JP5334520B2 - Pneumatic tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pneumatic tire capable of improving runflat durability. <P>SOLUTION: The pneumatic safety tire includes rubber component and not less than 55 mass part of carbon black to the rubber component 100 mass part, uses rubber composition wherein elastic modulus (M100) at 100% extension is not less than 10 MPa and a &Sigma; value at 28 to 150&deg;C of tangent loss tan&delta; is not more than 6.0 in vulcanized rubber physical properties, and has a cord configuring a carcass layer, which is a polyethylene naphthalate fiber cord. The carbon black is preferably at least one kind selected from a group made of an FEF class grade, an FF class grade, an HAF class grade, an ISAF class grade, and an SAF class grade. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a pneumatic tire, and more particularly to a pneumatic tire having better run-flat durability.

  Conventionally, in a pneumatic tire, particularly a run-flat tire, it is known that a side reinforcing layer made of a rubber composition alone or a composite of a rubber composition and a fiber is provided to improve the rigidity of the sidewall portion. (For example, Patent Document 1). When such a run-flat tire is driven with the internal pressure of the tire decreased due to puncture or the like, that is, in a so-called run-flat running state, as the deformation of the sidewall portion of the tire increases, the deformation of the side reinforcing layer also increases. The heat generation proceeds, and in some cases reaches 200 ° C. or higher. If such a state continues, the side reinforcing layer exceeds the fracture limit, and eventually the tire breaks down.

  Therefore, as means for gaining time until such failure, there is one that increases the volume of rubber, such as increasing the maximum thickness of the side reinforcing layer and the bead filler to be disposed.

Conventionally, in order to increase the rigidity of the side wall part, a reinforcing rubber layer having a crescent cross section is mainly arranged inside the carcass layer of the side wall part, and the carcass layer is further divided into 2 to 4 layers to run the run flat. Technology that supports the load of time is known. However, polyethylene terephthalate (ΡET) cord, which has been widely used in tires for passenger cars, has a tendency to generate heat due to various inputs during run-flat running and becomes high temperature, so even ΡET, which is said to have excellent heat resistance, is a rubber at high temperatures. The failure during run-flat running is mainly due to peeling at the interface between the ET / adhesive layer, and there is a problem in reliability during run-flat running. Further, in recent years, with a reduction in fuel consumption of vehicles, there has been a strong demand for reducing the mass of tires, and thinning of tire sidewalls has been increasingly aimed at reducing tire weight. Furthermore, it is naturally required to be able to run in a flat manner in which the internal pressure of the tire is 0 kg / cm ² , and at the same time to perform in normal running at the time of filling with internal pressure.

Therefore, Patent Document 2 discloses a technique of using a polyethylene naphthalate fiber cord for the carcass layer of the sidewall portion. When polyethylene naphthalate (PEN) that satisfies certain physical properties is used as an alternative to polyethylene terephthalate (PET) for the ply cord, the run-flat durability is 1.09 to 1.23 compared to when PET is used. It has been confirmed that it is improved up to twice.
JP 11-310019 A Japanese Patent Laid-Open No. 11-227426

  However, if the above-mentioned method of increasing the volume of rubber is used, undesirable situations such as deterioration in ride comfort, increase in weight and increase in noise level occur, and in order to avoid deterioration in ride comfort and reduce mass If the volume of the side reinforcing layer and bead filler to be disposed is reduced, the load during run flat cannot be supported, and the deformation of the sidewall portion of the tire during run flat becomes extremely large, leading to an increase in heat generation of the rubber composition. As a result, there is a problem that the tire is likely to break down earlier. Further, during running at zero internal pressure, the reinforcing rubber generates heat by bending the side portions, thereby increasing the deflection of the tire and further generating heat. As a result, the periphery of the side portion eventually breaks, and further improvement is desired.

  In addition, the method described in Patent Document 2 can improve the run-flat durability by using PEN as a cord constituting the carcass layer as compared with the case where PET is used. Flat durability is required, and further improvements are desired.

  Therefore, an object of the present invention is to provide a pneumatic tire having a better run-flat durability by eliminating such problems of the prior art.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by adopting the following configuration, and have completed the present invention.

That is, the pneumatic tire of the present invention has a pair of left and right bead portions and a pair of sidewall portions, and a tread portion connected to the sidewall portions, and a bead filler disposed on the radial outside of the bead core. The tread portion includes a side reinforcing layer disposed on the pair of sidewall portions along the inner surface of the carcass layer, with a carcass layer extending in a toroidal shape between the pair of left and right bead portions including In the pneumatic tire in which a belt composed of a belt layer is arranged on the outer side in the tire radial direction,
The rubber component contains 55 parts by mass or more of carbon black with respect to 100 parts by mass thereof, and in the vulcanized rubber properties, the elastic modulus at 100% elongation (M100) is 10 MPa or more and the tangent loss tan δ at 28 to 150 ° C. Using a rubber composition having a value of 6.0 or less,
The cord constituting the carcass layer is a polyethylene naphthalate fiber cord.

  In the present invention, the carbon black is preferably at least one selected from the group consisting of FEF grade, FF grade, HAF grade, ISAF grade and SAF grade, and the rubber component is an amine. It is preferable to include a modified conjugated diene polymer.

  Furthermore, in the present invention, the amine-modified conjugated diene polymer is preferably a protonic amine-modified conjugated diene polymer, and the amine-modified conjugated diene polymer is preferably a primary amine-modified conjugated polymer. A diene polymer is preferred.

  In the present invention, the primary amine-modified conjugated diene polymer is preferably obtained by reacting a protected primary amine compound with the active terminal of the conjugated diene polymer. The conjugated diene polymer may be obtained by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound in an organic solvent using an organic alkali metal compound as an initiator. preferable.

  In the present invention, the conjugated diene polymer is preferably polybutadiene, and the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropyltriethoxysilane. preferable.

  Furthermore, in this invention, it is preferable that the said side reinforcement layer and / or the said bead filler consist of the said rubber composition.

In the present invention, the twist coefficient R is the following formula:
R = N × (0.125 × D / ρ) ^1/2 × 10 ⁻³
Where N is the number of twists of the cord (times / 10 cm), D is the total number of decitex of the cord, and ρ is the density of the cord, and the twisting factor R of the polyethylene naphthalate fiber cord is 0 It is preferable that it is 70-0.85.

  Furthermore, in the present invention, the polyethylene naphthalate fiber cord is preferably formed by twisting two filament bundles made of polyethylene naphthalate having a fineness of 1200 to 1800 dtex.

  Furthermore, in the present invention, the polyethylene naphthalate fiber cord is preferably formed by twisting a filament bundle made of polyethylene naphthalate having a fineness of 3000 to 4000 dtex.

  In the present invention, the polyethylene naphthalate fiber cord has an elongation under a load of 1.4 gf / d at 50 ± 5 ° C. of 2.7% or less and 0.7 gf / d at 170 ± 5 ° C. It is preferable that elongation under load is 1.5 to 6.0%.

  Furthermore, in the present invention, it is preferable that at least one belt reinforcement layer is disposed on the entire tread portion on the outer peripheral side of the belt layer, and further, from the vicinity of the bead core, the sidewall portion and It is preferable that at least one down carcass layer is further disposed between the outer surface of the carcass layer and the vicinity of the other bead core.

  According to the present invention, a pneumatic tire having better run-flat durability can be provided.

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a partial cross-sectional view of a preferred example of the pneumatic tire of the present invention. The tire shown in FIG. 1 has a pair of left and right bead portions 1 and a pair of sidewall portions 2 and a tread portion 3 connected to both sidewall portions 2, and extends in a toroidal shape between the pair of bead portions 1. A carcass layer composed of one or more carcass plies 4 that reinforce each of these parts 1, 2, and 3, and a pair of crescent-shaped side reinforcing layers (reinforcing rubber layers) disposed inside the carcass ply 4 of the side wall 2 ) 5.

  In the illustrated tire, a bead filler 7 is disposed on the outer side in the tire radial direction of each ring-shaped bead core 6 embedded in the bead portion 1, and the outer side in the tire radial direction of the tread portion of the carcass ply 4. A belt 8 composed of two belt layers is disposed in the belt. Here, the belt layer is usually composed of a rubberized layer of a cord extending in an inclined manner with respect to the tire equatorial plane, preferably a rubberized layer of a steel cord, and the two belt layers constitute the belt layer. The belt 8 is formed by laminating the cords so as to cross each other with the equator plane interposed therebetween. In the illustrated example, the belt 8 includes two belt layers. However, in the pneumatic tire of the present invention, the number of belt layers constituting the belt 8 is not limited thereto.

  Further, in the present invention, it is preferable that at least one belt reinforcing layer is disposed on the entire tread portion 3 on the outer peripheral side of the belt layer. In the illustrated tire, a belt reinforcing layer 9A is disposed so as to cover the entire belt 8 on the outer side in the tire radial direction of the belt 8, and a pair of belts so as to cover only both ends of the belt reinforcing layer 9A. A reinforcing layer 9B is disposed. Here, the belt reinforcing layers 9A and 9B are usually made of rubberized layers of cords arranged substantially parallel to the tire circumferential direction. In the pneumatic tire of the present invention, the belt reinforcing layers 9A and 9B are not necessarily provided, and a belt reinforcing layer having a different structure may be provided.

  The carcass ply 4 in the illustrated example is composed of one carcass ply formed by coating a plurality of reinforcing cords arranged in parallel with a coating rubber, and each carcass ply 4 is embedded in the bead portion 1. A main body portion extending in a toroidal shape between the pair of bead cores 6 and a folded portion wound around each bead core 6 radially outward from the inner side to the outer side in the tire width direction. In the pneumatic tire, the number of plies and the structure of the carcass ply 4 are not limited to this. For example, a structure in which at least one down carcass layer is further disposed between the vicinity of the bead core 6, between the sidewall portion 2 and the outer surface of the carcass layer, and the vicinity of the other bead core 6 may be employed. .

  The pneumatic tire of the present invention contains 55 parts by mass or more of carbon black with respect to 100 parts by mass of a rubber component, and has a vulcanized rubber physical property of an elastic modulus at 100% elongation (M100) of 10 MPa or more and tangent It is important to use a rubber composition having a Σ value of loss tan δ at 28 to 150 ° C. of 6.0 or less and that the cord constituting the carcass layer is a polyethylene naphthalate fiber cord. By adopting the above-described configuration, the low exothermic mixed side reinforcing rubber can drastically improve the run flat durability by suppressing heat generation to a minimum even when subjected to bending deformation during running at zero internal pressure.

  First, the rubber composition according to the present invention will be described. The rubber composition according to the present invention contains 55 parts by mass or more of carbon black with respect to 100 parts by mass of the rubber component, and has a vulcanized rubber property having an elastic modulus at 100% elongation (M100) of 10 MPa or more and The Σ value at 28 to 150 ° C. of the tangent loss tan δ is 6.0 or less. By using the rubber composition according to the present invention particularly for the side reinforcing layer 8 and / or the bead filler 7 of the pneumatic tire, the pneumatic tire of the present invention can obtain the above-described effects more favorably.

  Examples of the rubber component of the rubber composition used in the present invention include natural rubber (NR) and diene synthetic rubber. Examples of the diene-based synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), styrene-isoprene copolymer (SIR), butyl rubber (IIR), halogenated butyl rubber, and ethylene. -Propylene-diene terpolymer (EPDM) and mixed rubbers thereof. Moreover, it is preferable that part or all of the diene-based synthetic rubber is a diene-based modified rubber having a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride.

  As the rubber composition according to the present invention, a rubber component containing an amine-modified conjugated diene polymer obtained by amine-modifying a conjugated diene polymer can be preferably used. Moreover, it is preferable that 30 mass parts or more of such an amine modified conjugated diene polymer is included, and it is more preferable that it is 50 mass parts or more. By containing 30 parts by mass or more of the amine-modified conjugated diene polymer as a rubber component, the resulting rubber composition can reduce the heat generation, and a pneumatic tire with improved run-flat durability can be obtained.

  As the amine-modified conjugated diene polymer, a polymer in which a protonic amino group which is an amine functional group and / or an amino group protected by a detachable group is introduced into the molecule as a functional group for modification is preferable. Further, those having a silicon atom-containing functional group introduced are more preferable. Examples of the functional group containing a silicon atom include a silane group formed by bonding a hydrocarbyloxy group and / or a hydroxy group to a silicon atom. Such a modified functional group may be present at any of the polymerization initiation terminal, the side chain, and the polymerization active terminal of the conjugated diene polymer, but is preferably a protic amino group at the polymerization terminal, more preferably at the same polymerization active terminal. An amino group protected by a group and / or a detachable group and a silicon atom to which a hydrocarbyloxy group and / or hydroxy group is bonded, particularly preferably one or two hydrocarbyloxy groups and / or hydroxy groups are bonded It has a silicon atom.

  Examples of the protic amino group include at least one selected from a primary amino group, a secondary amino group, and salts thereof. On the other hand, examples of the amino group protected with a detachable group include an N, N-bis (trihydrocarbylsilyl) amino group and an N- (trihydrocarbylsilyl) imino group. From the viewpoint of improvement, a trialkylsilyl group in which the hydrocarbyl group is an alkyl group having 1 to 10 carbon atoms can be exemplified, and a trimethylsilyl group can be particularly preferably exemplified. An example of a primary amino group protected with a detachable group (also referred to as a protected primary amino group) is N, N-bis (trimethylsilyl) amino group, which is protected with a detachable group. Examples of the secondary amino group include N- (trimethylsilyl) imino group. The N- (trimethylsilyl) imino group-containing group may be either an acyclic imine residue or a cyclic imine residue.

  Among the amine-modified conjugated diene polymers described above, as the primary amine-modified conjugated diene polymer modified with a primary amino group, a protected primary amine compound is reacted with the active terminal of the conjugated diene polymer. A primary amine-modified conjugated diene polymer modified with a protected primary amino group obtained by the above-described method is preferable.

  The conjugated diene copolymer used for modification may be a conjugated diene compound homopolymer or a copolymer of a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3 dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. Is mentioned. These may be used alone or in combination of two or more, and among these, 1,3-butadiene is particularly preferable. Examples of the aromatic vinyl compound used for polymerization with the conjugated diene compound include styrene, a-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2 , 4,6-trimethylstyrene and the like. These may be used alone or in combination of two or more. Among these, styrene is particularly preferable. As the conjugated diene polymer, polybutadiene or styrene-butadiene copolymer is preferable, and polybutadiene is particularly preferable.

  In order to modify the active end of the conjugated diene polymer by reacting with a protected primary amine, it is preferable that the conjugated diene polymer has at least 10% polymer chain having living or pseudo-living properties. . As the polymerization reaction having such a living property, an organic alkali metal compound is used as an initiator, and a conjugated diene compound alone or a reaction in which an conjugated diene compound and an aromatic vinyl compound are anionically polymerized in an organic solvent, or an organic solvent. Among them, a conjugated diene compound alone or a reaction in which a conjugated diene compound and an aromatic vinyl compound are coordinated anionic polymerized with a catalyst containing a lanthanum series rare earth element compound can be mentioned. The former is preferable because a conjugated diene moiety having a higher vinyl bond content than the latter can be obtained. Heat resistance can be improved by increasing the amount of vinyl bonds.

  As the organic alkali metal compound used as the above-mentioned anionic polymerization initiator, an organic lithium compound is preferable. The organolithium compound is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal is polymerized. A conjugated diene polymer which is an active site is obtained. When a lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.

  As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable. For example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n- Examples include decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butylphenyl lithium, 4-phenylbutyl lithium, cyclohexyl lithium, cyclobenthyl lithium, and reaction products of diisopropenylbenzene and butyl lithium. Of these, n-butyllithium is particularly preferable.

  On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, and lithium dipropyl amide. , Lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethyl Examples include amides. Of these, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable from the viewpoint of the interaction effect on carbon black and the ability to initiate polymerization. In particular, lithium hexamethylene imide and lithium pyrrolidide are preferred.

  As these lithium amide compounds, those prepared in advance from secondary amines and lithium compounds can be used for the polymerization, but they can also be prepared in the polymerization system (in-situ). The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

  There is no restriction | limiting in particular as a method of manufacturing a conjugated diene type polymer by anionic polymerization using the said organolithium compound as a polymerization initiator, A conventionally well-known method can be used. Specifically, a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, A conjugated diene polymer having a target active terminal can be obtained by anionic polymerization in the presence of a randomizer to be used, if desired, using the lithium compound as a polymerization initiator. Further, when an organolithium compound is used as a polymerization initiator, it has not only a conjugated diene polymer having an active end but also an active end, compared to the case of using a catalyst containing the above-mentioned lanthanum rare earth element compound. Copolymers of conjugated dienes and aromatic vinyl compounds can also be obtained efficiently.

  The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans- Examples include 2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene. These may be used alone or in combination of two or more. The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. In addition, when copolymerizing using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably in the range of 55% by mass or less.

  The randomizer used as desired is the control of the microstructure of the conjugated diene copolymer, for example, an increase in 1,2 bonds in the butadiene moiety in the butadiene-styrene copolymer, an increase in 3,4 bonds in isoprene, or the like. , A compound having a function of controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing butadiene units and styrene units in a butadiene-styrene copolymer. . The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, oxolanylpropane oligomers (especially those containing 2,2-bis (2-tetrahydrofuryl) -propane), triethylamine, pyridine N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, ethers such as 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium tert-amylate and potassium tert-butoxide, and sodium salts such as sodium tert-amylate can also be used.

  These randomizers may be used individually by 1 type, and may be used in combination of 2 or more type. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound. The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually preferred to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization solvent used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Is performed by an appropriate method such as pressurizing.

  In the present invention, a primary amine-modified conjugated diene polymer is obtained by reacting a protected primary amine as a modifier on the active terminal of the conjugated diene polymer having an active terminal obtained as described above. Can be manufactured. As the protected primary amine compound, an alkoxysilane compound having a protected primary amino group is suitable. Examples of the alkoxysilane compound having a protected primary amino group used as the modifier include N, N, -bis (trimethylsilyl) aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza. -2-silacyclopentane, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane and N, N-bis (trimethyl) Yl) aminoethylmethyldiethoxysilane, preferably N, N, -bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N, -bis (trimethylsilyl) aminopropylmethyldiethoxysilane, or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane.

  Further, as modifiers, N-methyl-N-trimethylsilylaminopropyl (methyl) dimethoxysilane, N-methyl-N-trimethylsilylaminopropyl (methyl) diethoxysilane, N-trimethylsilyl (hexamethyleneimin-2-yl) propyl (Methyl) dimethoxysilane, N-trimethylsilyl (hexamethyleneimin-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (pyrrolidin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (pyrrolidine-2) -Yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) diethoxysilane N-trimethylsilyl (imidazol-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (imidazol-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) Alkoxysilane compounds having a protected secondary amino group such as propyl (methyl) dimethoxysilane and N-trimethylsilyl (4,5-dihydroimidazol-5-yl) propyl (methyl) diethoxysilane; N- (1,3dimethyl) Butylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylide) ) -3- (Triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene)- Alkoxysilane compounds having an imino group such as 3- (triethoxysilyl) -1-propanamine; 3-dimethylaminopropyl (triethoxy) silane, 3-dimethylaminopropyl (trimethoxy) silane, 3-diethylaminopropyl (triethoxy) silane 3-diethylaminopropyl (trimethoxy) silane, 2-dimethylaminoethyl (triethoxy) silane, 2-dimethylaminoethyl (trimethoxy) silane, 3-dibutylaminopropyl (diethoxy) methylsilane, 3-dibutylaminopropyl (triethoxy) silane Examples thereof include alkoxysilane compounds having an amino group such as These modifiers may be used alone or in combination of two or more. The modifier may be a partial condensate. Here, the partial condensate means a product in which a part (not all) of the modifier SiOR is bonded to SiOSi by condensation.

  In the modification reaction with the modifying agent, the amount of the modifying agent is preferably 0.5 to 200 mmol / kg · conjugated diene polymer. The amount used is more preferably 1 to 100 mmol / kg · conjugated diene polymer, and particularly preferably 2 to 50 mmol / kg · conjugated diene polymer. Here, the conjugated diene polymer means the mass of only a polymer not containing an additive such as an anti-aging agent added at the time of production or after production. By making the usage-amount of a modifier into the said range, it is excellent in the dispersibility of a filler, especially carbon black, and the fracture resistance after vulcanization and low heat build-up are improved. The method for adding the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, and a continuous addition method. A batch addition method is preferable. . Further, the modifier can be bonded to any of the polymer main chain and the side chain other than the polymerization initiation terminal and the polymerization termination terminal, but it can suppress the loss of energy from the polymer terminal and improve the low heat generation. Therefore, it is preferably introduced at the polymerization initiation terminal or the polymerization termination terminal.

  In the present invention, a condensation accelerator is preferably used in order to accelerate the condensation reaction involving the alkoxysilane compound having a protected primary amino group used as the modifier. As such a condensation accelerator, a compound containing a tertiary amino group or a group 3, 4, 5, 12, 13, 14, or 15 of the periodic table (long period type) is used. An organic compound containing one or more elements belonging to any one of them can be used. Furthermore, as a condensation accelerator, an alkoxide containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn), a carboxyl An acid salt or an acetylacetonate complex salt is preferable.

  The condensation accelerator used here can be added before the above-mentioned modification reaction, but is preferably added to the modification reaction system during and / or after the modification reaction. When added before the denaturation reaction, a direct reaction with the active end may occur, and a hydrocarboxy group having a protected primary amino group at the active end may not be introduced. The addition time of the condensation accelerator is usually 5 minutes to 5 hours after the start of the modification reaction, preferably 15 minutes to 1 hour after the start of the modification reaction.

  Specific examples of the condensation accelerator include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-n-butoxytitanium oligomer, tetra-sec-butoxy. Titanium, tetra-tert-butoxytitanium, tetra (2-ethylhexyl) titanium, bis (octanediolate) bis (2-ethylhexyl) titanium, tetra (octanediolate) titanium, titanium lactate, titanium dipropoxybis (triethanolamido) Nate), titanium dibutoxybis (triethanolamate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium ethylhex Ludiolate, Titanium tripropoxyacetylacetonate, Titanium dipropoxybis (acetylacetonate), Titanium tripropoxyethylacetoacetate, Titaniumpropoxyacetylacetonatebis (ethylacetoacetate), Titanium tributoxyacetylacetonate, Titanium tributoxybis ( Acetylacetonate), titanium tributoxyethyl acetate, titanium butoxyacetylacetonate bis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) ) Titanium oxide, bis (laurate) titanium oxide, bis (naphthenate) Nium oxide, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexyl) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, tetrakis (stearate) Examples include titanium-containing compounds such as titanium, titanium (oleate) titanium, and tetrakis (linoleate) titanium.

  Examples of the condensation accelerator include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, and tris (linoleate). Bismuth, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, tetra (2-ethylhexyl) zirconium, zirconium tributoxy Stearate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate Zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium tetrakis (acetylacetonate), zirconium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, Bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexyl) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) zirconium, tetrakis (Stearate) Zirconium, Tetrakis (oleate) Zirconium, Tetra Scan (linoleate) zirconium, and the like can be given.

  Also, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tri (2-ethylhexyl) aluminum, aluminum dibutoxy Stearate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethylhexanoate) ) Aluminum, Tris (laurate) aluminum, Tris (naphthenate) aluminum, Tris (stearate) aluminum, Scan (oleate) aluminum, tris (linolate) aluminum, and the like.

  Of the above-described polymerization accelerators, titanium compounds are preferred, and titanium metal alkoxides, titanium metal carboxylates, or titanium metal acetylacetonate complex salts are particularly preferred. The amount of the condensation accelerator used is preferably such that the number of moles of the compound is 0.1 to 10 as the molar ratio to the total amount of hydrocarbyloxy groups present in the reaction system, and 0.5 to 5 Particularly preferred. By setting the amount used as the condensation accelerator within the above range, the condensation reaction proceeds efficiently.

  The condensation reaction in the present invention proceeds in the presence of the above condensation accelerator and water vapor or water. An example of the presence of water vapor is a solvent removal treatment by steam stripping, and the condensation reaction proceeds during steam stripping. The condensation reaction may be performed in an aqueous solution, and the condensation reaction temperature is preferably 85 to 180 ° C. More preferably. 100-170 degreeC, Most preferably, it is 110-150 degreeC. By setting the temperature during the condensation reaction within the above range, the condensation reaction can be efficiently progressed and completed, and the deterioration of the quality due to the aging reaction of the polymer due to the aging of the resulting modified conjugated diene polymer is suppressed. Can do.

  The condensation reaction time is usually about 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. The pressure of the reaction system during the condensation reaction time is usually 0.01 to 20 MPa, preferably 0.05 to 10 MPa. There is no restriction | limiting in particular about the type in the case of performing a condensation reaction in aqueous solution, You may carry out continuously using apparatuses, such as a batch type reactor or a multistage continuous reactor. Moreover, you may perform this condensation reaction and desolvent simultaneously.

  The primary amino group derived from the modifier of the modified conjugated diene polymer of the present invention is generated by performing a deprotection treatment as described above. Specific examples of suitable deprotection treatments other than the solvent removal treatment using steam such as steam stripping described above will be described in detail below. That is, the protecting group on the primary amino group is converted to a free primary amino group by hydrolysis. By removing the solvent from this, a modified conjugated diene polymer having a primary amino group can be obtained. In addition, the deprotection treatment of the protected primary amino group derived from the modifier can be performed as necessary in any stage from the stage including the condensation treatment to the solvent removal and the dry polymer.

The amine-modified diene rubber thus obtained has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of preferably 10 to 150, more preferably _{15 to} 100. When the Mooney viscosity is less than 10, sufficient rubber properties such as fracture resistance are not obtained. On the other hand, when it exceeds 150, workability is poor and it is difficult to knead with the compounding agent. Moreover, the Mooney viscosity (ML1 _{+ 4} , 130 degreeC) of the unvulcanized rubber composition based on this invention which mix | blended the said amine modified diene rubber becomes like this. Preferably it is 10-150, More preferably, it is 30-100.

  The modified conjugated diene rubber polymer used in the rubber composition according to the present invention has a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn), that is, a molecular weight distribution (Mw / Mn). Is preferably 1 to 3, and more preferably 1.1 to 2.7. By making the molecular weight distribution (Mw / Mn) of the modified conjugated diene rubber polymer within the above range, even if the modified conjugated diene rubber polymer is added to the rubber composition, the workability of the rubber composition is reduced. Therefore, kneading is easy and the physical properties of the rubber composition can be sufficiently improved.

  Further, the modified conjugated diene rubber polymer used in the rubber composition according to the present invention preferably has a number average molecular weight (Mn) of 100,000 to 500,000, preferably 150,000 to 300,000. More preferably. By setting the number average molecular weight of the modified conjugated diene rubber polymer within the above range, the elastic modulus of the vulcanizate is reduced and the increase in hysteresis loss is suppressed to obtain excellent fracture resistance, and the modified conjugated diene rubber weight Excellent kneading workability of the rubber composition containing the coalescence is obtained. The modified conjugated diene rubber polymer used in the rubber composition according to the present invention may be one kind or a combination of two or more kinds.

  In the rubber composition according to the present invention, the carbon black needs to be contained in an amount of 55 parts by mass or more with respect to 100 parts by mass of the rubber component. When the content of carbon black is less than 55 parts by mass, a sufficient reinforcing effect cannot be exerted, and in the vulcanized rubber properties of the resulting rubber composition, an elastic modulus at 100% elongation (M100) described later is obtained. It may not be 10 MPa or more. On the other hand, if the content of carbon black is too large, the Σ value at 28 to 150 ° C. of a tangent loss tan δ described later may not be 6.0 or less in the vulcanized rubber properties of the resulting rubber composition. Therefore, the preferable amount of carbon black is 55 to 70 parts by mass, and more preferably 60 to 70 parts by mass.

  As carbon black used in the present invention, in order that the vulcanized rubber properties of the obtained rubber composition satisfy the above vulcanized rubber properties, FEF grade, FF grade, HAF grade, ISAF grade and SAF It is preferable to use at least one selected from the group consisting of grade grades, and FEF grade grades are particularly suitable for achieving low heat generation.

  The rubber composition according to the present invention is required to have a vulcanized rubber property having an elastic modulus at 100% elongation (M100) of 10 MPa or more. When the elastic modulus (M100) is less than 10 MPa, the tire is not sufficiently bent and retained during run-flat running, and the run-flat durability of the tire is reduced. Preferred M100 is 10.5 MPa or more, and the upper limit is not particularly limited, but is usually about 13 MPa.

  Further, the Σ value at 28 to 150 ° C. of the tangent loss tan δ is required to be 6.0 or less. When the Σ value of tan δ (28 to 150 ° C.) exceeds 6.0, tire heat generation during run flat running is large, and the run flat running durability of the tire is lowered. The lower limit of the Σ value of tan δ (28 to 150 ° C.) is not particularly limited, but is usually about 5. The Σ values of the elastic modulus at 100% elongation (M100) and tan δ (28 to 150 ° C.) are values measured by the following method.

(Measurement method of elastic modulus at 100% elongation (M100))
An elastic modulus at 100% elongation is measured based on JIS K 6251 for a slab sheet having a thickness of 2 mm obtained by vulcanizing the rubber composition at 160 ° C. for 12 minutes.

(Measurement method of tan δ (28 to 150 ° C.))
A sheet having a width of 5 mm and a length of 40 mm was cut out from a slab sheet having a thickness of 2 mm obtained by vulcanizing the rubber composition at 160 ° C. for 12 minutes to prepare a sample. With respect to this sample, a tangent loss tan δ was measured using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. under measurement conditions of a chuck interval of 10 mm, an initial strain of 200 μm, a dynamic strain of 1%, a frequency of 52 Hz, and a measurement start temperature of 25 to 200 ° C. As shown in FIG. 5, the relationship between temperature and tan δ is graphed, the area of the shaded portion is obtained, and the value is set as the Σ value of tan δ (28 to 150 ° C.).

  The rubber composition according to the present invention includes various chemicals usually used in the rubber industry as desired, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an antioxidant, as long as the effects of the present invention are not impaired. Further, a scorch inhibitor, zinc white, stearic acid, and the like can be contained. Examples of the vulcanizing agent include sulfur, and the amount thereof used is preferably 0.1 to 10.0 parts by weight, more preferably 1.0 to 5 parts by weight, based on 100 parts by weight of the rubber component. 0.0 part by mass. If the amount is less than 0.1 parts by mass, the fracture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. On the other hand, if it exceeds 10.0 parts by mass, the rubber elasticity is lost.

  The vulcanization accelerator that can be used in the present invention is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothia). Thiol accelerators such as thiazoles such as disulfurenamide), guanidines such as DPC (diphenylguanidine), or thiurams such as TOT (tetrakis (2-ethylhexyl) thiuram disulfide). The amount used is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, as a sulfur content, with respect to 100 parts by weight of the rubber component.

  Examples of the process oil used as a softening agent that can be used in the rubber composition according to the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the deterioration of the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber is suppressed. can do.

  Furthermore, examples of the anti-aging agent that can be used in the rubber composition according to the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine), 6C (N- (1,3-dimethylbutyl)- N'-phenyl-p-phenylenediamine), AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), a high-temperature condensate of diphenylamine and acetone, and the like. The amount used is preferably 0.1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, with respect to 100 parts by mass of the rubber component.

  The rubber composition according to the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer or the like by the above blending, vulcanized after molding, and air in FIG. It is used for the side reinforcing part 8 and / or the bead filler 7 of the entering tire.

Then, the fiber cord which comprises the carcass layer of the pneumatic tire of this invention is demonstrated.
It is important that the fiber cord according to the present invention is a polyethylene naphthalate fiber cord. As a result, the deformation on the inside and outside of the sidewall can be suppressed by the high elastic modulus fiber (ΡEN), so that the heat generation at the tire side portion during the run-flat running can be reduced and the adhesion between the cord and the rubber can be improved. Even when heat is generated, the ΡEN fiber cord of the present invention can be better bonded at a higher temperature than the conventional ΡET fiber cord.

In the present invention, the twist coefficient R is the following formula:
R = N × (0.125 × D / ρ) ^1/2 × 10 ⁻³
Where N is the number of twists of the cord (times / 10 cm), D is the total number of decitex of the cord, and ρ is the density of the cord, and the twist coefficient R of the polyethylene naphthalate fiber cord is 0 .70 to 0.85 is preferable in terms of achieving a high elastic modulus and high temperature adhesiveness. If the twist coefficient R is less than 0.70, the elastic modulus can be improved, but the adhesiveness is lowered, so that the run-flat durability may be inferior. On the other hand, if the twist coefficient R exceeds 0.85, the adhesiveness is deteriorated. However, since the elastic modulus is lowered, the side wall of the tire has a large deflection, and the run-flat durability may be deteriorated.

  Furthermore, in the present invention, the polyethylene naphthalate fiber cord is preferably formed by twisting two or three filament bundles made of polyethylene naphthalate having a fineness of 1200 to 1800 dtex. Is more preferable. For example, it is possible to obtain a twisted cord with a double twist structure by applying a lower twist to the filament bundle made of polyethylene naphthalate, then combining a plurality of them and applying an upper twist in the opposite direction. If the fineness of the filament bundle used for the polyethylene naphthalate fiber cord is less than 1200 dtex, both the elastic modulus and the heat shrinkage stress are insufficient, and if it exceeds 1800 dtex, the cord diameter becomes thick and the driving cannot be made dense.

  Alternatively, the polyethylene naphthalate fiber cord is preferably formed by twisting a filament bundle made of polyethylene naphthalate having a fineness of 3000 to 4000 dtex. For example, it is possible to obtain a twisted cord having a single-twist structure by subjecting one filament bundle made of polyethylene naphthalate to a lower twist or an upper twist. If the fineness of the filament bundle used for the polyethylene naphthalate fiber cord is less than 3000 dtex, both the elastic modulus and the heat shrinkage stress are insufficient, and if it exceeds 4000 dtex, the cord diameter becomes thick and the driving cannot be made dense.

  When pneumatic tires are used for SUVs (sports multipurpose vehicles), the load is large during run-flat travel, so it is necessary to significantly improve the durability during run-flat. By adopting such a twisted structure, run-flat durability can be greatly improved.

  The polyethylene naphthalate fiber cord has an elongation under a load of 1.4 gf / d at 50 ± 5 ° C. of 2.7% or less and an elongation under a load of 0.7 gf / d at 170 ± 5 ° C. It is preferable that it is 1.5 to 6.0%. In the present invention, since the high-strength side reinforcing layer 5 is disposed inside the sidewall portion, the rigidity of the entire tire is higher than that of a tire not provided with the side reinforcing layer 5, and the bumps and the like are overcome during normal running. This is preferable from the viewpoint of road noise. Therefore, road noise can be improved by using a cord having physical properties having a relatively large elastic modulus as described above.

  The pneumatic tire of the present invention can be manufactured by a conventional method by applying the polyethylene naphthalate fiber cord to the carcass ply of the carcass 4. In the pneumatic tire of the present invention, as the gas filled in the tire, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen can be used.

Hereinafter, the present invention will be specifically described based on examples.
Eight types of rubber compositions having the compounding compositions A to C shown in Table 1 below were prepared, and vulcanized rubber properties, that is, Σ values at 28 to 150 ° C. of M100 and tan δ were determined. Next, cords were produced using the materials, cord structures, twist numbers, twist coefficients, and blending compositions shown in Tables 2 to 5 below. The primary amine-modified polybutadiene was prepared by the following procedure.

<Production Example 1 Production of primary amine-modified polybutadiene>
A nitrogen-substituted 5 L autoclave was injected under nitrogen as a solution of 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, 2,2-ditetrahydrofurylpropane (0.0285 mmol) in cyclohexane, and 2.85 mmol of n- After adding butyl lithium (Bu—Li), polymerization was carried out in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. This polymerization solution was drawn into a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping and dried with a roll at 110 ° C. Thus, polybutadiene was obtained. The resulting polybutadiene was measured for microstructure (vinyl bond amount), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn). As a result, the vinyl bond content was 14%, Mw was 150,000, and Mw / Mn was 1.1.

  The obtained polymer solution was kept at a temperature of 50 ° C. without deactivating the polymerization catalyst, and 1129 mg (3.364 mmol) of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane in which the primary amino group was protected. ) And the denaturation reaction was carried out for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymerization solution after the reaction. Next, the primary amino group that was desolvated and protected by steam stripping was removed, and the rubber was dried by a hot roll adjusted to 110 ° C. to obtain primary amine-modified polybutadiene. The resulting modified polybutadiene was measured for microstructure (vinyl bond amount), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and primary amino group content. As a result, the vinyl bond content was 14%, Mw was 150,000, Mw / Mn was 1.2, and the primary amino group content was 4.0 mmol / kg. The microstructure is analyzed by infrared method (Morello method), and Mn, Mw, and Mw / Mn are measured by GPC (manufactured by Tosoh Corporation: HLC-8020) using a refractometer as a detector, and monodisperse It was shown in terms of polystyrene using polystyrene as a standard. The column is GMHXL (manufactured by Tosoh Corporation) and the eluent is tetrahydrofuran.

<Measurement of primary amino group content>
First, after dissolving the polymer in toluene, the amino group-containing compound not bound to the polymer was separated from the rubber by precipitation in a large amount of methanol, and then dried. Using this treated polymer as a sample, the total amino group content was quantified by the “total amine value test method” described in JIS K 7237. Subsequently, secondary amino groups and tertiary amino groups were quantified by the “acetylacetone blocked method” using the polymer subjected to the above treatment as a sample. As a solvent for dissolving the sample, o-nitrotoluene was used, acetylacetone was added, and potentiometric titration was performed with a perchloracetic acid solution. The primary amino group content (mmol) is obtained by subtracting the secondary amino group content and tertiary amino group content from the total amino group content, and is divided by the polymer mass used in the analysis, thereby binding to the polymer primary. The amino group content (mmol / kg) was determined.

<Production Example 2 Production of DMBTESPA-modified polybutadiene>
In Production Example 1, 1129 mg (3.364 mmol) of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was converted to N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine. DMBTESPA-modified polybutadiene was obtained in the same manner as in Production Example 1, except that the amount was changed to 3.364 mmol.

  A run flat tire of the type shown in FIG. 1 was produced using the previously produced cord. About each obtained test tire, run-flat durability was evaluated. The evaluation method is as follows. In addition, the maximum thickness of the side reinforcement layer was calculated | required as a reinforcement rubber gauge, and was shown in Tables 2-5.

<Runflat durability>
Each test tire (passenger car radial tire of tire size 215 / 45R17) is assembled with rims at normal pressure, filled with 230 kPa of internal pressure, allowed to stand at room temperature of 38 ° C. for 24 hours, then the valve core is removed to increase the internal pressure. The drum running test was performed under the conditions of a pressure of 4.17 kN (425 kgf), a speed of 89 km / h, and an indoor temperature of 38 ° C. as atmospheric pressure. Measure the distance traveled until the failure of each test tire, the distance of Comparative Example 1 as 100,
Run-flat durability (index) = (travel distance of test tire / travel distance of tire of Comparative Example 1)
The index was displayed. The larger the index, the better the run flat durability.

※１ 天然ゴム：ＴＳＲ２０
※２ 未変性ＢＲ：未変性ポリブタジエン（ＪＳＲ社製ＢＲ０１）
※３ 変性ＢＲ１：１級アミン変性ポリブタジエン（製造例１で得られたもの）
※４ 変性ＢＲ２：ＤＭＢＴＥＳＰＡ変性ポリブタジエン（製造例２で得られたもの）
※５ カーボンブラック：ＦＥＦ（Ｎ５５０）（旭カーボン社製、旭＃６０）
※６ プロセスオイル：アロマティックオイル（富士興産社製、アロマックス＃２）
※７ 老化防止剤６Ｃ：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（大内新興化学工業社製、ノクラック６Ｃ）
※８ 加硫促進座剤ＤＺ：Ｎ，Ｎ’−ジシクロヘキシル−２−ベンゾチアジルスルフェンアミド（大内新興化学工業社製、ノクセラーＤＺ）
※９ 加硫促進座剤ＴＯＴ：テトラキス（２−エチルヘキシル）チウラムジスルフィド（大内新興化学工業社製、ノクセラーＴＯＴ−Ｎ）

* 1 Natural rubber: TSR20
* 2 Unmodified BR: Unmodified polybutadiene (BR01 manufactured by JSR)
* 3 Modified BR1: primary amine modified polybutadiene (obtained in Production Example 1)
* 4 Modified BR2: DMBTESPA modified polybutadiene (obtained in Production Example 2)
* 5 Carbon black: FEF (N550) (Asahi Carbon Corporation, Asahi # 60)
* 6 Process oil: Aromatic oil (Fujikosan, Aromax # 2)
* 7 Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., NOCRACK 6C)
* 8 Vulcanization accelerating suppository DZ: N, N'-dicyclohexyl-2-benzothiazylsulfenamide (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DZ)
* 9 Vulcanization accelerating suppository TOT: tetrakis (2-ethylhexyl) thiuram disulfide (manufactured by Ouchi Shinko Chemical Industries, Noxeller TOT-N)

  From the said Tables 2-5, it was confirmed that the pneumatic tire which concerns on this invention can improve run flat durability.

It is a half sectional view of the pneumatic tire of the present invention. It is explanatory drawing for calculating | requiring tan (delta) (28-150 degreeC) in the vulcanization | cure property of a rubber composition.

Explanation of symbols

1 Bead part 2 Side wall part 3 Tread part 4 Carcass ply 5 Side reinforcement layer (reinforcement rubber layer)
6 Bead core 7 Bead filler 8 Belt 9A, 9B Belt reinforcement layer

Claims (18)

A pair of left and right bead portions including a pair of left and right bead portions and a pair of sidewall portions, and a tread portion connected to the sidewall portions, and including a bead core and a bead filler disposed radially outside the bead core. And a carcass layer extending in a toroid form as a skeleton, and a side reinforcing layer disposed on a pair of the side wall portions along the inner surface of the carcass layer. In the pneumatic tire in which the belt is arranged, the rubber component contains 55 parts by mass or more of carbon black with respect to 100 parts by mass, and the vulcanized rubber has a 100% elongation elasticity modulus (M100) of 10 MPa or more. And a rubber composition having a tangent loss tan δ of Σ value at 28 to 150 ° C. of 6.0 or less,
Cord constituting the carcass layer, the air inlet Rita ear, which is a polyethylene naphthalate fiber cord.   The pneumatic tire according to claim 1, wherein the carbon black is at least one selected from the group consisting of FEF grade, FF grade, HAF grade, ISAF grade and SAF grade.   The pneumatic tire according to claim 1 or 2, wherein the rubber component contains an amine-modified conjugated diene polymer. The pneumatic tire according to claim 3, wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer.   The pneumatic tire according to claim 3 or 4, wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.   The pneumatic tire according to claim 5, wherein the primary amine-modified conjugated diene polymer is obtained by reacting a protected primary amine compound with an active end of a conjugated diene polymer.   7. The conjugated diene polymer is obtained by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound in an organic solvent using an organic alkali metal compound as an initiator. Pneumatic tire described in 2. The pneumatic tire according to claim 7, wherein the conjugated diene polymer is polybutadiene.   The pneumatic tire according to any one of claims 6 to 8, wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropyltriethoxysilane.   The pneumatic tire according to claim 1, wherein the side reinforcing layer is made of the rubber composition.   The pneumatic tire according to claim 1, wherein the bead filler is made of the rubber composition.   The pneumatic tire according to claim 1, wherein the side reinforcing layer and the bead filler are made of the rubber composition. The twist coefficient R is the following formula:
R = N × (0.125 × D / ρ) ^1/2 × 10 ⁻³
Where N is the number of twists of the cord (times / 10 cm), D is the total number of decitex of the cord, and ρ is the density of the cord, and the twisting factor R of the polyethylene naphthalate fiber cord is 0 The pneumatic tire according to any one of claims 1 to 12, which is 70 to 0.85.   The pneumatic tire according to any one of claims 1 to 13, wherein the polyethylene naphthalate fiber cord is formed by twisting two filament bundles made of polyethylene naphthalate having a fineness of 1200 to 1800 dtex.   The pneumatic tire according to any one of claims 1 to 13, wherein the polyethylene naphthalate fiber cord is formed by twisting a filament bundle made of polyethylene naphthalate having a fineness of 3000 to 4000 dtex.   The polyethylene naphthalate fiber cord has an elongation under a load of 1.4 gf / d at 50 ± 5 ° C. of 2.7% or less, and an elongation under a load of 0.7 gf / d at 170 ± 5 ° C. is 1. The pneumatic tire according to any one of claims 1 to 15, which is 5 to 6.0%.   The pneumatic tire according to any one of claims 1 to 16, wherein a belt reinforcing layer made of at least one sheet is further disposed on the entire tread portion on the outer peripheral side of the belt layer.   The at least 1 down carcass layer is further arrange | positioned between the said bead core vicinity between the said side wall part and the outer surface of the said carcass layer, and the other bead core vicinity. A pneumatic tire according to claim 1.

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