JP5638749B2 - Pneumatic tire - Google Patents

Description

  The present invention relates to a pneumatic tire, and more particularly, to a side-reinforced run-flat tire that has greatly improved durability during run-flat running without impairing riding comfort during normal running.

  Conventionally, tires that can safely travel a certain distance without losing their load bearing capacity even when the internal pressure of the tire is reduced due to puncture, etc. The side reinforcing rubber layer is placed on the inner surface of the carcass with a relatively high modular crescent shape to improve the rigidity of the side wall. Various types of side-reinforced run-flat tires that can bear a load without significantly increasing the load have been proposed. (See Patent Documents 1 to 4).

  However, the conventional side-reinforced run-flat tire has a large deflection of the tire during run-flat running, and the sidewall portion becomes hot during run-flat running, and the rigidity of the sidewall portion is increased due to softening of rubber. Since the lowering and the bending become larger, the main cause of the failure at the end of the run-flat traveling is due to the crack of the side reinforcing rubber layer having a crescent cross section. Therefore, the conventional side reinforcement type run-flat tire has a problem that the durability distance in the run-flat running is short.

On the other hand, if the side wall is reinforced by increasing the gauge of the side reinforcing rubber layer to increase the durability of the tire during run-flat running, the tire weight increases and the tire rolls during normal running. There is a problem that the resistance increases and the fuel efficiency decreases, and the vertical spring of the tire during normal driving rises, and the riding comfort during normal driving deteriorates.
If the volume of the side reinforcing layer and the bead filler to be disposed is reduced in order to avoid the above-mentioned situation, for example, deterioration of the ride comfort, the load at the time of run flat cannot be supported. Deformation becomes very large, leading to an increase in heat generation of the rubber composition, and as a result, the tire has a problem of causing failure earlier.
Similarly, when the rubber used is made to be less elastic by changing the compounding material, the rubber composition is not able to support the load during run-flat, and the deformation of the sidewall portion of the tire becomes very large. As a result, the tires are likely to break down earlier as a result.

JP 2000-264012 A Special table 2002-500587 gazette Japanese translation of PCT publication No. 2002-500589 JP 2004-306658 A

  Under such circumstances, an object of the present invention is to provide a pneumatic tire with improved run-flat durability without impairing rolling resistance and riding comfort during normal driving.

As a result of intensive studies to develop a pneumatic tire having the above-mentioned preferable properties, the present inventor has found that the region A from the belt end to the maximum width portion of the tire side portion and the vicinity of the bead core of the side reinforcing type run-flat tire By disposing a reinforcing cord layer formed by rubberizing a polyketone fiber cord having a specific heat shrinkage stress and elastic modulus in at least a part of the region B from the bead filler to the bead filler, the riding comfort of the tire during normal running is improved. Suppresses the tire deflection during run-flat running without deteriorating, and the vulcanized rubber properties have a modulus of elasticity at 100% elongation equal to or greater than a certain value, and the sigma value of tangent loss tan δ at 28 ° C. to 150 ° C. Pneumatic tires that use rubber compositions with a certain value or less, especially for side reinforcing layers and / or bead fillers, are suitable for that purpose. I found out that I could do it. The present invention has been completed based on such findings.
That is, the present invention
[1] A radial carcass composed of one or more carcass plies extending in a toroidal shape between bead cores embedded in a pair of bead portions, and a radial carcass crown portion of the radial carcass disposed on the outer side in the tire radial direction. A tread portion; a pair of buttress portions located at both ends of the tread portion; a pair of sidewall portions connecting the buttress portion and the bead portion; and the radial extending from the buttress portion to the sidewall portion. In a pneumatic tire provided with a pair of crescent-shaped side reinforcing rubber layers disposed inside the carcass, a region A from the belt end to the maximum width portion of the tire side portion and a region from the vicinity of the bead core to the bead filler At least a part of B is formed by twisting a plurality of filament bundles made of polyketone, and the following formula (I) and Formula (II):
σ ≧ −0.01 × E + 1.2 (I)
σ ≧ 0.02 (II)
[Wherein σ is a heat shrinkage stress (cN / dtex) at 177 ° C .; E is an elastic modulus (cN / dtex) at a load of 49 N at 25 ° C.] A reinforcing cord layer coated with rubber is disposed, and (B) carbon black is 55 parts by mass or more with respect to 100 parts by mass of (A) rubber component as the side reinforcing rubber and / or bead filler rubber. And a rubber composition having a 100% elongation elastic modulus (M100) of 10 MPa or more and a tangent loss tan δ of Σ value at 28 ° C. to 150 ° C. of 6.0 or less. Features pneumatic tires,
[2] The pneumatic tire according to [1], wherein the reinforcing cord layer is disposed in a region A from the belt end to the maximum width portion of the tire side portion.
[3] The pneumatic tire according to [1], wherein an angle of the polyketone fiber cord in the reinforcing cord layer with respect to a tire radial direction is 0 to 85 °.
[4] The polyketone fiber cord has the following formula (III):
Nt = tan θ = 0.001 × N × (0.125 × D / ρ) ^1/2 (III)
[Where N is the number of twists (times / 10 cm), ρ is the specific gravity of the cord (g / cm ³ ), and D is the total decitex number (dtex) of the cord] The pneumatic tire of the above-mentioned [1], wherein is 0.25 or more,
[5] The pneumatic tire according to [1], wherein the number of driven polyketone fiber cords in the reinforcing cord layer is 5 to 60 (lines / 50 mm),
[6] The pneumatic tire according to the above [1], wherein the polyketone fiber cord is formed by twisting two or three filament bundles made of polyketone having a fineness of 500 to 2000 dtex,
[7] The pneumatic tire according to any one of [1] to [6], wherein the polyketone fiber cord has a reversibility that shrinks at a high temperature and expands when returned to room temperature.
[8] The polyketone is represented by the following general formula (IV):

[Wherein A is a portion derived from an unsaturated compound polymerized by an unsaturated bond, and each repeating unit may be the same or different], and substantially consists of the repeating unit represented by the above [1] to [7] Any of the pneumatic tires,
[9] The pneumatic tire according to the above [8], wherein A in the formula (IV) is an ethylene group,
[10] The pneumatic composition according to [1], wherein in the rubber composition, (B) carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade. tire,
[11] (B) The pneumatic tire according to [10], wherein the carbon black is FEF grade grade,
[12] The pneumatic tire according to any one of claims 1, 10 and 11, wherein in the rubber composition, (A) the rubber component contains an amine-modified conjugated diene polymer.
[13] The pneumatic tire according to [12], wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer,
[14] The pneumatic tire according to the above [12] or [13], wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.
[15] The pneumatic tire according to [14], wherein the primary amine-modified conjugated diene polymer is obtained by reacting a protected primary amine compound with an active terminal of the conjugated diene polymer.
[16] The above 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. [15] a pneumatic tire,
[17] The pneumatic tire of [16] above, wherein the conjugated diene polymer is polybutadiene.
[18] The pneumatic tire according to any one of the above [15] to [17], wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropyltriethoxysilane.
[19] The pneumatic tire according to any one of the above [1] to [18], wherein the rubber composition is used for the side reinforcing layer.
[20] A pneumatic tire according to any one of the above [1] to [18] using the rubber composition as a bead filler, and [12] using the rubber composition as a side reinforcing layer and a bead filler. The pneumatic tire according to any one of claims 1 to 18,
Is to provide.

  According to the present invention, the polyketone fiber cord having specific heat shrinkage stress and elastic modulus is coated on at least a part of the region A from the belt end to the maximum width portion of the tire side portion and the region B from the vicinity of the bead core to the bead filler. Reinforcement cord layer formed by covering with rubber is disposed, and in vulcanized rubber properties, the elastic modulus at 100% elongation is 10 MPa or more, and the Σ value of tangent loss tan δ at 28 ° C. to 150 ° C. is 6.0 or less. A pneumatic tire with improved run-flat durability without sacrificing rolling resistance and riding comfort during normal running by using the rubber composition in particular for the side reinforcing layer and / or bead filler of the tire. can do.

[Pneumatic tire]
First, the pneumatic tire of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic view showing a cross section of one embodiment of the pneumatic tire of the present invention, and FIGS. 2, 3, 4 and 5 are partial cross sections of other embodiments of the pneumatic tire of the present invention. FIG.

  The illustrated tire includes a main body portion extending in a toroid shape between bead cores 2 embedded in a pair of bead portions 1 and a folded portion wound around the bead core 2 radially outward from the inside in the tire width direction to the outside. A radial carcass 3, a tread portion 4 disposed on the outer side in the tire radial direction of the crown portion of the radial carcass 3, a pair of buttress portions 5 located at both ends of the tread portion 4, and the buttress portion 5, A pair of sidewall portions 6 that connect the bead portion 1 and a pair of crescent-shaped side reinforcing rubber layers 7 that are disposed inside the radial carcass 3 extending from the buttress portion 5 to the sidewall portion 6. And at least part of the region A from the belt end to the maximum width portion of the tire side portion and the region B from the vicinity of the bead core to the bead filler And a pair of reinforcing cord layer 8 disposed outside of the radial carcass 3.

  In the illustrated tire, a bead filler 9 is disposed between the radial carcass 3 main body portion and the folded portion and outside the bead core 2 in the tire radial direction, and the radial carcass 3 has a crown portion. A belt 10 composed of two belt layers is disposed on the outer side in the tire radial direction, and a belt reinforcing layer 11A is further disposed on the outer side in the tire radial direction of the belt 10 so as to cover the entire belt 10. A pair of belt reinforcing layers 11B is disposed so as to cover only both ends of the reinforcing layer 11A. 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 10 is configured by laminating cords so as to cross each other with the tire equator plane interposed therebetween. The belt reinforcing layers 11A and 11B are usually made of rubberized layers of cords arranged substantially parallel to the tire circumferential direction.

  Note that the radial carcass 3 of the illustrated tire is composed of one carcass ply. However, in the pneumatic tire of the present invention, the number of carcass plies constituting the radial carcass 3 is not limited to this. It may be more than one, and the structure is not particularly limited. Moreover, although the belt 10 of the example of illustration consists of two belt layers, in the pneumatic tire of this invention, the number of the belt layers which comprise the belt 10 is not restricted to this. Furthermore, the belt reinforcement layers 11A and 11B in the illustrated example are composed of a single belt reinforcement layer 11A that covers the entire belt 10 and two belt reinforcement layers 11B that cover only both ends of the belt reinforcement layer 11A. However, in the pneumatic tire of the present invention, the belt reinforcing layers 11A and 11B are not necessarily provided, and a belt reinforcing layer having a different structure and the number of layers may be provided.

  Furthermore, the tire of the illustrated example includes a rim guard 12 having a substantially triangular cross section on the outer side in the tire width direction of the folded portion of the radial carcass 3 in the region extending from the sidewall portion 6 to the bead portion 1. In the tire, the rim guard 12 is not essential, and rim guards of other shapes can be provided. In the present invention, the maximum width portion of the tire side portion refers to the maximum width portion of the tire side portion when the rim guard 12 is not provided.

  Here, in the tire shown in FIG. 1, a single reinforcing cord layer 8 is disposed outside the radial carcass 3 in a region extending from the buttress portion 5 to the sidewall portion 6. As long as at least one reinforcing cord layer 8 is disposed in at least a part of the region A from the end portion of the belt 10 to the maximum width portion of the tire side portion and the region B from the vicinity of the bead core to the bead filler. The reinforcing cord layer 8 may be provided with two or more layers, or the reinforcing cord layer 8 may extend to a portion other than the region A and the region B.

For example, in the pneumatic tire of the present invention, as shown in FIG. 2, the reinforcing cord layer 8 is disposed outside the radial carcass 3 in the region from the end portion of the belt 10 to the end portion of the folded portion of the carcass. As shown in FIG. 3, the reinforcing cord layer 8 extends from the end of the belt 10 along the outer side of the radial carcass 3 to the bead portion 1 through the space between the main body portion of the radial carcass 3 and the bead filler 9. 4, the reinforcing cord layer 8 extends from the end of the belt 10 along the outer side of the radial carcass 3. As shown in FIG. 4, the reinforcing cord layer 8 is folded and locked around the bead core 2 embedded in the bead portion 1. 5, a mode extending between the main body portion of the radial carcass 3 and the bead filler 9 and the vicinity of the bead core 2 embedded in the bead portion 1, as shown in FIG. 5, the reinforcing cord layer 8 is attached to the end of the belt 10. And outer radial carcass 3 in the region up to the end of the folded portion of the carcass from, also respectively arranged manner and between the main body and a bead filler 9 of the radial carcass 3 preferred.
By using the rubber composition according to the present invention for the side reinforcing layer 7 and / or the bead filler 9 of the pneumatic tire according to the embodiment shown in FIGS. 1 to 5, the pneumatic tire of the present invention has the above-described effects. Can be played.

[Polyketone fiber cord]
In the pneumatic tire of the present invention, the reinforcing cord layer 8 disposed in at least a part of the region A and the region B is formed by twisting a plurality of filament bundles made of polyketone, and the following formulas (I) and ( II):
σ ≧ −0.01 × E + 1.2 (I)
σ ≧ 0.02 (II)
[Wherein σ is a heat shrinkage stress (cN / dtex) at 177 ° C .; E is an elastic modulus (cN / dtex) at a load of 49 N at 25 ° C.] It needs to be covered with rubber.

  Since the above polyketone fiber cord has a large thermal shrinkage stress at high temperatures, it exhibits high rigidity from the initial relatively small tire distortion during run-flat running where the tire is hot, and the diameter of the sidewall portion of the tire. The bending rigidity of the direction can be increased to suppress the bending of the tire, and as a result, the run flat durability of the tire can be improved. On the other hand, the polyketone fiber cord is low in rigidity when the tire strain in the cord extension direction during normal running is small, so the vertical spring of the tire during normal running is not raised, and the riding comfort of the tire is deteriorated. I will not let you.

  If the cord to be used does not satisfy the relationship of the above formula (I), the use of a cord having a large heat shrinkage stress σ but a low elastic modulus E sufficiently suppresses the deflection of the tire during run-flat running. If a cord with a high elastic modulus E but a small heat shrinkage stress σ is used, the vertical spring of the tire during normal running increases, and the tire during normal running The ride comfort is worse. Further, when the heat shrinkage stress σ at 177 ° C. of the cord to be used is less than 0.02 cN / dtex, the amount of deflection at the time of run-flat running becomes large and the run-flat durability distance becomes insufficient.

  Here, the polyketone fiber cord preferably has a heat shrinkage stress σ at 177 ° C. of 1.5 cN / dtex or less. When the heat shrinkage stress σ of polyketone fiber cords at 177 ° C exceeds 1.5 cN / dtex, the shrinkage force during vulcanization becomes too large, resulting in the damage of the cord inside the tire and the rubber placement, resulting in durability. It will cause deterioration of sex and uniformity. The polyketone fiber cord preferably has a heat shrinkage stress σ at 177 ° C. of 0.20 cN / dtex or more from the viewpoint of sufficiently suppressing deformation of the tire during run flat running. From the viewpoint of surely suppressing the deformation, the heat shrinkage stress σ at 177 ° C. is more preferably 0.30 cN / dtex or more, and further preferably more than 0.4 cN / dtex. In addition, the effect which suppresses the deformation | transformation of the tire at the time of run-flat driving | running | working is so high that heat contraction stress (sigma) is high. Further, the polyketone fiber cord preferably has an elastic modulus E at a load of 49 N at 25 ° C. of 30 cN / dtex or more from the viewpoint of sufficiently suppressing deformation of the tire during run flat running. From the viewpoint of reliably suppressing the deformation of the tire, the elastic modulus E at a load of 49 N is more preferably 80 cN / dtex or more. Furthermore, the polyketone fiber cord preferably has an elastic modulus E at a load of 49 N at 25 ° C. of 170 cN / dtexx or less from the viewpoint of sufficiently ensuring fatigue resistance, from the viewpoint of improving fatigue resistance. More preferably, the elastic modulus E at a load of 49 N is 150 cN / dtex or less.

  The angle of the polyketone fiber cord in the reinforcing cord layer 8 with respect to the tire radial direction is preferably in the range of 0 to 85 °. If the angle of the polyketone fiber cord with respect to the tire radial direction exceeds 85 °, it is not possible to sufficiently suppress the deflection of the tire during run-flat running, and the tire run-flat durability tends not to be sufficiently improved. There is. 0 ° is particularly preferred.

The polyketone fiber cord used for the reinforcing cord layer 8 has the following formula (III):
Nt = tan θ = 0.001 × N × (0.125 × D / ρ) ^1/2 (III)
[Where N is the number of twists (times / 10 cm), ρ is the specific gravity of the cord (g / cm ³ ), and D is the total decitex number (dtex) of the cord] Is preferably 0.25 or more. When the twist coefficient (Nt) of the polyketone fiber cord is less than 0.25, the fatigue property is lowered and the durability is insufficient.

  In the reinforcing cord layer 8 of the pneumatic tire of the present invention, the number of driven polyketone fiber cords is preferably in the range of 5 to 60 (lines / 50 mm). If the number of driven polyketone fiber cords in the reinforcing cord layer 8 is less than 5 (lines / 50 mm), the deflection of the tire during run-flat running cannot be sufficiently suppressed, and the run-flat durability of the tire is sufficiently improved. On the other hand, if it exceeds 60 (lines / 50 mm), the vertical spring of the tire during normal running tends to rise, and the riding comfort of the tire during normal running tends to deteriorate.

  The polyketone fiber cord used for the reinforcing cord layer 8 is preferably formed by twisting two or three filament bundles made of polyketone having a fineness of 500 to 2000 dtex. If the fineness of the filament bundle used for the polyketone fiber cord is less than 500 dtex, both the elastic modulus and the heat shrinkage stress are insufficient, and if it exceeds 2000 dtex, the cord diameter becomes thick and the driving cannot be made dense. Even if the number of filament bundles made of polyketone is 4 or more, there is no particular limitation as long as the relationship of the above formulas (I) and (II) can be satisfied.

  The polyketone fiber cord used for the reinforcing cord layer 8 preferably has reversibility that shrinks at a high temperature and expands when returned to room temperature. In this case, the rigidity increases when the polyketone fiber cord in the reinforcing cord layer 8 is shrunk at a high temperature, that is, at the time of run flat running, and the bending of the sidewall portion of the tire can be suppressed. When the normal running, the polyketone fiber cord in the reinforcing cord layer 8 tends to expand, the rigidity is lowered, and the longitudinal spring of the tire is lowered, so that deterioration in riding comfort during normal running of the tire can be suppressed. Further, by using a reversible polyketone fiber cord having a difference in heat shrinkage stress between 20 ° C. and 177 ° C. of 0.20 cN / dtex or more, preferably 0.25 cN / dtex or more, during normal running and run flat running Both effects can be achieved.

The reinforcing cord layer 8 of the pneumatic tire of the present invention is formed by coating a polyketone fiber cord obtained by twisting a plurality of filament bundles made of polyketone with a coating rubber, and the polyketone as a raw material of the polyketone fiber cord is represented by the above formula ( Polyketones consisting essentially of the repeating units represented by IV) are preferred. Among the polyketones, polyketones in which 97 mol% or more of repeating units are 1-oxotrimethylene [—CH ₂ —CH ₂ —CO—] are preferable, and polyketones in which 99 mol% or more are 1-oxo trimethylene. Is more preferable, and a polyketone in which 100 mol% is 1-oxotrimethylene is most preferable.

  The polyketone as the raw material of the polyketone fiber cord may be partially bonded with ketone groups and with unsaturated compounds. However, the unsaturated compound-derived portions and ketone groups are alternately arranged. Is preferably 90% by mass or more, more preferably 97% by mass or more, and most preferably 100% by mass.

  In the formula (IV), the unsaturated compound forming A is most preferably ethylene, but propylene, butene, pentene, cyclopentene, hexene, cyclohexene, heptene, octene, nonene, decene, dodecene, styrene, acetylene. , Allene and other unsaturated hydrocarbons, and methyl acrylate, methyl methacrylate, vinyl acetate, acrylamide, hydroxyethyl methacrylate, undecenoic acid, undecenol, 6-chlorohexene, N-vinylpyrrolidone, diethyl ester of sulphonylphosphonic acid , A compound containing an unsaturated bond, such as sodium styrenesulfonate, sodium allylsulfonate, vinylpyrrolidone, and vinyl chloride.

［式中、ｔ及びＴは、純度９８％以上のヘキサフルオロイソプロパノール及び該ヘキサフルオロイソプロパノールに溶解したポリケトンの希釈溶液の２５℃での粘度管の流過時間であり；Ｃは、上記希釈溶液１００ｍＬ中の溶質の質量（ｇ）である］で定義される極限粘度［η］が１〜２０ｄＬ／ｇの範囲にあることが好ましく、２〜１０ｄＬ／ｇの範囲にあることが更に好ましく、３〜８の範囲にあることがより一層好ましい。極限粘度が１ｄＬ／ｇ未満では、分子量が小さ過ぎて、高強度のポリケトン繊維コードを得ることが難しくなる上、紡糸時、乾燥時及び延伸時に毛羽や糸切れ等の工程上のトラブルが多発することがあり、一方、極限粘度が２０ｄＬ／ｇを超えると、ポリマーの合成に時間及びコストがかかる上、ポリマーを均一に溶解させることが難しくなり、紡糸性及び物性に悪影響が出ることがある。 Furthermore, as the polymerization degree of the polyketone, the following formula:

[Wherein t and T are the flow times of a viscosity tube at 25 ° C. of a diluted solution of hexafluoroisopropanol having a purity of 98% or more and a polyketone dissolved in the hexafluoroisopropanol; The intrinsic viscosity [η] defined by the solute mass (g) is preferably in the range of 1 to 20 dL / g, more preferably in the range of 2 to 10 dL / g, More preferably, it is in the range of 8. If the intrinsic viscosity is less than 1 dL / g, the molecular weight is too small to obtain a high-strength polyketone fiber cord, and troubles such as fluff and yarn breakage occur frequently during spinning, drying and stretching. On the other hand, if the intrinsic viscosity exceeds 20 dL / g, it takes time and cost to synthesize the polymer, and it becomes difficult to uniformly dissolve the polymer, which may adversely affect the spinnability and physical properties.

  As the method for fiberizing the polyketone, (1) after spinning an unstretched yarn, performing multi-stage heat stretching, and stretching at a specific temperature and magnification in the final stretching step of the multi-stage heat stretching, (2 ) A method in which after the undrawn yarn is spun, hot drawing is performed, and the fiber after completion of the hot drawing is rapidly cooled with high tension applied. A desired filament suitable for production of the polyketone fiber cord can be obtained by fiberizing the polyketone by the method (1) or (2).

  Here, the spinning method of the unstretched yarn of the polyketone is not particularly limited, and a conventionally known method can be employed. Specifically, JP-A-2-112413, JP-A-4-228613, Wet spinning method using an organic solvent such as hexafluoroisopropanol and m-cresol as described in JP-A-4-505344, WO99 / 18143, WO00 / 09611, JP2001-164422 No., JP-A No. 2004-218189, JP-A No. 2004-285221, and the wet spinning method using an aqueous solution of zinc salt, calcium salt, thiocyanate, iron salt, etc., among these, A wet spinning method using an aqueous solution of is preferred.

  For example, in a wet spinning method using an organic solvent, a polyketone polymer is dissolved in hexafluoroisopropanol or m-cresol at a concentration of 0.25 to 20% by mass, extruded from a spinning nozzle to be fiberized, and then toluene, ethanol, isopropanol , N-hexane, isooctane, acetone, methyl ethyl ketone, etc., a solvent can be removed and washed in a non-solvent bath to obtain a polyketone undrawn yarn.

  On the other hand, in the wet spinning method using an aqueous solution, for example, a polyketone polymer is dissolved in an aqueous solution of zinc salt, calcium salt, thiocyanate, iron salt or the like at a concentration of 2 to 30% by mass, and a spinning nozzle is formed at 50 to 130 ° C. Then, it is extruded into a coagulation bath and subjected to gel spinning, followed by desalting and drying to obtain an undrawn polyketone yarn. Here, in the aqueous solution in which the polyketone polymer is dissolved, it is preferable to use a mixture of zinc halide and a halogenated alkali metal salt or a halogenated alkaline earth metal salt. An organic solvent such as an aqueous solution, acetone, or methanol can be used.

  Further, as a drawing method of the obtained undrawn yarn, a hot drawing method in which the undrawn yarn is heated and drawn to a temperature higher than the glass transition temperature of the undrawn yarn is preferable. The method (2) may be carried out in one stage, but it is preferably carried out in multiple stages. There is no restriction | limiting in particular as this heat drawing method, For example, the method etc. which run a thread | yarn on a heating roll or a heating plate are employable. Here, the heat stretching temperature is preferably in the range of 110 ° C. to (the melting point of the polyketone), and the total stretching ratio is preferably 10 times or more.

  When polyketone fiberization is carried out by the method of (1) above, the temperature in the final stretching step of the multistage hot stretching is in the range of 110 ° C. to (the stretching temperature of the stretching step one step before the final stretching step). Moreover, the draw ratio in the final drawing step of multistage hot drawing is preferably in the range of 1.01 to 1.5 times. On the other hand, when polyketone fiberization is carried out by the method of (2) above, the tension applied to the fiber after completion of the hot drawing is preferably in the range of 0.5 to 4 cN / dtex, and the cooling rate in rapid cooling is 30 The cooling end temperature in the rapid cooling is preferably 50 ° C. or less. Here, there is no restriction | limiting in particular as a rapid cooling method of the heat-stretched polyketone fiber, A conventionally well-known method can be employ | adopted, Specifically, the cooling method using a roll is preferable. In addition, since the polyketone fiber obtained in this way has a large residual elastic strain, it is usually preferable to perform relaxation heat treatment so that the fiber length is shorter than the fiber length after hot drawing. Here, the temperature of the relaxation heat treatment is preferably in the range of 50 to 100 ° C., and the relaxation ratio is preferably in the range of 0.980 to 0.999 times.

  The polyketone fiber cord is formed by twisting a plurality of filament bundles made of the polyketone, preferably two or three strands. For example, the filament bundle made of the polyketone is twisted, and then a plurality of the bundles are joined together. By applying an upper twist in the opposite direction, it can be obtained as a twisted cord having a double twist structure.

  A cord / rubber composite used for the reinforcing cord layer 8 can be obtained by coating the polyketone fiber cord obtained as described above with a coating rubber. Here, there is no restriction | limiting in particular as coating rubber of a polyketone fiber cord, The coating rubber used for the cord / rubber composite for the conventional tire can be used. Prior to coating the polyketone fiber cord with the coating rubber, the polyketone fiber cord may be subjected to an adhesive treatment to improve the adhesion to the coating rubber.

  In the pneumatic tire of the present invention, the reinforcing cord layer 8 formed by coating the above polyketone fiber cord with a coating rubber includes a region A from the belt end to the maximum width portion of the tire side portion and a region B from the vicinity of the bead core to the bead filler. It can arrange | position to at least one part and can manufacture by a conventional method. 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.

[Rubber composition]
In the pneumatic tire of the present invention described above, the side reinforcing layer 8 and / or the bead filler 7 includes (A) a rubber component and 100 parts by mass of (B) 55 parts by mass of carbon black, and A rubber composition having an elastic modulus at 100% elongation (M100) of 10 MPa or more and a sigma value of tangent loss tan δ at 28 ° C. to 150 ° C. of 6.0 or less in vulcanized rubber properties can be used.
((A) rubber component)
As the rubber component (A) in the rubber composition according to the present invention, one containing an amine-modified conjugated diene polymer obtained by amine-modifying a conjugated diene polymer can be preferably used. A polymer containing 30% by mass or more, preferably 50% by mass or more can be used. When the rubber component contains the modified conjugated diene polymer in an amount of 30% by mass or more, the resulting rubber composition can provide a pneumatic tire with low heat generation and improved run-flat running durability.

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 as a functional group for modification in the molecule is preferable. Further, those having a silicon atom-containing functional group introduced are preferred.
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 functional group for modification may be present at any of the polymerization initiation terminal, side chain and polymerization active terminal of the conjugated diene polymer. In the present invention, it is preferably a polymerization terminal, more preferably the same polymerization. A silicon atom having an amino group protected with a protic amino group and / or a detachable group and a hydrocarbyloxy group and / or a hydroxy group, particularly preferably one or two hydrocarbyloxy groups, And / or a silicon atom having a hydroxy group bonded thereto.

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 N, N-bis (trihydrocarbylsilyl) amino group and N- (trihydrocarbylsilyl) imino group. Preferably, the hydrocarbyl group is carbon. The trialkylsilyl group which is a C1-C10 alkyl group can be mentioned, Especially preferably, a trimethylsilyl group can be mentioned.
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 an acyclic imine residue or a cyclic imine residue.

  Among the amine-modified conjugated diene polymers described above, a primary amine-modified conjugated diene polymer modified with a primary amino group from the viewpoint of low heat generation is a protected primary class at the active end of the conjugated diene polymer. A primary amine-modified conjugated diene polymer modified with a protected primary amino group obtained by reacting an amine compound is preferred.

<Conjugated diene polymer>
The conjugated diene polymer 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 copolymerization with the conjugated diene compound include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexylstyrene. 2,4,6-trimethylstyrene and the like. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.
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 chains having a living property or pseudo-living property. As such a polymerization reaction having 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 by 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 an initiator for the above-mentioned anionic polymerization, 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 has polymerization activity. A conjugated diene polymer as a site is obtained. When the latter 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-decyl. Examples include lithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, and reactive organisms of diisopropenylbenzene and butyllithium. Of these, n-butyllithium is particularly preferred.

On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, and lithium disulfide. Heptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, from the viewpoint of the interaction effect on carbon black and the ability of initiating polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable. In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.
In general, these lithium amide compounds prepared from a secondary amine and a lithium compound can be used for polymerization, but can also be prepared in a 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.

A method for producing a conjugated diene polymer by anionic polymerization using the organolithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound are If desired, a conjugated diene polymer having an active terminal can be obtained by anionic polymerization in the presence of a randomizer to be used, if desired, using a lithium compound as a polymerization initiator.
In addition, when an organic lithium 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 lanthanum series rare earth element compound described above. A copolymer of a conjugated diene compound and an aromatic vinyl compound can also be obtained efficiently.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. 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. When copolymerization is performed 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 a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene portion in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an effect 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, oxolanyl propane oligomers [particularly those containing 2,2-bis (2-tetrahydrofuryl) -propane, etc.], 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.

One of these randomizers may be used alone, or two or more thereof may be used in combination. 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 desirable 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 medium 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. Can be obtained by an appropriate method such as pressurizing.

<Modifier>
In the present invention, a primary amine-modified conjugated diene polymer is reacted with a protected primary amine compound 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 (trimethylsilyl) Aminoethylmethyldiethoxysilane and the like, preferably N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane or 1-trimethylsilyl-2 , 2-dimethoxy-1-aza-2-silacyclopentane.

Moreover, as a modifier, 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) diethoxysila 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 protected secondary amino groups such as propyl (methyl) dimethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) propyl (methyl) diethoxysilane; N- (1,3 -Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxy Silyl) -1-propanamine, N- (1-methylpropiyl) Den) -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-dimethylaminopropyl (diethoxy) methylsilane, 3-dibutylaminopropyl (triethoxy) silane Examples thereof include alkoxysilane compounds having an amino group such as lan.
These modifiers may be used individually by 1 type, and may be used in combination of 2 or more types. 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 SiOSi bonded 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 that does not contain an additive such as an anti-aging agent added during or after the 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 of adding the modifier is not particularly limited, and examples thereof include a method of adding all at once, a method of adding in divided portions, a method of adding continuously, and the like. 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.

<Condensation accelerator>
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.
Examples of such a condensation accelerator include a compound containing a tertiary amino group, or among group 3, 4, 5, 12, 13, 14, and 15 of the periodic table (long period type). An organic compound containing one or more elements belonging to any of the above can be used. Furthermore, as a condensation accelerator, an alkoxide, a carboxyl containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn). It is preferably an acid salt or an acetylacetonate complex salt.
The condensation accelerator used here can be added before the 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 hydrocarbyloxy 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- Butoxytitanium, tetra-tert-butoxytitanium, tetra (2-ethylhexyl) titanium, bis (octanediolate) bis (2-ethylhexyl) titanium, tetra (octanediolate) titanium, titanium lactate, titanium dipropoxybis (triethanol Aminate), titanium dibutoxybis (triethanolaminate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium ethyl Sildiolate, Titanium tripropoxyacetylacetonate, Titanium dipropoxybis (acetylacetonate), Titanium tripropoxyethylacetoacetate, Titaniumpropoxyacetylacetonatebis (ethylacetoacetate), Titanium tributoxyacetylacetonate, Titanium dibutoxybis ( Acetylacetonate), titanium tributoxyethyl acetoacetate, titanium butoxyacetylacetonate bis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) Ate) titanium oxide, bis (laurate) titanium oxide, bis (naphthene) ) Titanium oxide, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, tetrakis Examples thereof include compounds containing titanium such as (stearate) titanium, tetrakis (oleate) titanium, tetrakis (linoleate) titanium, and the like.

  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-ethylhexanoate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) Zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, Tetrakis (linolate) zirconium and the like.

  Also, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tri (2-1 ethylhexyl) aluminum, aluminum di Butoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethylhexanoate) Ate) aluminum, tris (laurate) aluminum, tris (naphthenate) aluminum, tris (stearate) aluminum, Squirrel (oleate) aluminum, tris (linolate) aluminum, and the like.

Of the above condensation accelerators, titanium compounds are preferable, and titanium metal alkoxides, titanium metal carboxylates, or titanium metal acetylacetonate complex salts are particularly preferable.
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 use amount of 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-described 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 carried out in an aqueous solution, and the condensation reaction temperature is preferably 85 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 110 to 150 ° C.
By setting the temperature during the condensation reaction within the above range, the condensation reaction can be efficiently advanced and completed, and the deterioration of the quality due to the aging reaction of the polymer due to the change over time of the resulting modified conjugated diene polymer can be suppressed. Can do.

The condensation reaction time is usually about 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly.
In addition, the pressure of the reaction system at the time of condensation reaction is 0.01-20 Mpa normally, Preferably it is 0.05-10 Mpa.
There is no restriction | limiting in particular about the format in the case of performing a condensation reaction in aqueous solution, You may carry out by a continuous type using apparatuses, such as a batch type reactor and a multistage continuous type reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.
The primary amino group derived from the modifying agent of the modified conjugated diene polymer of the present invention is generated by performing the 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, 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 step including the condensation treatment to the solvent removal to the dry polymer.

<Modified conjugated diene polymer>
The modified conjugated diene polymer 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, and when it exceeds 150, workability is poor and it is difficult to knead with the compounding agent.
The Mooney-viscosity (ML _{1 + 4} , 130 ° C.) of the unvulcanized rubber composition according to the present invention containing the modified conjugated diene polymer is preferably 10 to 150, more preferably 30 to 100. is there.
The modified conjugated diene polymer used in the rubber composition according to the present invention has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, the molecular weight distribution (Mw / Mn) is 1. It is preferable that it is -3, and it is more preferable that it is 1.1-2.7.
By making the molecular weight distribution (Mw / Mn) of the modified conjugated diene polymer within the above range, even if the modified conjugated diene polymer is blended with the rubber composition, the workability of the rubber composition may be reduced. And kneading is easy, and the physical properties of the rubber composition can be sufficiently improved.

The modified conjugated diene 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. Is more preferable. By setting the number average molecular weight of the modified conjugated diene polymer within the above range, the elastic modulus of the vulcanizate is reduced and an increase in hysteresis loss is suppressed to obtain excellent fracture resistance, and the modified conjugated diene polymer Excellent kneading workability of the rubber composition containing can be obtained.
The modified conjugated diene polymer used in the rubber composition according to the present invention may be used singly or in combination of two or more.

<Other rubber components>
(A) In the rubber component, examples of the rubber component used in combination with the modified conjugated diene polymer include natural rubber and other diene synthetic rubbers. Examples of other diene synthetic rubbers include styrene-butadiene copolymer. Polymer (SBR), polybutadiene (BR), polyisoprene (IR), styrene-isoprene copolymer (SIR), butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene-diene terpolymer (EPDM) and These mixtures are mentioned. Further, some or all of the other diene-based synthetic rubber is more preferably a diene-based modified rubber having a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride. .

((B) Carbon black)
In the rubber composition according to the present invention, it is necessary to use carbon black as the component (B) at a ratio of 55 parts by mass or more with respect to 100 parts by mass of the rubber component (A) described above. When the amount of carbon black is less than 55 parts by mass, sufficient reinforcing effect is not exhibited, and in the vulcanized rubber properties of the resulting rubber composition, the elastic modulus at 100% elongation (M100) described later does not exceed 10 MPa. There is. If the amount of carbon black is too large, the Σ value at 28 ° C. to 150 ° C. of the tangent loss tan δ described later may not be 6.0 or less in the physical properties of the vulcanized rubber of the resulting rubber composition. Therefore, the preferable amount of the carbon black is 55 to 70 parts by mass, and more preferably 60 to 70 parts by mass.
As the carbon black, in order that the vulcanized rubber physical properties of the obtained rubber composition satisfy the above vulcanized rubber physical properties, FEF grade, FF grade, HAF grade, ISAF grade and SAF grade It is preferable to use at least one selected from among them, and the FEF grade grade is particularly preferable.

Further, the rubber composition according to the present invention includes various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, an aging, as desired, as long as the effects of the present invention are not impaired. An inhibitor, a scorch inhibitor, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as sulfur content with respect to 100 mass parts of (A) rubber components, More preferably, it is 1.0. -5.0 parts by mass. If the amount is less than 0.1 parts by mass, the rupture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount 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, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Thiophene vulcanization accelerators such as thiazoles such as sulfenamide), guanidines such as DPG (diphenylguanidine), or thiurams such as TOT (tetrakis (2-ethylhexyl) thiuram disulfide). The amount used is preferably from 0.1 to 5.0 parts by weight, more preferably from 0.2 to 3.0 parts by weight, per 100 parts by weight of the (A) 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 (A), and if it is 100 parts by mass or less, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber deteriorate. Can be suppressed.
Furthermore, examples of the antioxidant 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), high-temperature condensate of diphenylamine and acetone, etc. (A) 0.1-5.0 mass part is preferable with respect to 100 mass parts of rubber components, More preferably, it is 0.3-3.0 mass part.

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

Further, as the physical property of the vulcanized rubber, the Σ value [Σtan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of the tangent loss tan δ is required to be 6.0 or less. When the sigma value of tan δ exceeds 6.0, the heat generation of the tire during run-flat running is large, and the run-flat running durability of the tire is lowered. The lower limit of Σtan δ (28 to 150 ° C.) is not particularly limited, but is usually about 5.
The Σtanδ (28 to 150 ° C.) is a value measured by the following method.
<Measuring method of Σtan 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. About this sample, a tangent loss tan δ was measured under the measurement conditions of a distance between chucks 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. using a spectrometer manufactured by Ueshima Seisakusho. As shown in FIG. 6, the relationship between the temperature and tan δ is graphed, the area of the hatched portion is obtained, and the value is Σ tan δ (28 to 150 ° C.).

(Preparation of rubber composition, production of pneumatic tire)
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 according to the above compounding prescription, vulcanized after molding, and in FIG. Used as a side reinforcing layer 7 and / or a bead filler 9 of a pneumatic tire.
The tire of the present invention is manufactured by a normal method for manufacturing a run flat tire using the rubber composition according to the present invention for the side reinforcing layer 7 and / or the bead filler 9. That is, as described above, the rubber composition according to the present invention containing various chemicals is processed into each member at an unvulcanized stage, and pasted and molded by a normal method on a tire molding machine, and a raw tire is molded. Is done. The green tire is heated and pressed in a vulcanizer to obtain a tire.
The pneumatic tire of the present invention thus obtained has improved run-flat durability without impairing rolling resistance and riding comfort during normal running.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Cord / Rubber composite)
8 types of cord / rubber composites (fabricated structure) with fiber cords of the material, structure, twist coefficient, elastic modulus, and heat shrinkage stress shown in Table 1 arranged in parallel with the number of drivings shown in Table 1 and covered with coating rubber Examples bi) were made. Next, the cord / rubber composite is used for the reinforcing cord layer 8 of the tire having the structure shown in FIG. A side-reinforced type run-flat tire of size 215 / 45ZR17 was prototyped using the rubber composition as a side rubber reinforcing layer 7. In addition, the angle with respect to the tire radial direction of the cord in the reinforcing cord layer 8 is as shown in Table 1, and the reinforcing rubber gauge of the side rubber reinforcing layer 7 is as shown in Table 2. For comparison, a tire having the same structure except that the reinforcing cord layer 8 is not provided (comparative structure example a) was made as a prototype.
In addition, the longitudinal spring and run flat durability of the obtained tire were measured by the following evaluation methods.

(1) A load-deflection curve of a test tire filled with an internal pressure of a longitudinal spring of 230 kPa was measured, and the slope of a tangent at a certain load on the obtained load-deflection curve was defined as a longitudinal spring constant with respect to the load. The value of the vertical spring constant of the tire was expressed as an index with the value being 100. A larger index value indicates a larger longitudinal spring constant.

(2) Run flat durability Drum test is performed under the environment of load 4.17kN, speed 89km / h, temperature 38 ° C without filling the test tire with internal pressure. The distance measured until the failure of the tire of Comparative Example 1 was taken as 100 and indicated as an index. The larger the index value, the longer the distance traveled until failure, and the better the run-flat durability.

Next, a primary amine-modified polybutadiene rubber used for the rubber composition was synthesized.
Various characteristics were measured according to the following methods.
<< Physical Properties of Unmodified or Modified Conjugated Diene Polymer >>
<Microstructure analysis method>
The vinyl bond content (%) was measured by an infrared method (Morero method).
<Measurement of number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
It measured using GPC [The Tosoh make, HLC-8020] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.

<Measurement of primary amino group content (mmol / kg)>
First, the polymer was dissolved in toluene, and then the amino group-containing compound not bound to the polymer was separated from the rubber by precipitation in a large amount of methanol, followed by drying. Using this treated polymer as a sample, the total amino group content was quantified by the “total amine value test method” described in JIS K7237. Subsequently, the contents of 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 bound to the polymer by subtracting the secondary amino group content and tertiary amino group content from the total amino group content to determine the primary amino group content (mmol) and dividing by the polymer mass used in the analysis. The content (mmol / kg) was determined.

<< Physical properties of vulcanized rubber of rubber composition >>
The Σ value at 28 ° C. to 150 ° C. [Σ tan δ (28 to 150 ° C.)] of the 100% elastic modulus (M100) and the tangent loss tan δ was measured according to the method described in the specification.

Production Example 1 Production of Primary Amine-Modified Polybutadiene (1) Polybutadiene In a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, 2,2-ditetrahydrofurylpropane (0.0285 mmol) cyclohexane under nitrogen. The solution was injected as a solution, and 2.85 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization 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 polymer 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.
(2) Production of primary amine-modified polybutadiene The polymer solution obtained in (1) above is maintained at a temperature of 50 ° C. without deactivating the polymerization catalyst, and the primary amino group protected N, N-bis ( 1129 mg (3.364 mmol) of trimethylsilyl) aminopropylmethyldiethoxysilane was added and the modification reaction was carried out for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the primary amino group, which was desolvated and protected by steam stripping, was removed, and the rubber was dried with a ripening 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.

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

Example Formulation A , Reference Formulation Example B, and Comparative Formulation Example C
Three types of rubber compositions having the compounding compositions A to C shown in Table 2 were prepared, and physical properties of vulcanized rubber, that is, M100 and Σtanδ (28 to 150 ° C.) were obtained. Table 2 shows the results.
Next, a side reinforcement type of size 215 / 45ZR17 using the eight types of cord / rubber composites (embodiment examples bi) shown in Table 1 and A, B, and C of the above composition as the side rubber reinforcement layer 7. Run-flat tires were prototyped and tested for longitudinal spring and run-flat durability during normal driving. The evaluation results are shown in Tables 3, 4 and 5.

［注］
１）天然ゴム：ＴＳＲ２０
２）未変性ポリブタジエン：ＪＳＲ社製ＢＲ０１
３）一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）カーボンブラック：ＦＥＦ（Ｎ５５０）、旭カーボン社製「旭＃６０」
５）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＃３」
６）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」
７）加硫促進剤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」
８）加硫促進剤ＴＯＴ：テトラキス（２−エチルへキシル）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」
９）ＤＭＢＴＥＳＰＡ変性ポリブタジエン：製造例２で得られたもの

[note]
1) Natural rubber: TSR20
2) Unmodified polybutadiene: BR01 manufactured by JSR
3) Primary amine-modified polybutadiene: obtained in Production Example 1 4) Carbon black: FEF (N550), “Asahi # 60” manufactured by Asahi Carbon Co., Ltd.
5) Process oil: Aromatic oil, “Aromax # 3” manufactured by Fuji Kosan Co., Ltd.
6) Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
7) Vulcanization accelerator DZ: N, N′-dicyclohexyl-2-benzothiazylsulfenamide, “Noxeller DZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
8) Vulcanization accelerator TOT: Tetrakis (2-ethylhexyl) thiuram disulfide, “Noxeller TOT-N” manufactured by Ouchi Shinsei Chemical Co., Ltd.
9) DMBTESPA modified polybutadiene: obtained in Production Example 2

表３〜表５から明らかなように、サイド補強タイプのランフラットタイヤのベルト端からタイヤサイド部の最大幅部までの領域Ａ及びビードコア近傍からビードフィラーまでの領域Ｂの少なくとも一部に、上記式(I)及び式(II)の条件を満たすポリケトン繊維コードを用いた補強コード層を配設し、加硫ゴム物性において、１００％伸張時弾性率が１０ＭＰａ以上であり、かつ正接損失ｔａｎδの２８℃〜１５０℃におけるΣ値が６．０以下のゴム組成物を、特にタイヤのサイド補強層用いることにより、通常走行時の乗り心地を損なうことなく、ランフラット耐久性を大幅向上することがわかる。

As apparent from Tables 3 to 5, at least part of the region A from the belt end of the side-reinforced type run-flat tire to the maximum width portion of the tire side portion and the region B from the vicinity of the bead core to the bead filler, A reinforcing cord layer using a polyketone fiber cord satisfying the conditions of the formulas (I) and (II) is disposed, and in the vulcanized rubber properties, the elastic modulus at 100% elongation is 10 MPa or more, and the tangent loss tan δ By using a rubber composition having a Σ value of 6.0 or less at 28 ° C. to 150 ° C., particularly a side reinforcing layer of a tire, run-flat durability can be greatly improved without impairing riding comfort during normal driving. Recognize.

  In the pneumatic tire of the present invention, at least part of the region A from the belt end to the maximum width portion of the tire side portion and the region B from the vicinity of the bead core to the bead filler of the side reinforcing type run-flat tire is represented by the above formula (I ) And a reinforced rubber layer using a polyketone fiber cord satisfying the conditions of the formula (II), the vulcanized rubber has an elastic modulus at 100% elongation of 10 MPa or more and a tangent loss tan δ of 28 ° C. By using a rubber composition having a Σ value of 6.0 or less at 150 ° C., particularly for the side reinforcing layer and / or bead filler of a tire, the run-flat durability is maintained without impairing rolling resistance and riding comfort during normal driving. A tire with significantly improved performance can be provided.

It is sectional drawing of the right half of an example of the pneumatic tire of this invention. It is sectional drawing of the right half of the other example of the pneumatic tire of this invention. It is sectional drawing of the right half of the other example of the pneumatic tire of this invention. It is sectional drawing of the right half of the other example of the pneumatic tire of this invention. It is sectional drawing of the right half of the other example of the pneumatic tire of this invention. It is explanatory drawing for calculating | requiring (SIGMA) tan (delta) (28-150 degreeC) in the vulcanized rubber physical property of a rubber composition.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Bead part 2 Bead core 3 Radial carcass 4 Tread part 5 Buttress part 6 Side wall part 7 Side reinforcement rubber layer 8 Reinforcement cord layer 9 Bead filler 10 Belt 11A, 11B Belt reinforcement layer 12 Rim guard A Maximum width of tire side part from belt end Area B to the area from the vicinity of the bead core to the bead filler

Claims (17)

A radial carcass composed of one or more carcass plies extending in a toroidal manner between bead cores embedded in a pair of bead portions, and a tread portion disposed on the outer side in the tire radial direction of the crown portion of the radial carcass, A pair of buttress portions positioned at both ends of the tread portion; a pair of sidewall portions connecting the buttress portion and the bead portion; and an inner side of the radial carcass extending from the buttress portion to the sidewall portion In the pneumatic tire provided with a pair of crescent-shaped side reinforcing rubber layers disposed in the region, at least a region A from the belt end to the maximum width portion of the tire side portion and a region B from the vicinity of the bead core to the bead filler In part, a plurality of filament bundles made of polyketone are twisted together, and the following formula (I) and formula (II) :
σ ≧ −0.01 × E + 1.2 (I)
σ ≧ 0.02 (II)
[Wherein σ is a heat shrinkage stress (cN / dtex) at 177 ° C .; E is an elastic modulus (cN / dtex) at a load of 49 N at 25 ° C.] A reinforcing cord layer coated with rubber is disposed, and (B) carbon black is 55 parts by mass or more with respect to 100 parts by mass of (A) rubber component as the side reinforcing rubber and / or bead filler rubber. hints, and the vulcanized rubber properties, 100% elongation at the elastic modulus (M100) is the Σ value at 28 ° C. to 150 DEG ° C. of 10MPa or higher and the loss tangent tanδ of a rubber composition is 5.06 or less, the rubber in the composition, it is characterized in that comprising (a) the rubber component, amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer sky Tire enters.   The pneumatic tire according to claim 1, wherein an angle of the polyketone fiber cord in the reinforcing cord layer with respect to a tire radial direction is 0 to 85 °. The polyketone fiber cord has the following formula (III):
Nt = tan θ = 0.001 × N × (0.125 × D / ρ) ^1/2 (III)
[Where N is the number of twists (times / 10 cm), ρ is the specific gravity of the cord (g / cm ³ ), and D is the total decitex number (dtex) of the cord] The pneumatic tire according to claim 1, wherein is 0.25 or more.   The pneumatic tire according to claim 1, wherein the number of driving of the polyketone fiber cord in the reinforcing cord layer is 5 to 60 (lines / 50 mm).   2. The pneumatic tire according to claim 1, wherein the polyketone fiber cord is formed by twisting two or three filament bundles made of polyketone having a fineness of 500 to 2000 dtex.   The pneumatic tire according to any one of claims 1 to 5, wherein the polyketone fiber cord has reversibility that contracts at a high temperature and expands when returned to room temperature. The polyketone is represented by the following general formula (IV):

[Wherein A is a moiety derived from an unsaturated compound polymerized by an unsaturated bond, and may be the same or different in each repeating unit], The pneumatic tire according to any one of the above.   The pneumatic tire according to claim 7, wherein A in the formula (IV) is an ethylene group.   2. The pneumatic tire according to claim 1, wherein in the rubber composition, (B) the carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade. The pneumatic tire according to claim 9 , wherein (B) carbon black is FEF grade grade. The pneumatic tire according to claim 1, wherein the primary amine-modified conjugated diene polymer is obtained by reacting a protected primary amine compound with an active terminal of the conjugated diene polymer. Conjugated diene polymer, an organic alkali metal compound as an initiator, claim 1 1 is obtained by conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound is anionically polymerized in an organic solvent Pneumatic tire described in 2. Conjugated diene polymer, the pneumatic tire according to claim 1 2 is polybutadiene. Protected primary amine compound, N, N-bis (trimethylsilyl) The pneumatic tire according to any one of claims 1 1 to 1 3 is aminopropyltriethoxysilane. The side reinforcing layer, the pneumatic tire according to any one of claims 1 to 1 4 obtained by using the above rubber composition. The bead filler, the pneumatic tire according to any one of claims 1 to 1 4 obtained by using the above rubber composition. The side reinforcing layer and a bead filler, pneumatic tire according to any one of claims 1 to 1 4 obtained by using the above rubber composition.

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