製〕
5)含水ケイ酸の製造例A~D又は市販のシリカ
6)シランカップリング剤Si75(一分子中のSの数が平均2.4であるビス(3-トリエトキシシリルプロピル)ポリスルフィド)〔Degussa社製〕
7)N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン
8)ジフェニルグアニジン
9)N-t-ブチル-2-ベンゾチアジルスルフェンアミド
注
1)RSS#3グレードの天然ゴム
2)BR150L〔宇部興産社製〕
3)低分子量芳香族ビニル化合物-ジエン化合物共重合体B-1~B-10
4)旭#70〔旭カーボン社製〕
5)含水ケイ酸の製造例A~D又は市販のシリカ
6)シランカップリング剤Si75(一分子中のSの数が平均2.4であるビス(3-トリエトキシシリルプロピル)ポリスルフィド)〔Degussa社製〕
7)2,2,4-トリメチル-1,2-ジヒドロキノリン重合体
8)ジベンゾチアジルジスルフィド
9)N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド
Claims (15)
- 天然ゴム及び合成ジエン系ゴムの少なくとも1つからなるゴム成分(A)100質量部に対して、重量平均分子量(ゲルパーミエーションクロマトグラフィーによるポリスチレン換算)4千~25万を有する芳香族ビニル化合物-ジエン化合物共重合体(B)で、芳香族ビニル化合物が0~80質量%からなり、ジエン化合物部分のビニル結合が0~80質量%である該共重合体(B)5~60質量部含んでなるゴム成分と含水ケイ酸を配合したゴム組成物であって、含水ケイ酸が含水ケイ酸のセチルトリメチルアンモニウムブロミド吸着比表面積(CTAB)(m2/g)と音響式粒度分布測定によって求められる一次凝集体の直径の最頻値Aac(nm)とが下記式(I)
Aac≧-0.76×(CTAB)+274・・・(I)
を満たす含水ケイ酸であるゴム組成物を用いることを特徴とする空気入りタイヤ。 - 含水ケイ酸が、その灼熱減量(750℃で3時間加熱した時の質量減少%)と加熱減量(105℃で2時間加熱した時の質量減少%)とが下記式(II)
(灼熱減量)-(加熱減量)≦3・・・(II)
を満たすことを特徴とする請求項1に記載の空気入りタイヤ。 - 含水ケイ酸が、音響式粒度分布測定によって求められる一次凝集体の直径の最頻値が1μm以下であることを特徴とする請求項1または2に記載の空気入りタイヤ。
- 含水ケイ酸が、CTABが50~250m2/gであることを特徴とする請求項1~3のいずれかに記載の空気入りタイヤ。
- ゴム成分(A)100質量部に対して含水ケイ酸を10~150質量部を配合してなる請求項1~4のいずれかに記載の空気入りタイヤ。
- シランカップリング剤を含水ケイ酸の配合量の1~20質量%配合したことを特徴とする請求項1~5のいずれかに記載の空気入りタイヤ。
- シランカップリング剤が、下記一般式(III)で表される化合物:
AmB3-mSi-(CH2)a-Sb-(CH2)a-SiAmB3-m・・・(III)
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、mは1~3の整数、aは1~9の整数、bは1以上の整数で分布を有していてもよい。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]、
下記一般式(IV)で表される化合物:
AmB3-mSi-(CH2)c-Y・・・(IV)
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、Yはメルカプト基、ビニル基、アミノ基、グリシドキシ基又はエポキシ基であり、mは1~3の整数、cは0~9の整数である。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]
および下記一般式(V)で表される化合物:
AmB3-mSi-(CH2)a-Sb-Z・・・(V)
[式中、AはCnH2n+1O(nは1~3の整数)又は塩素原子であり、Bは炭素数1~3のアルキル基であり、Zはベンゾチアゾリル基、N,N-ジメチルチオカルバモイル基又はメタクリロイル基であり、mは1~3の整数、aは1~9の整数、bは1以上の整数で分布を有していてもよい。但し、mが1の時、2つのBは同一でも異なってもよく、mが2又は3の時、2つ又は3つのAは同一でも異なってもよい。]
からなる群から選択される少なくとも一種であることを特徴とする請求項6に記載の空気入りタイヤ。 - 補強用充填剤としてカーボンブラックをゴム成分(A)100質量部に対して80質量部以下含有し、カーボンブラックと含水ケイ酸との総配合量が120質量部以下であることを特徴とする請求項1~7のいずれかに記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)の重量平均分子量(ゲルパーミエーションクロマトグラフィーによるポリスチレン換算)が1万~20万である請求項1~8のいずれかに記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)の重量平均分子量(ゲルパーミエーションクロマトグラフィーによるポリスチレン換算)が3万~15万である請求項9に記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)の重量平均分子量(ゲルパーミエーションクロマトグラフィーによるポリスチレン換算)が5万~15万である請求項10に記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)が、芳香族ビニル化合物が0~60質量%からなり、ジエン化合物部分のビニル結合が0~80質量%であることを特徴とする請求項1~11のいずれかに記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)が、芳香族ビニル化合物が0~50質量%からなり、ジエン化合物部分のビニル結合が0~70質量%であることを特徴とする請求項12に記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)の芳香族ビニル化合物がスチレンであることを特徴とする請求項1~13のいずれかに記載の空気入りタイヤ。
- 芳香族ビニル化合物-ジエン化合物共重合体(B)のジエン化合物がブタジエンであることを特徴とする請求項1~14のいずれかに記載の空気入りタイヤ。
Priority Applications (4)
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US13/386,097 US20120220693A1 (en) | 2009-07-22 | 2010-07-21 | Pneumatic tire |
CN201080042351.9A CN102510875B (zh) | 2009-07-22 | 2010-07-21 | 充气轮胎 |
JP2011523675A JP5734187B2 (ja) | 2009-07-22 | 2010-07-21 | 空気入りタイヤ |
EP10802285.6A EP2457947B1 (en) | 2009-07-22 | 2010-07-21 | Pneumatic tire |
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JP2009-171492 | 2009-07-22 | ||
JP2009171492 | 2009-07-22 |
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WO2011010665A1 true WO2011010665A1 (ja) | 2011-01-27 |
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PCT/JP2010/062249 WO2011010665A1 (ja) | 2009-07-22 | 2010-07-21 | 空気入りタイヤ |
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US (1) | US20120220693A1 (ja) |
EP (1) | EP2457947B1 (ja) |
JP (1) | JP5734187B2 (ja) |
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WO (1) | WO2011010665A1 (ja) |
Cited By (1)
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WO2011100660A1 (en) | 2010-02-12 | 2011-08-18 | Rhodia Operations | Compositions with freeze thaw stability |
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JP5545619B2 (ja) * | 2009-07-22 | 2014-07-09 | 株式会社ブリヂストン | タイヤ |
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- 2010-07-21 JP JP2011523675A patent/JP5734187B2/ja not_active Expired - Fee Related
- 2010-07-21 US US13/386,097 patent/US20120220693A1/en not_active Abandoned
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CN102510875B (zh) | 2014-11-05 |
EP2457947A1 (en) | 2012-05-30 |
US20120220693A1 (en) | 2012-08-30 |
CN102510875A (zh) | 2012-06-20 |
EP2457947B1 (en) | 2014-10-15 |
JPWO2011010665A1 (ja) | 2013-01-07 |
EP2457947A4 (en) | 2013-06-05 |
JP5734187B2 (ja) | 2015-06-17 |
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