JP2011255881A - Pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pneumatic tire enhancing run-flat durability without impairing rolling resistance and riding comfortability during normal travel.SOLUTION: The pneumatic tire includes bead cores 1, 1', a carcass ply, a tread rubber layer 4, an inner liner 6, a side reinforcing layer 8, and a bead filler 7. Reinforcing fiber cords constituting the carcass ply are formed of cords including at least 50 mass% of polyketone fibers subjected to drying hardening treatment after coating of resorcin formaldehyde resin-rubber latex adhesive, and satisfy (1) tensile strength of cords in a drying process and a heat treatment process is 2.9-49.0 N per one cord, (2) a drying treatment temperature in the drying process is 100-200°C, and (3) when a hardening treatment temperature in the heat treatment process is Tm (°C) and a hardening treatment time is s (sec), Tm×s/1,000 is 10-55.

Description

  The present invention relates to a pneumatic tire. More specifically, the present invention applies to a carcass ply a reinforcing fiber cord including a polyketone fiber formed by adhering and impregnating an RFL adhesive (resorcin / formaldehyde resin-rubber latex adhesive) under specific drying and vulcanizing conditions. And preferably, by using a rubber composition having a specific property for at least one of the tire members, in particular, the side reinforcing layer and / or the bead filler, it is possible to increase the number of troubles and quality troubles during production. The present invention relates to a pneumatic tire with improved runfoot durability without impairing rolling resistance and riding comfort during traveling.

2. Description of the Related Art Conventionally, in a pneumatic tire, particularly a run flat tire, 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 a sidewall portion. (For example, see Patent Document 1)
Pneumatic tires run when the internal pressure of the tire (hereinafter referred to as internal pressure) drops due to puncture, etc., so-called run-flat running state, the deformation of the tire sidewall and bead filler increases, and heat is generated. In some cases, it reaches 200 ° C. or higher.
In such a state, even in a pneumatic tire having a side reinforcing layer, the side reinforcing layer and the bead filler exceed the fracture limit, leading to a tire failure.

As a means for earning 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 bead filler to be disposed, but when such a method is taken Undesirable situations such as deterioration of riding comfort during normal driving, an increase in weight, and an increase in noise level occur.
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.

Further, cellulose fibers (rayon fibers) having a higher Young's modulus than polyester (PET) fibers are mainly used in conventional side-reinforced run-flat tire carcass plies at room temperature and high temperatures.
However, with the elastic modulus of conventional rayon fibers, the tire flexure during run-flat is large, and at high temperatures, the flexure of the tire increases due to reduced rigidity of the carcass ply. The problem was that the run-flat durability distance was short.
Further, if the reinforcing rubber layer is thickened or the side portion and the shoulder portion are reinforced, the tire longitudinal spring constant at the time of internal pressure is increased as the weight increases, and the riding comfort during normal running is impaired.

On the other hand, Patent Document 2 proposes that a rubber composition containing various modified conjugated diene-aromatic vinyl copolymers and a heat resistance improver is used for the side reinforcing layer and the bead filler.
Further, Patent Document 3 proposes that a rubber composition containing a specific conjugated diene polymer and a phenol resin is used for the side reinforcing layer and the bead filler.
These are intended to increase the elastic modulus of the rubber composition used for the side reinforcing layer and bead filler, and to suppress a decrease in the elastic modulus at high temperatures, and greatly improve the run-flat durability. However, the rolling resistance during normal running is significantly deteriorated.

JP 11-310019 A WO02 / 02356 brochure JP 2004-74960 A

  The present invention has been made under such circumstances, and has improved run-flat durability without increasing trouble during production and quality trouble, and without impairing rolling resistance and riding comfort during normal driving. The object is to provide a pneumatic tire.

  As a result of intensive studies to achieve the above object, the present inventors have made 50 mass% of polyketone fiber formed by adhering and impregnating resorcin / formaldehyde resin-rubber latex adhesive under specific drying and heating conditions. The reinforcing fiber cord including the above is applied to the carcass ply, and preferably, the rubber composition (1) or (2) having a specific property is applied to at least one of the tire members, particularly the side reinforcing layer and / or the bead filler. It has been found that the purpose can be achieved by use. The present invention has been completed based on such findings.

That is, the present invention
[1] A pneumatic tire comprising a bead core, a carcass ply, a tread rubber layer, an inner liner, a side reinforcing layer, and a bead filler, wherein the reinforcing fiber cord constituting the carcass ply is bonded to resorcin / formaldehyde resin-rubber latex After applying the agent, the cord is a cord containing at least 50% by mass of a polyketone fiber, which is dried and cured through a drying step and a heat treatment step, and the following condition (1) The cord tension in the drying step and the heat treatment step is one. 2.9-49.0N per hit,
(2) The drying treatment temperature in the drying step is 100 to 200 ° C., and (3) Tm × when the curing treatment temperature in the heat treatment step is Tm (° C.) and the curing treatment time is s (seconds). s / 1000 is 10 to 55,
Pneumatic tire, characterized by satisfying

[2] A pneumatic tire comprising at least one reinforcing cord layer, wherein at least one of the reinforcing cord layers comprises a reinforcing cord made of a polyester fiber cord, and from the end of the belt layer The angle with respect to the tire radial direction is 0 to 85 ° in at least part of the region A up to the maximum width portion of the tire side portion and / or at least part of the region B from the vicinity of the bead core to the tire radial outer end of the bead filler. The pneumatic tire according to [1], wherein the pneumatic tire is disposed so as to become
[3] The amount of the adhesive attached to the reinforcing fiber cord formed by applying a resorcinol / formaldehyde resin-rubber latex adhesive and then dried and cured is 1.5 to 9.0 with respect to the mass of the cord before the treatment. The pneumatic tire according to [1] or [2], wherein the pneumatic tire is% by mass;
[4] The reinforcing fiber cord constituting the carcass ply according to any one of [1] to [3], wherein the twist coefficient N represented by the following formula (1) satisfies the relationship of the following formula (2): Pneumatic tires,
N = n × (0.125D / ρ) ^1/2 × 10 ⁻³ (1)
0.34 ≦ N (2)
[In the formula, n represents the number of upper twists (times / 10 cm), D represents the total display decitex, and ρ represents the density (g / cm ³ ) of the fiber containing at least 50% by mass of the polyketone fiber. ]
[5] The twist coefficient N is the following formula (2-a)
0.6 ≦ N ≦ 0.9 (2-a)
The pneumatic tire according to [4], which satisfies the relationship:
[6] The pneumatic tire according to any one of the above [1] to [5], wherein the number of reinforcing fiber cords constituting the carcass ply is 30 to 60/50 mm,
[7] The pneumatic tire according to any one of [1] to [6], wherein the reinforcing fiber cord constituting the carcass ply is formed by twisting a filament bundle having a fineness of 500 to 2000 dtex.
[8] The polyketone constituting the polyketone fiber is represented by the following general formula (I):

[In formula, A shows the residue derived from the unsaturated compound superposed | polymerized by the unsaturated bond, and may be same or different in a repeating unit. ]
The pneumatic tire according to any one of the above [1] to [7], having a repeating unit represented by:
[9] The pneumatic tire according to [8], wherein A in the general formula (I) is an ethylene group,
[10] (A) The rubber component and 100 parts by mass of (B) the carbon black contains 55 parts by mass or more, and in the physical properties of vulcanized rubber, the elastic modulus at 100% elongation (M100) is 10 MPa or more, and Any one of [1] to [9] above, wherein the rubber composition (1) having a loss tangent (tan δ) of Σ value at 28 to 150 ° C. of 6.0 or less is used for at least one of the tire members. Pneumatic tires as described,
[11] In the rubber composition (1), (B) the carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade [10] Pneumatic tires as described in the
[12] The pneumatic tire according to [11], wherein (B) carbon black is an FEF grade grade,
[13] The pneumatic tire according to any one of [10] to [12], wherein in the rubber composition (1), (A) the rubber component contains an amine-modified conjugated diene polymer.
[14] The pneumatic tire according to [13], wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer,

[15] The pneumatic tire according to [13] or [14], wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.
[16] The pneumatic tire according to the above [15], 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.
[17] The above, wherein 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. [16] The pneumatic tire according to
[18] The pneumatic tire according to [17], wherein the conjugated diene polymer is polybutadiene,
[19] The pneumatic tire according to any one of [16] to [18], wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane.
[20] The pneumatic tire according to any one of [10] to [19], wherein the rubber composition (1) is used as a side reinforcing layer.
[21] The pneumatic tire according to any one of [10] to [19], wherein the rubber composition (1) is used as a bead filler.
[22] The pneumatic tire according to any one of [10] to [19], wherein the rubber composition (1) is used for the side reinforcing layer and the bead filler.

[23] (A) Rubber component, and 100 parts by mass of the rubber component (B) 50 parts by mass or less of the filler, and in the physical properties of vulcanized rubber, dynamic strain 1%, dynamic storage elasticity at 25 ° C. The rubber composition (2) having a rate (E ′) of 10 MPa or less and a loss tangent (tan δ) of 28 to 150 ° C. having a Σ value of 5.0 or less is used. 9] Any pneumatic tire,
[24] In the rubber composition (2), the filler (B) is carbon black, silica, and general formula (II)
nM · xSiO _y · zH ₂ O (II)
[Wherein, M is at least selected from metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of the metals. N, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. ]
The pneumatic tire according to [23], which is at least one selected from inorganic fillers represented by:
[25] The pneumatic tire according to [23] or [24], wherein (B) the filler is carbon black,
[26] The pneumatic tire according to [25], wherein the carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade,
[27] The pneumatic tire of [25] above, wherein the carbon black is FEF grade grade,
[28] The pneumatic tire according to any one of the above [23] to [27], wherein in the rubber composition (2), (A) the rubber component contains a modified conjugated diene polymer.
[29] The pneumatic tire according to [28], wherein the modified conjugated diene polymer is an amine-modified conjugated diene polymer,
[30] The pneumatic tire according to [29], wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer,

[31] The pneumatic tire of [29] or [30] above, wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.
[32] The pneumatic tire according to [31] above, 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.
[33] 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. The pneumatic tire according to [32],
[34] The pneumatic tire according to [33], wherein the conjugated diene polymer is polybutadiene,
[35] The pneumatic tire according to any one of [32] to [34], wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropyltriethoxysilane.
[36] The pneumatic tire according to any one of the above [23] to [35], wherein the rubber composition (2) is used for a side reinforcing layer.
[37] The pneumatic tire according to any one of the above [23] to [35], wherein the rubber composition (2) is used as a bead filler, and [38] the rubber composition ( 2) The pneumatic tire according to any one of the above [23] to [35],
Is to provide.

The pneumatic tire of the present invention has the following effects.
(A) A cord containing 50% by mass or more of polyketone fiber is adhered and impregnated with a resorcin / formaldehyde resin-rubber latex adhesive (hereinafter sometimes referred to as RFL adhesive) under specific drying and heating conditions. By applying this to the carcass ply, a pneumatic tire with improved run-flat durability can be obtained without impairing rolling resistance and riding comfort during normal driving.
(B) Furthermore, by using the rubber composition (1) or (2) having specific vulcanized rubber properties as a reinforcing rubber, at least one of the tire members, particularly the side reinforcing layer and / or the bead filler, A pneumatic tire in which the effect (a) is further improved can be obtained.
Further, at least one reinforcing cord layer, at least one of the reinforcing cord layers is provided with a reinforcing cord layer including a reinforcing cord made of a polyester fiber cord at a specific portion of the pneumatic tire. As a result, the run-flat durability can be further improved without impairing the rolling resistance and riding comfort during normal driving.

It is sectional drawing which shows one embodiment of the pneumatic tire of this invention. It is a cross-sectional schematic diagram of the right half of the other embodiment of the pneumatic tire of the present invention. It is a cross-sectional schematic diagram of the right half of the other embodiment of the pneumatic tire of the present invention. It is a cross-sectional schematic diagram of the right half of the other embodiment of the pneumatic tire of the present invention. It is a cross-sectional schematic diagram of the right half of the other embodiment of the pneumatic tire of the present invention. It is a cross-sectional schematic diagram of the right half of the other embodiment of the pneumatic tire of the present invention. It is explanatory drawing for calculating | requiring (SIGMA) tan (delta) (28-150 degreeC) in the vulcanized rubber physical property of a rubber composition.

The pneumatic tire of the present invention comprises a bead core, a carcass ply, a tread rubber layer, an inner liner, a side reinforcing layer, and a bead filler, and as a reinforcing fiber cord constituting the carcass ply, a drying step after applying an RFL adhesive And a cord containing at least 50% by mass of a polyketone fiber, which is dried and cured through a heat treatment step, and the following conditions (1) The cord tension in the drying step and the heat treatment step is 2.9 to 49 per one .0N,
(2) The drying treatment temperature in the drying step is 100 to 200 ° C., and (3) Tm × when the curing treatment temperature in the heat treatment step is Tm (° C.) and the curing treatment time is s (seconds). It is characterized by satisfy | filling that s / 1000 is 10-55.

FIG. 1 is a schematic view showing a cross-sectional view of one embodiment of the pneumatic tire of the present invention.
In FIG. 1, a preferred embodiment of the pneumatic tire of the present invention is toroidally connected between a pair of bead cores 1, 1 ′ (1 ′ is not shown), and both ends of the bead core 1 are located outside the tire from the inside. A carcass layer 2 composed of at least one radial carcass ply wound up, a side rubber layer 3 disposed on the outer side in the tire axial direction of the side region of the carcass layer 2, and a crown region of the carcass layer 2 A tread rubber layer 4 disposed on the outer side in the tire radial direction to form a ground contact portion, a belt layer 5 disposed between the tread rubber layer 4 and the crown region of the carcass layer 2 to form a reinforcing belt, An inner liner 6 disposed on the entire inner surface of the tire of the carcass layer 2 to form an airtight film, and the case extending from one bead core 1 to the other bead core 1 ′. The bead filler 7 disposed between the main body portion of the dregs layer 2 and the winding portion wound up on the bead core 1, and the carcass layer 2 extending from the side of the bead filler 7 in the side region of the carcass layer to the shoulder region 10. A pneumatic tire having at least one side reinforcing layer 8 having a cross-sectional shape along the tire rotation axis and a substantially crescent shape between the inner liner 6 and the inner liner 6. By using the rubber composition (1) and the rubber composition (2) according to the present invention, which will be described later, for the side reinforcing layer 8 and / or the bead filler 7 of the pneumatic tire, the pneumatic tire of the present invention is the above-described one. The effect of this can be achieved.

The pneumatic tire of the present invention is a pneumatic tire having the above-described configuration and further including at least one reinforcing cord layer, wherein at least one of the reinforcing cord layers is made of a polyester fiber cord. At least a part of the region A from the end of the belt layer to the maximum width of the tire side portion and / or at least one of the region B from the vicinity of the bead core to the outer end of the bead filler in the radial direction of the tire. It is further preferable that the portion is disposed so that the angle with respect to the tire radial direction is 0 to 85 °.
If the angle of the polyester fiber cord in the reinforcing cord layer with respect to the tire radial direction is within 85 °, it becomes possible to sufficiently suppress the deflection of the tire during run-flat running, and further improve the run-flat durability of the tire. be able to. From the viewpoint of sufficiently suppressing the deflection of the tire during run-flat running, 0 ° is particularly preferable.
Hereinafter, a more preferable pneumatic tire according to the present invention will be described with reference to the drawings. FIGS. 2-6 is a cross-sectional schematic diagram of the right half of the suitable embodiment of the pneumatic tire of this invention.

  The tire of the embodiment shown in FIG. 2 to FIG. 6 is a radial direction from the inner side to the outer side in the tire width direction around the bead core 1 and the main body part extending in a toroid shape between the bead cores 1 embedded in the pair of bead parts 20. A carcass layer 2 having a folded portion wound outward, a tread rubber layer 4 disposed on the outer side in the tire radial direction of the crown portion of the carcass layer 2, and a pair of tread rubber layers 4 located at both ends of the tread rubber layer 4 A buttress portion 30, a pair of sidewall portions 40 connecting the buttress portion 30 and the bead portion 20, and a pair disposed inside the carcass layer 2 extending from the buttress portion 30 to the sidewall portion 40. A side reinforcing layer 8 having a crescent-shaped cross section, a region A from the end of the belt layer to the maximum width of the tire side, and / or a bead filler from the vicinity of the bead core. Comprising 7 a pair of reinforcing cord layer 11 disposed outside of the carcass layer 2 in at least a portion of the region B to the radially outer end of.

  In the tire of the embodiment shown in FIGS. 2 to 6, a bead filler 7 is disposed between the main body portion and the folded portion of the carcass layer 2 and outside the bead core 1 in the tire radial direction, A belt layer 5 composed of two belt cord layers is disposed on the outer side of the crown portion of the carcass layer 2 in the tire radial direction. Further, the entire belt layer 5 is disposed on the outer side of the belt layer 5 in the tire radial direction. A belt reinforcing layer 12a is disposed so as to cover, and a pair of belt reinforcing layers 12b are disposed so as to cover only both end portions of the belt reinforcing layer 12a. Here, the belt cord layer is usually composed of a rubberized layer of a cord extending at an inclination with respect to the tire equatorial plane, preferably a rubberized layer of a steel cord, and the two belt cord layers are composed of the belt cord layer. Are laminated so as to intersect with each other across the tire equator plane to form the belt layer 5. The belt reinforcing layers 12a and 12b are usually made of rubberized layers of cords arranged substantially parallel to the tire circumferential direction.

  The carcass layer 2 of the embodiment shown in FIGS. 2 to 6 is composed of one carcass ply. However, in the pneumatic tire of the present invention, the number of carcass plies constituting the carcass layer 2 is the same. It is not limited, Two or more sheets may be sufficient, and the structure is not particularly limited. The belt layer 5 of the embodiment shown in FIGS. 2 to 6 is composed of two belt cord layers. In the pneumatic tire of the present invention, the number of belt cord layers constituting the belt layer 5 is equal to this. It is not limited. Furthermore, the belt reinforcing layers 12a and 12b of the embodiment shown in FIGS. 2 to 6 are formed of a single belt reinforcing layer 12a that covers the entire belt layer 5, and a two-layer belt that covers only both ends of the belt reinforcing layer 12a. The reinforcing layer 12b has a so-called cap layer structure. However, in the pneumatic tire of the present invention, the belt reinforcing layers 12a and 12b are not necessarily provided. Can also be provided.

  Furthermore, the tire of the embodiment shown in FIGS. 2 to 6 includes a rim guard 13 having a substantially triangular cross section outside the folded portion of the carcass layer 2 in the region extending from the sidewall portion 40 to the bead portion 20 in the tire width direction. However, in the pneumatic tire of the present invention, it is not essential to dispose the rim guard 13, and a rim guard having another shape can be disposed. 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 13 is not provided.

  Here, in an embodiment of the more preferable pneumatic tire of the present invention shown in FIG. 2, the reinforcing cord layer 11 extends from the end of the belt layer 5 along the outer side of the carcass layer 2. It extends between the part and the bead filler 7 to the bead part 20, and is folded and locked around the bead core 1 embedded in the bead part 20. The pneumatic tire has a reinforcing cord made of a polyester fiber cord, and at least one reinforcing cord layer 11 is at least a part of the region A from the end of the belt layer 5 to the maximum width portion of the tire side portion and / or Or as long as it is arrange | positioned in at least one part of the area | region B from the bead core vicinity to the tire radial direction outer side edge part of the bead filler 7, it does not restrict | limit, Two or more layers of the reinforcing cord layers 11 May be provided, the reinforcing cord layer 11 may extend to portions other than the regions A and B.

For example, as a more preferable pneumatic tire of the present invention, as shown in FIG. 3, the reinforcing cord layer 11 includes a main body portion of the carcass layer 2 along the outer side of the carcass layer 2 from the end portion of the belt layer 5. A mode in which the reinforcing cord layer 11 extends from the end portion of the belt layer 5 to the folded portion of the carcass, as shown in FIG. 4, through the space between the bead fillers 7 and to the vicinity of the bead core 1 embedded in the bead portion 20. As shown in FIG. 5, an aspect disposed on the outside of the carcass layer 2 in the region up to the end portion and between the main body portion of the carcass layer 2 and the bead filler 7, a single reinforcing cord layer 11 includes: An aspect disposed outside the carcass layer 2 in a region extending from the buttress portion 30 to the sidewall portion 40, particularly from the maximum width portion of the tire side portion to the inside in the tire radial direction, as shown in FIG. 11 Aspect which is disposed on the outer side of the carcass layer 2 in the region from the end portion of the belt layer 5 to the end portion of the folded portion of the carcass is also preferred.
By using the rubber composition (1) or the rubber composition (2) according to the present invention described later for the side reinforcing layer 8 and / or the bead filler 7 of the pneumatic tire of the embodiment shown in FIGS. The further preferable pneumatic tire of the present invention can exhibit the above-described effects.

[Reinforcing fiber cords constituting the carcass ply]
In the pneumatic tire of the present invention, an RFL adhesive is applied to a cord containing at least 50% by mass of a polyketone fiber as a reinforcing fiber cord constituting a carcass ply, and then dried and cured through a drying step and a heat treatment step. Use things.
(Polyketone fiber)
In the present invention, as the polyketone constituting the polyketone fiber, the following general formula (I)

[In formula, A shows the residue derived from the unsaturated compound superposed | polymerized by the unsaturated bond, and may be same or different in a repeating unit. And those having a repeating unit represented by the formula:
Among these polyketones, a polyketone in which 97 mol% or more of repeating units is 1-oxotrimethylene [—CH ₂ —CH ₂ —CO—] is preferable, and a polyketone in which 99 mol% or more is 1-oxo trimethylene is more preferable. Most preferred are polyketones in which 100 mol% is 1-oxotrimethylene. As the proportion of 1-oxotrimethylene in the repeating unit is higher, the regularity of the molecular chain is improved, and a fiber with high crystallinity and high degree of orientation can be obtained.

  In the above polyketone, the ketones may be partially bonded to each other and the unsaturated compound-derived parts may be bonded to each other, but the ratio of the unsaturated compound-derived residues and ketone groups alternately arranged is 90% by mass or more. It is preferable that it is 97 mass% or more, and it is most preferable that it is 100 mass%.

  In the above formula (I), the unsaturated compound constituting A is most preferably ethylene, but propylene, butene, pentene, cyclopentene, hexene, cyclohexene, heptene, octene, nonene, decene, dodecene, styrene, acetylene. , Unsaturated hydrocarbons other than ethylene such as allene, methyl acrylate, vinyl acetate, acrylamide, hydroxyethyl methacrylate, undecenoic acid, undecenol, 6-chlorohexene, N-vinylpyrrolidone, diester of styrylphosphonic acid, sodium styrenesulfonate Further, it may be a compound containing an unsaturated bond such as sodium allyl sulfonate and vinyl chloride.

  As a method for fiberizing this polyketone, (1) after spinning an undrawn yarn, performing multistage hot drawing, and drawing at a specific temperature and magnification in the final drawing step of the multistage hot drawing, (2 ) A method is preferred in which after unspun yarns are spun, hot drawing is performed, and after the hot drawing, the fibers are rapidly cooled while high tension is 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 hexafluorooisopropanol and m-cresol as described in JP-T-505344, WO99 / 18143, WO00 / 09611, JP2001-164422, A wet spinning method using an aqueous solution of zinc salt, calcium salt, thiocyanate, iron salt or the like as described in JP-A Nos. 2004-218189 and 2004-285221 is preferable.

Further, as a stretching method of the obtained unstretched yarn, a hot stretching method in which the unstretched yarn is stretched by heating to a temperature higher than the glass transition temperature of the unstretched yarn is preferable. The method (2) may be performed in one stage, but it is preferably performed 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 (melting point of polyketone), and the total stretching ratio is preferably 10 times or more.

The polyketone fiber preferably has a crystal structure with a crystallinity of 50 to 90% and a crystal orientation of 95% or more. When the degree of crystallinity is less than 50%, the fiber structure is not sufficiently formed and sufficient strength cannot be obtained, and the shrinkage property and dimensional stability during heating may be unstable. For this reason, the crystallinity is preferably 50 to 90%, more preferably 60 to 85%.
The cord can be made by twisting filament bundles. There is no restriction | limiting in particular about the number of filament bundles twisted, The code | cord | chord which twisted two or three filament bundles normally is used.

In the present invention, examples of the cord used for the production of the reinforcing fiber cord constituting the carcass ply include (a) a cord made only of a polyketone fiber, and (b) a polyketone fiber and a fiber other than the polyketone fiber mixed or twisted. A code etc. are mentioned. It is necessary that at least 50% by mass of the polyketone fiber is contained in one cord. Polyketone fibers are used in the cord at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, and most preferably 100% by weight.
By setting the ratio of the polyketone fiber in the cord within the above range, excellent heat shrinkability, strength, dimensional stability, heat resistance, adhesion to rubber, and the like of the cord can be obtained.

  The fibers other than polyketone fibers are not particularly limited as long as the ratio is 50% by mass or less, and known fibers such as polyamide fibers, polyester fibers, rayon fibers, and aramid fibers are used depending on the application and purpose. When the amount of fibers other than polyketone fibers exceeds 50% by mass, for example, in the case of cords made of polyester fibers or polyamide fibers, the strength and dimensional stability are impaired, and in the case of warp yarns made of rayon fibers, the strength is greatly impaired. In the case of warp made of aramid fibers, the adhesiveness with rubber is greatly impaired.

(Production of reinforcing fiber cord)
In the pneumatic tire of the present invention, the reinforcing fiber cord constituting the carcass ply is applied with the RFL adhesive on the cord containing at least 50% by mass of the polyketone fiber obtained as described above, followed by a drying step and a heat treatment step. In this case, the cord tension in the drying step and the heat treatment step is 2.9 to 49.0 N per one of the following conditions (1):
(2) The drying process temperature in the said drying process is 100-200 degreeC,
(3) When the curing temperature in the heat treatment step is Tm (° C.) and the curing time is s (seconds), Tm × s / 1000 is 10 to 55,
It is necessary to satisfy.

If the cord tension in the drying step and the heat treatment step is less than 2.9 N per yarn, the yarn is not sufficiently modified in the heat treatment step, whereas if it exceeds 49.0 N, the yarn is often broken. , Tire molding becomes difficult. The cord tension is preferably 9.8 to 39.2 N per cord from the viewpoint of sufficiently performing heat treatment and preventing the yarn from being cut.
In addition, when the drying process temperature in the drying step is less than 100 ° C., moisture in the RFL adhesive is difficult to evaporate and drying becomes insufficient. On the other hand, when it exceeds 200 ° C., evaporation of moisture in the RFL adhesive occurs at a stretch. As a result, there is a problem that the adhesive is not uniformly adhered and impregnated on the cord. This drying treatment temperature is preferably 120 to 190 ° C., more preferably 140 to 180 ° C. from the viewpoints of drying properties and homogeneous adhesion impregnation of the adhesive.
Further, in the heat treatment step, if Tm × s / 1000 is less than 10, the heat amount is small and the adhesiveness is lowered, and if it exceeds 55, the heat amount is increased and the cord is burnt to reduce the cord strength. This Tm × s / 1000 is preferably 14 to 52, more preferably 20 to 45, from the viewpoint of adhesiveness and cord strength. The curing treatment temperature Tm in the heat treatment step is usually about 150 to 260 ° C., preferably 160 to 250 ° C., and the curing treatment time is usually about 40 to 240 s, preferably 60 to 180 s.

As the RFL adhesive used in the present invention, either a conventionally known one-bath type or two-bath type can be used.
Specifically, after a cord containing at least 50% by mass of polyketone fiber is treated with a first liquid containing an epoxy compound or a blocked isocyanate compound, resorcin, formaldehyde, various latexes, sodium hydroxide and / or aqueous ammonia are contained. A two-bath type adhesion method in which treatment is performed with the second solution (RFL solution); treatment with a mixed solution of a solution commonly called N3 produced from triallyl cyanurate, resorcin, formaldehyde, and aqueous ammonia and an RFL solution A one-bath type adhesion method; a reaction product mainly composed of 2,6-bis (2 ′, 4′-dihydroxyphenylmethyl) -4-chlorophenol formed from p-chlorophenol and formaldehyde; A liquid called form PEXUL consisting of formaldehyde and aqueous ammonia A one-bath type adhesion method in which treatment is performed with a liquid mixed with an RFL liquid; a liquid obtained by aging a polyhydric phenol polysulfide and a condensate of resorcin and formaldehyde, as disclosed in JP-A-60-72972, in an alkali And a one-bath type bonding method in which a treatment is performed with a mixture of the RFL liquid and the like.
In addition, it is good to provide a heat set zone and a normalizing zone in the heating tension treatment in the drying treatment step and the heat treatment step.

As the RFL adhesive, a dip solution containing resorcin / formaldehyde resin and rubber latex is used.
The dip liquid can be obtained, for example, by condensing resorcin and formaldehyde or resorcin / formaldehyde precondensate with formaldehyde by resorification reaction in the presence of rubber latex. This resolation reaction is usually carried out at a pH of 8.0 or higher, preferably 8.5 to 10.0. Here, the said resorcin-formaldehyde initial condensate contains the structural unit derived from formaldehyde and the structural unit derived from resorcin, and refers to the state where the structural unit derived from formaldehyde is stoichiometrically insufficient. That is, this makes the resin low in molecular weight and soluble.

As the rubber latex, styrene-butadiene copolymer latex and / or vinylpyridine-styrene-butadiene terpolymer latex can be used. Particularly, vinylpyridine-styrene-butadiene terpolymer is used. Latex is preferable, and the mass ratio of the structural unit derived from vinylpyridine, the structural unit derived from styrene, and the structural unit derived from butadiene is preferably 10:10:80 to 20:50:30.
This vinylpyridine-styrene-butadiene terpolymer latex can be obtained as a commercial product, and examples thereof include those manufactured by Japan A & L, trade name “PYRATEX”, and a solid content of 41% by mass.

In the present invention, vinylpyridine-styrene-butadiene terpolymer latex may be used alone, or one or more other rubber latexes may be used in combination as long as the effects of the present invention are not impaired. .
Examples of other rubber latex include modified latex obtained by modifying a vinylpyridine-styrene-butadiene copolymer with a carboxy group, styrene-butadiene latex and modified latex thereof, natural rubber latex, acrylate copolymer latex, butyl rubber In addition to latex and chloroprene rubber latex, latex prepared by dispersing a rubber component of the same type as the rubber component blended in the adherend rubber in water or an organic solvent can be used.

  The vinylpyridine-styrene-butadiene terpolymer is obtained by terpolymerization of a vinylpyridine compound, a styrene compound, and a butadiene compound. Here, the vinylpyridine-based compound includes vinylpyridine and a substituted vinylpyridine in which a hydrogen atom in the vinylpyridine is substituted with a substituent. Examples of the vinylpyridine compounds include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. Among these, 2 -Vinylpyridine is preferred. These vinylpyridine compounds may be used alone or in combination of two or more.

The styrene compound includes styrene and substituted styrene in which a hydrogen atom in the styrene is substituted with a substituent. Examples of the styrene compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Examples thereof include hydroxymethylstyrene, and among these, styrene is preferable. These styrenic compounds may be used alone or in combination of two or more.
Examples of the butadiene compound include 1,3-butadiene and 2-methyl-1,3-butadiene. Among these, 1,3-butadiene is preferable. These butadiene compounds may be used alone or in combination of two or more.

  In the two-bath type adhesion method, the epoxy compound used in the first liquid is diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol / diglycidyl ether, glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythritol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, etc. Products of Polyhydric Alcohols with Epichlorohydrin; Phenol Novolac Type Epoxy Resin, Cresol Novolac Novolak epoxy resins such as epoxy resins; bisphenol A type epoxy resins.

In the two-bath type adhesion method, the blocked isocyanate compound used in the first liquid is a free isocyanate group of the isocyanate compound blocked with a thermal dissociation blocking agent, and does not react with water at room temperature, By heating, the blocking agent is dissociated and the active isocyanate group is regenerated.
As the blocked isocyanate compound, those obtained by blocking an organic polyisocyanate compound such as diphenylmethane diisocyanate (MDI) or tolylene diisocyanate (TDI) with a blocking agent are preferably used. Examples of the blocking agent include phenols such as phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, and p-nonylphenol; Secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; aromatic secondary amines such as diphenylamine; phthalimides; lactams such as δ-valerolactam; caprolactams such as ε-caprolactam Active methylene compounds such as malonic acid dialkyl ester, acetylacetone and acetoacetic acid alkyl ester; ketoximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; 3-hydroxy Examples thereof include basic nitrogen compounds such as pyridine and acidic sodium sulfite.
Phenol, ε-caprolactam and ketoxime are preferred as the blocking agent.

In the present invention, the adhesion amount of the reinforcing fiber cord obtained by applying the RFL adhesive as described above and then subjected to a drying and curing treatment is 1.5 to 9.9 with respect to the mass of the cord before the treatment. It is preferably 0% by mass. If the adhesion amount is 1.5% by mass or more, good adhesiveness can be exhibited, and if it is 9.0% by mass or less, the occurrence of a decrease in cord strength due to an increase in cord hardness is suppressed. can do. A more preferable adhesion amount is 2.5 to 7.0% by mass.
In the present invention, the reinforcing fiber cord constituting the carcass ply preferably has a twist coefficient N represented by the following formula (1) satisfying the relationship of the following formula (2).
N = n × (0.125D / ρ) ^1/2 × 10 ⁻³ (1)
0.34 ≦ N (2)
[In the formula, n represents the number of upper twists (times / 10 cm), D represents the total display decitex, and ρ represents the density (g / cm ³ ) of the fiber containing at least 50% by mass of the polyketone fiber. ]
If the twist coefficient N is 0.34 or more, fatigue resistance necessary as a carcass ply can be ensured. As the twist coefficient N, the formula (2-a)
0.6 ≦ N ≦ 0.9 (2-a)
It is more preferable to satisfy. If the twist coefficient N is 0.9 or less, deterioration of workability due to twisting back of the twisted yarn can be suppressed. A more preferable twist coefficient N is in a range of 0.7 ≦ N ≦ 0.8.

In the present invention, it is preferable that the number of reinforcing fiber cords constituting the carcass ply is 30 to 60/50 mm. The strength and durability of the carcass can be more suitably obtained by setting the number of reinforcing fiber cords constituting the carcass ply to be within the above range. Even if the number of driving exceeds 60/50 mm, there is no particular limitation as long as driving can be performed.
Further, the reinforcing fiber cord constituting the carcass ply containing at least 50% by mass of the polyketone fiber is preferably twisted in two or three filament bundles having a fineness of 500 to 2000 dtex.
By setting the fineness of the cord used for the reinforcing fiber cord within the above range, the elastic modulus and the heat shrinkage stress can be secured and the driving can be made dense. Moreover, it is preferable to twist two or three filament bundles.

(Function of reinforcing fiber cord)
In the pneumatic tire of the present invention, as a reinforcing fiber cord constituting a carcass ply, a general rayon fiber can be obtained by applying an RFL adhesive to a cord containing at least 50% by mass of a polyketone fiber, followed by drying and curing treatment. Compared with a carcass ply using a reinforcing cord using a sword, the longitudinal spring constant during run-flat traveling can be improved while maintaining the longitudinal spring constant of the tire during normal internal pressure traveling. As a result, by using the carcass ply to which the reinforcing fiber cord according to the present invention is applied for the pneumatic tire, it is possible to improve the run-flat durability while maintaining the tire riding comfort during normal running. This is an action utilizing the fact that the tensile strain generated in the cord during run-flat traveling is significantly larger than the tensile strain generated in the cord when the tire is filled with air.
In addition, the reinforcing fiber cord containing at least 50% by mass of the polyketone fiber is higher in strength than the reinforcing fiber cord using the rayon fiber, so even if the number of the reinforcing fiber cords arranged in the carcass ply is reduced, the run flat running By maintaining the longitudinal spring constant of the tire at the time, the run-flat durability performance can be maintained. On the other hand, by reducing the number of reinforcing fiber cords arranged, it is possible to reduce the longitudinal spring constant of the tire during normal running and to improve riding comfort.

[Reinforcing cords constituting the reinforcing cord layer]
In a more preferable pneumatic tire of the present invention, it is preferable to use a polyester fiber cord as the reinforcing cord constituting the reinforcing cord layer.
Examples of the polyester fiber cords include polyethylene terephthalate fiber cords and polybutylene terephthalate fiber cords, but polyethylene terephthalate fiber cords are more preferable from the viewpoint of preventing rolling resistance and riding comfort during normal running.
The polyester fiber cord described above preferably twists 2 to 3 filament bundles having a fineness of 200 to 2000 dtex, and the twist coefficient N is preferably 0.4 to 1.0. This is because if the fineness is within the above range, the elastic modulus and heat shrinkage stress can be secured, the driving can be made dense, and the strength and weight as a tire can be balanced. If the twist coefficient N is 0.4 or more, the fatigue resistance necessary for the reinforcing cord layer can be secured, and if the twist coefficient N is 1.0 or less, the reinforcing cord can be manufactured more suitably. it can.
The number of reinforcing cord layers to be driven is preferably 30 to 60/50 mm. The strength and durability of the reinforcing cord layer can be more suitably obtained by setting the number of driven wires within the above range.
As the above-mentioned polyester fiber cord adhesive, any of a conventionally known one-bath type and two-bath type can be used. Specifically, the above-described RFL adhesive can be used.

[Rubber composition (1)]
In the pneumatic tire of the present invention, as described above, the reinforcing fiber cord constituting the carcass ply is obtained by applying an RFL adhesive to a cord containing at least 50% by mass of a polyketone fiber, followed by drying and curing treatment. It is possible to improve the run flat durability without impairing the rolling resistance and riding comfort during normal driving. Although it is possible to further improve the flat durability, the rubber composition (1) having specific vulcanized rubber properties shown below is used as a reinforcing rubber, and at least one of the tire members, particularly the side reinforcing layer. And / or use in bead fillers to significantly improve run-flat durability through synergistic effects So it becomes possible.

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 (1) having an elastic modulus at 100% elongation (M100) of 10 MPa or more and a loss tangent (tan δ) of Σ value 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 (1) 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. What contains a conjugated diene polymer in the ratio of 30 mass% or more, preferably 50 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 secondary amino groups include N- (trimethylsilyl) imino groups. 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, from the viewpoint of improving the dispersibility of the filler, the primary amine-modified conjugated diene polymer modified with a primary amino group is used 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 a protected primary 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 preferred.
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. Examples of such a polymerization reaction having a living property include a reaction in which an organic alkali metal compound is used as an initiator and a conjugated diene compound alone or an conjugated diene compound and an aromatic vinyl compound are anionically polymerized in an organic solvent. .

  As the organic alkali metal compound used as an initiator for the above-mentioned anionic polymerization, a lithium compound is preferable. The lithium 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 a polymerization active site. A conjugated diene polymer 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.

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-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 a lithium compound is used as a polymerization initiator, not only a conjugated diene polymer having an active end but also a copolymer of a conjugated diene compound having an active end and an aromatic vinyl compound can be obtained efficiently. it can.

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, 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 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 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 tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) titanium, tetrakis (2-propyl-1). , 3-hexanediolato) titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1,3-pentanediolato) titanium, tetrakis (2-Methyl-1,3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3-pentanediolato) titanium, tetrakis (2 -Butyl-1,3-pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl-1, -Heptanediolato) titanium, tetrakis (2-ethyl-1,3-heptanediolato) titanium, tetrakis (2-propyl-1,3-heptanediolato) titanium, tetrakis (2-butyl-1,3-heptanediolato) titanium, tetrakis (2 -Ethylhexoxy) titanium, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra-sec-butoxy Titanium, tetra-tert-butoxytitanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolamate), Tantributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titanium propoxyacetylacetonatebis (ethylacetoacetate), Titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate), titanium tributoxyethylacetoacetate, titaniumbutoxyacetylacetonatebis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonatebis ( Ethyl acetoacetate), bis (2-ethylhexanoate) 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 (stearate) titanium, tetrakis (oleate) titanium, tetrakis (linoleate) titanium, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium oxide bis (tetramethylheptanedionate), titanium oxide Examples thereof include compounds containing titanium such as bis (pentanedionate) and titanium tetra (lactate). Among these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.

  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-ethylhexoxy) 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-ethylhexoxy) 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, 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.
Moreover, you may perform a condensation reaction in aqueous solution, 30-180 degreeC of condensation reaction temperature is preferable, 85-180 degreeC is more preferable, More preferably, it is 100-170 degreeC, Especially preferably, it is 110-150 degreeC.
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 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. 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 are no particular restrictions on the type of the condensation reaction carried out in an aqueous solution, and the reaction may be carried out continuously using a batch type reactor or an apparatus such as a multistage continuous reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.
The primary amino group derived from the modifier of the modified conjugated diene polymer according to 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, 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. .
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 loss tangent (tan δ) described later may not be 6.0 or less in the physical properties of the vulcanized rubber of the resulting rubber composition. is there. Therefore, the preferable amount of the carbon black is 55 to 80 parts by mass, more preferably 55 to 70 parts by mass, and particularly 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 in particular, the FEF grade grade is suitable for achieving low heat generation.

[Rubber composition (2)]
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) a filler of 50 parts by mass or less, and Rubber composition having vulcanized rubber properties of dynamic strain 1%, dynamic storage modulus (E ′) at 25 ° C. of 10 MPa or less, and loss tangent (tan δ) Σ value from 28 ° C. to 150 ° C. of 5.0 or less A thing (2) can also be used.
The rubber component (A) used in the rubber composition (2) and the conjugated diene polymer, modifier, condensation accelerator, modified conjugated diene polymer, and other rubbers related to the rubber component (A) The components are the same as those detailed in the rubber composition (1) described above.

((B) Filler)
In the rubber composition (2) according to the present invention, it is preferable to use the filler as the component (B) at a ratio of 50 parts by mass or less with respect to 100 parts by mass of the rubber component (A) described above. When the amount of the filler exceeds 50 parts by mass, effects such as sufficient low heat build-up and low elasticity are not exhibited, and in the vulcanized rubber properties of the resulting rubber composition, dynamic strain described later is 1%, 25 The dynamic storage modulus (E ′) at 0 ° C. may not be 10 MPa or less. If the amount of the filler is too large, the Σ value at 28 ° C. to 150 ° C. of the loss tangent (tan δ) described later may not be 5.0 or less in the physical properties of the vulcanized rubber of the resulting rubber composition. is there. Therefore, the preferable amount of the filler is 50 to 30 parts by mass, and more preferably 45 to 40 parts by mass. When the amount of the filler is 30 parts by weight or less, the breaking strength of the rubber is lowered, and the run-flat durability is remarkably impaired.

The (B) filler is carbon black, silica and general formula (II)
nM · xSiO _y · zH ₂ O (II)
[Wherein, M is at least selected from metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of the metals. N, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. ] It is at least 1 type chosen from the inorganic fillers represented by this.
As carbon black, in order for the vulcanized rubber properties of the resulting rubber composition to satisfy the above-mentioned vulcanized rubber properties, for example, various grades of carbon black such as SAF, HAF, ISAF, FEF, and FF can be used alone. Or it can be mixed and used. Among them, the FEF grade grade is preferable.
Silica is not particularly limited, but wet silica, dry silica, and colloidal silica are preferable. These can be used alone or in combination.

Specific examples of the inorganic filler represented by the general formula (II) include alumina (Al ₂ O ₃ ) such as γ-alumina and α-alumina, and alumina monohydrate (Al ₂ O such as boehmite and diaspore). ₃ · H ₂ O), Gibbsite, Bayerite, etc. Aluminum hydroxide [Al (OH) ₃ ], Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide ( MgO), magnesium carbonate (MgCO _3), talc _{(3MgO · 4SiO 2 · H 2} O), attapulgite _{(5MgO · 8SiO 2 · 9H 2} O), titanium white (TiO _2), titanium black (TiO _2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH) _2], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _{(Al 2 O 3 · 2SiO 2} ), Kao Down _{(Al 2 O 3 · 2SiO 2} · 2H 2 O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ · 3SiO ₄ · 5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ · SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], carbonic acid zirconium _{[Zr (CO 3) 2]} , crystalline aluminosilicate containing hydrogen, alkali metal or alkaline earth metal which corrects a charge as various zeolites There can be used.
The inorganic filler represented by the general formula (II) includes at least one selected from M selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate. preferable.
Among these, carbon black and silica are preferable as the filler, and carbon black is particularly preferable.

Furthermore, in the rubber composition (1) or (2) according to the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanizing agent, are used as long as the effects of the present invention are not impaired. Accelerators, process oils, antioxidants, scorch inhibitors, zinc white, stearic acid, and the like can be included.
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 (1))
The rubber composition (1) according to the present invention preferably has an elastic modulus at 100% elongation (M100) of 10 MPa or more as a vulcanized rubber property. 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.

Moreover, as said physical property of vulcanized rubber, it is preferable that Σ value [Σ tan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of loss tangent (tan δ) is 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. For this sample, a loss tangent (tan δ) was measured using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. 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. Then, as shown in FIG. 7, the relationship between the temperature and tan δ is graphed, the area of the shaded portion is obtained, and the value is Σ tan δ (28 to 150 ° C.).

(Physical properties of vulcanized rubber of rubber composition (2))
The rubber composition according to the present invention preferably has a vulcanized rubber property having a dynamic storage elastic modulus (E ′) of 10 MPa or less at a dynamic strain of 1% and 25 ° C. If the dynamic storage elastic modulus (E ′) at 1% dynamic strain and 25 ° C. exceeds 10 MPa, the tire during normal running becomes difficult to bend but the ride comfort is lowered. A preferable dynamic storage elastic modulus (E ′) is 8 MPa or more, and the upper limit thereof is not particularly limited, but is usually about 9.5 MPa.
The dynamic storage elastic modulus (E ′) is a value measured by the following method.
<Measuring method of dynamic storage elastic modulus (E ')>
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 side inner layer rubber composition at 160 ° C. for 12 minutes, and used as a sample. This sample is measured using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. under 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 temperature of 25 ° C.

Moreover, as said physical property of vulcanized rubber, it is preferable that Σ value [Σ tan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of loss tangent (tan δ) is 5.0 or less. When the Σ value of tan δ exceeds 5.0, 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 3.
The Σtan δ (28 to 150 ° C.) is a value measured based on the above-described measuring method of Σ tan δ (28 to 150 ° C.).

(Preparation of rubber composition, production of pneumatic tire)
The rubber composition (1) or (2) according to the present invention is kneaded using a kneading machine such as a Banbury mixer, a roll, an internal mixer or the like according to the formulation described in Tables 2 and 4 below. And is vulcanized after molding and used as the side reinforcing layer 8 and / or the bead filler 7 of the pneumatic tire in FIG.
In the pneumatic tire of the present invention, an RFL adhesive is applied to a cord containing at least 50% by mass of a polyketone fiber as a reinforcing fiber cord constituting a carcass ply used for the carcass layer 2, and is dried and cured under the specific conditions described above. The rubber composition (1) or (2) according to the present invention described above is preferably used for the side reinforcing layer 8 and / or the bead filler 7 and is produced by an ordinary run-flat tire manufacturing method. Can be manufactured.
In the pneumatic tire of the present invention thus obtained, both the rubber composition (1) and the rubber composition (2) have run-flat durability without impairing rolling resistance and riding comfort during normal running. However, the rubber composition (1) is superior in ride comfort and the rubber composition (2) is superior in run-flat durability.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
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) Measured by GPC [manufactured by Tosoh Corporation, HLC-8020] using a refractometer as a standard, and monodisperse polystyrene is standard It was shown in terms of polystyrene. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.

《Frequency of trouble during manufacturing》
The number of troubles such as yarn breakage during DIP processing and abnormal DIP scale adhesion was shown as an index with Comparative Example 1 being 100. The smaller the index, the less frequent the trouble.
《Quality trouble occurrence frequency》
-The number of cases in which troubles such as a decrease in adhesion and a decrease in strength occurred in the physical properties of the cord after DIP treatment was shown as an index with Comparative Example 1 as 100. The smaller the index, the lower the frequency of quality troubles.
<< Physical properties of vulcanized rubber of rubber composition >>
The Σ value [Σtan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of the elastic modulus at 100% elongation (M100), dynamic storage modulus (E ′) and loss tangent (tan δ) is described in the specification text. Measured according to the method.
<< Evaluation of pneumatic tire >>
・ Run-flat durability Each test tire (passenger car radial tire of tire size 215 / 45ZR17) is assembled with rim at normal pressure, filled with 230kPa of internal pressure, left in a room at 38 ℃ for 24 hours, and then the valve core is The drum running test was performed under the conditions of a load of 4.17 kN (425 kg), a speed of 89 km / h, and an indoor temperature of 38 ° C. The travel distance until failure of each test tire was measured, and the travel distance of Comparative Example 1 was taken as 100, and the index was displayed by the following formula. The larger the index, the better the run flat durability.
Run-flat durability (index) = (travel distance of test tire / travel distance of tire of Comparative Example 1) × 100
・ Riding Comfort Each test tire is mounted on a passenger car, a feeling test of riding comfort is conducted by two specialized drivers, and an average value of 1-10 is obtained. Is shown as an index with 100 being 100. The higher the index, the better the ride comfort.

Production Example 1 Production of Polyketone Fiber A polyketone polymer having an intrinsic viscosity of 5.3, which was prepared by a conventional method and was completely alternatingly copolymerized with ethylene and carbon monoxide, was added to an aqueous solution containing 65% by mass of zinc chloride / 10% by mass of sodium chloride. The mixture was stirred and dissolved at 80 ° C. for 2 hours to obtain a dope having a polymer concentration of 8% by mass.
This dope is heated to 80 ° C., filtered through a 20 μm sintered filter, passed through a 10 mm air gap from a 50-hole spout diameter maintained at 80 ° C., and 5% by mass of zinc chloride. Was extruded at a rate of 2.5 cm ³ / min. Into 18 ° C. water containing a coagulated yarn while drawing at a rate of 3.2 m / min.
Subsequently, the coagulated yarn was washed with a sulfuric acid aqueous solution having a concentration of 2 mass% and a temperature of 25 ° C., and further washed with water at 30 ° C., and then the coagulated yarn was wound at a speed of 3.2 m / min.
The coagulated yarn was impregnated with IRGANOX 1098 (manufactured by Ciba Specialty Chemicals) and IRGANOX 1076 (manufactured by Ciba Specialty Chemicals) in an amount of 0.05% by mass (with respect to polyketone polymer), and then the coagulated yarn was dried at 240 ° C. A finishing agent was applied to obtain an undrawn yarn.

As the finishing agent, oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20000) / polyethylene oxide 10 mol addition oleyl ether / polyethylene oxide 10 mol addition castor oil ether / The one having a composition of sodium stearyl sulfonate / sodium dioctyl phosphate = 30/30/10/5/23/1/1 (mass% ratio) was used.
The obtained undrawn yarn was drawn at 240 ° C. in the first stage, followed by the second stage at 258 ° C., the third stage at 268 ° C., the fourth stage at 272 ° C., and then the second stage at 200 ° C. The film was stretched five times at 1.08 times (stretching tension 1.8 cN / dtex) and wound with a winder. The total draw ratio from the undrawn yarn to the five-stage drawn yarn was 17.1 times.

Production Example 2: Production of polybutadiene Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 2,2-ditetrahydrofurylpropane (0.0285 mmol) cyclohexane solution were injected under nitrogen. Then, 2.85 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a 50 ° C. hot 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.

Production Example 3: Production of primary amine-modified polybutadiene N, N-bis in which the polymer solution obtained in Production Example 2 was maintained at a temperature of 50 ° C. without deactivating the polymerization catalyst, and the primary amino group was protected. (Trimethylsilyl) aminopropylmethyldiethoxysilane (1129 mg, 3.364 mmol) was added, and the modification reaction was performed 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 4: Production of DMBTESPA-modified polybutadiene In Production Example 3, 1129 mg (3.364 mmol) of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added to N- (1,3-dimethylbutylidene) -3- ( DMBTESPA-modified polybutadiene was obtained in the same manner as in Production Example 3 except that triethoxysilyl) -1-propanamine was changed to 3.364 mmol.

Production Example 5: Production of secondary amine-modified polybutadiene Using N-methyl-N- (trimethylsilyl) aminopropylmethyldiethoxysilane, which is a secondary amine, as a modifier, a modification reaction is carried out based on Production Example 3 above. A secondary amine-modified polybutadiene was obtained.

Production Example 6 Production of Tertiary Amine Modified Polybutadiene A modification reaction was carried out based on Production Example 3 using DMAPES: 3-dimethylaminopropyl (diethoxy) methylsilane as a modifying agent to obtain a tertiary amine modified polybutadiene.

Production Example 7: Production of tin-modified polybutadiene A butadiene cyclohexane solution (16%) was poured into a dry, nitrogen-substituted 800 ml pressure-resistant glass container so as to be 50 g of butadiene monomer. After adding 0.44 mmol of tetrahydrofurylpropane and 0.48 mmol of n-butyllithium (BuLi), polymerization was performed at 50 ° C. for 1.5 hours. The polymerization conversion was almost 100%.
After 0.43 mmol of tin tetrachloride was added to this polymerization system, a modification reaction was further performed at 50 ° C. for 30 minutes. Thereafter, the reaction is stopped by adding 0.5 ml of a 5 wt% solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol to the polymerization system, and further drying according to a conventional method. A tin tetrachloride-modified polybutadiene rubber was obtained. Wn after modification was 570,000.

Examples 1 to 5 and Comparative Examples 1 to 3 (change in cord tension in the drying process and the heat treatment process)
(1) Production of reinforcing fiber cord for carcass ply Table 1 consisting of polyketone fibers (Examples 1 to 4) obtained in Production Example 1, rayon fibers (Comparative Example 1), and polyketone fibers (Comparative Examples 2 to 3) After applying a one-bath type dip solution containing an RFL adhesive having the following composition to each cord having the cord structure shown in Fig. 1, a drying step and a heat treatment step are performed, followed by drying and curing treatment, and a reinforcing fiber cord for carcass ply Produced. In addition, the twist coefficient N of the cord represented by N = n × (0.125 D / ρ) ^1/2 × 10 ⁻³ was 0.83. The number of upper twists n was 47 times / 10 cm, the total display decitex D was 3340 dtex, and the fiber density ρ was 1.33 g / cm ³ .
Moreover, the cord tension per one in the drying step and the heat treatment step, the drying treatment temperature in the drying step, Tm × s / 1000 in the heat treatment step, and the adhesive adhesion amount are as shown in Table 1.
<Composition of one bath type dip solution>
Resorcin and formaldehyde relative to the solids mass (L) of the total latex with a molar ratio (F / R) of formaldehyde (F) to resorcin (R) of about 2.0 (preferably 1.8 to 2.2) The ratio (RF / L) of the total mass (RF) is about 20% by mass (preferably 15 to 25% by mass), and the ratio of the solid content mass of the vinylpyridine (VP) latex in the total mass of latex solid content is About 41% by mass, the proportion of the solid content of styrene butadiene rubber (SBR) latex is about 40% by mass, and the molar ratio of sodium hydroxide to resorcin (R) (NaOH / R) is about 0.3. A bath-type dip solution was used.
(2) Production and Evaluation of Pneumatic Tire A radial tire for a passenger car having a tire size of 215 / 45ZR17 consisting of only one layer of a carcass ply using the reinforcing fiber cord obtained in Production Example 1 was produced in accordance with a conventional method. Run-flat durability and ride comfort were evaluated.
The cord tension in the drying process and the heat treatment process was changed to evaluate the frequency of troubles during production (dip processing) and the frequency of troubles (quality of cords after dip processing). The evaluation results are shown in Table 1.
The tires of Examples 1 to 5 and Comparative Examples 1 to 3 are side reinforcing except for Example 3 in which the composition D shown in Table 4 is used and the reinforcing rubber gauge of the side reinforcing layer 8 is 6.3 mm. The rubber composition A shown in Table 2 was used for the layer 8 and the bead filler 7. The reinforced rubber gauges of the side reinforcing layers 8 were all 5.7 mm. The number of reinforcing fiber cords constituting the carcass ply of any tire was 45/50 mm.

Examples 6 to 9 and Comparative Examples 4 to 5 (change in Tm × s / 1000 value)
(1) Carcass ply reinforcing fiber cords were produced in the same manner as in Example 1. The composition of the one-bath dip solution was the same as that in Example 1.
In addition, the cord tension per one in the drying step and the heat treatment step, the drying treatment temperature in the drying step, Tm × s / 1000 in the heat treatment step, and the adhesive adhesion amount are as shown in Table 1.
(2) Production and Evaluation of Pneumatic Tire A radial tire for a passenger car having a tire size of 215 / 45ZR17 consisting of only one layer of a carcass ply using the reinforcing fiber cord obtained in Production Example 1 was produced in accordance with a conventional method. Run-flat durability and ride comfort were evaluated.
Change the value of Tm x s / 1000 when the curing temperature in the heat treatment process is Tm (° C) and the curing time s, and the frequency of troubles during production (dip processing), quality (code properties after dip processing) ) Evaluated the frequency of trouble occurrence. The evaluation results are shown in Table 1-2.
In the tires of Examples 6 to 9 and Comparative Examples 4 to 5, the rubber composition A shown in Table 2 was used for the side reinforcing layer 8 and the bead filler 7. The reinforced rubber gauges of the side reinforcing layers 8 were all 5.7 mm. The number of reinforcing fiber cords constituting the carcass ply of any tire was 45/50 mm.

Examples 10-13 and Comparative Examples 6-7 (change drying temperature)
(1) Carcass ply reinforcing fiber cords were produced in the same manner as in Example 1. The composition of the one-bath dip solution was the same as that in Example 1.
In addition, the cord tension per one in the drying step and the heat treatment step, the drying treatment temperature in the drying step, Tm × s / 1000 in the heat treatment step, and the adhesive adhesion amount are as shown in Table 1-2.
(2) Production and Evaluation of Pneumatic Tire A radial tire for a passenger car having a tire size of 215 / 45ZR17 consisting of only one layer of a carcass ply using the reinforcing fiber cord obtained in Production Example 1 was produced in accordance with a conventional method. Run-flat durability and ride comfort were evaluated.
The value of the drying process temperature in the drying process was changed to evaluate the frequency of troubles during production (dip process) and the frequency of troubles (code physical properties after dip process). The evaluation results are shown in Table 1-3.
In the tires of Examples 9 to 13 and Comparative Examples 6 to 7, the rubber composition A shown in Table 2 was used for the side reinforcing layer 8 and the bead filler 7. The reinforced rubber gauges of the side reinforcing layers 8 were all 5.7 mm. The number of reinforcing fiber cords constituting the carcass ply of any tire was 45/50 mm.

［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３で得られたもの
４）ＤＭＢＴＥＳＰＡ変性ポリブタジエン：製造例４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、商品名「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、商品名「アロマックス＃３」
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、商品名「ノクラック６Ｃ」
８）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、商品名「ノクセラーＤＺ」
９）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、商品名「ノクセラーＴＯＴ−Ｎ」

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

Examples 2, 14-15
It consists of only one layer of carcass ply using the reinforcing fiber cord of Example 2 (the number of reinforcing fiber cords forming the carcass ply is 45/50 mm), and the rubber compositions A to C in Table 2 are used as side reinforcing layers. No. 8 and bead filler 7 used in Example 2, 14-15, tire size 215 / 45ZR17 radial tires for passenger cars were manufactured in accordance with conventional methods, and run-flat durability and riding comfort were evaluated. The results are shown in Table 3.
In addition, although the tire using the rubber composition A is a tire of Example 2, it re-displayed in Table 3 for the comparison with the tire of Examples 14-15. The reinforcing rubber gauge of the side reinforcing layer 8 is based on the values described in Table 3.

Examples 3, 16-23
It consists of only one layer of carcass ply using the reinforcing fiber cord of Example 3 (the number of driven reinforcing fiber cords constituting the carcass ply is 45/50 mm), and the rubber compositions D to L in Table 4 are used as side reinforcing layers. No. 8 and bead filler 7 were used, and radial tires for passenger cars of tire sizes 215 / 45ZR17 of Examples 3 and 16 to 23 were produced according to a conventional method, and run-flat durability and riding comfort were evaluated. The results are shown in Table 5.
In addition, although the tire using the rubber composition D is a tire of Example 3, it re-displayed in Table 5 for the comparison with the tire of Examples 16-23. The reinforcing rubber gauge of the side reinforcing layer 8 is based on the values described in Table 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３で得られたもの
４）二級アミン変性ポリブタジエン：製造例５で得られたもの
５）三級アミン変性ポリブタジエン：製造例６で得られたもの
６）スズ変性ポリブタジエン：製造例７で得られたもの
７）カーボンブラック：ＦＥＦ（Ｎ５５０）、旭カーボン社製、商品名「旭＃６０」
８）プロセスオイル：アロマティックオイル、富士興産社製、商品名「アロマックス＃３」
９）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、商品名「ノクラック６Ｃ」
１０）加硫促進剤ＣＺ：Ｎ−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、商品名「ノクセラーＣＺ」
１２）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、商品名「ノクセラーＴＯＴ−Ｎ」

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

Examples 3, 24-28
It consists of only one layer of carcass ply using the reinforcing fiber cord of Example 3 (the number of the reinforcing fiber cords forming the carcass ply is 45/50 mm). Used for the bead filler 7, the reinforcing cord layer has a fineness of 1670/2 (dtex / piece), an upper twist number of 40 (times / 10 cm), a twist coefficient N of 0.70, and a fiber density ρ of 1.38 (g / cm ³ ) polyethylene terephthalate fiber cords of 45/50 mm, and tire sizes 215 / of Examples 24-28 arranged as shown in FIGS. 2-6 such that the angle with respect to the tire radial direction is 0 ° A 45ZR17 radial tire for passenger cars was manufactured according to a conventional method, and run-flat durability and ride comfort were evaluated. The results are shown in Table 6.
The tire of Example 3 is shown again in Table 6 for comparison. The reinforcing rubber gauges of the side reinforcing layers 8 in Examples 3 and 24 to 28 are all 6.3 mm.

  In the pneumatic tire of the present invention, the reinforcing fiber cord containing the polyketone fiber is applied to the carcass ply, and preferably, the rubber composition (1) or (2) having a specific property is added to at least one of the tire members, In particular, by using it as a side reinforcement layer and / or bead filler, it is possible to improve run-flat durability without increasing trouble during production and quality trouble, and without impairing rolling resistance and riding comfort during normal running. it can.

DESCRIPTION OF SYMBOLS 1, 1 'bead core 2 Carcass layer 3 Side rubber layer 4 Tread rubber layer 5 Belt layer 6 Inner liner 7 Bead filler 8 Side reinforcement layer 10 Shoulder area 11 Reinforcement cord layer 12a, 12b Belt reinforcement layer 13 Rim guard 20 Bead part 30 Buttress part 40 Side wall part A Area from the end of the belt layer to the maximum width part of the tire side part B Area from the vicinity of the bead core to the outer end in the tire radial direction of the bead filler

Claims (38)

A pneumatic tire comprising a bead core, a carcass ply, a tread rubber layer, an inner liner, a side reinforcing layer and a bead filler, wherein the reinforcing fiber cord constituting the carcass ply is coated with a resorcin / formaldehyde resin-rubber latex adhesive Later, the cord is a cord containing at least 50% by mass of polyketone fiber, which is dried and cured through a drying step and a heat treatment step, and the cord tension in the following condition (1) in the drying step and the heat treatment step is 2 .9-49.0 N
(2) The drying treatment temperature in the drying step is 100 to 200 ° C., and (3) Tm × when the curing treatment temperature in the heat treatment step is Tm (° C.) and the curing treatment time is s (seconds). s / 1000 is 10 to 55,
A pneumatic tire characterized by satisfying   Further, the pneumatic tire includes at least one reinforcing cord layer, wherein at least one of the reinforcing cord layers includes a reinforcing cord made of a polyester fiber cord, and the tire side portion extends from the end of the belt layer. An angle with respect to the tire radial direction is 0 to 85 ° in at least a part of the region A up to the maximum width portion and / or at least a part of the region B from the vicinity of the bead core to the outer end in the tire radial direction of the bead filler. The pneumatic tire according to claim 1, wherein the pneumatic tire is disposed.   After the application of resorcin / formaldehyde resin-rubber latex adhesive, the adhesion amount of the reinforcing fiber cord formed by drying and curing is 1.5 to 9.0 mass% with respect to the mass of the cord before the treatment. The pneumatic tire according to claim 1 or 2. The pneumatic tire according to any one of claims 1 to 3, wherein the reinforcing fiber cord constituting the carcass ply has a twist coefficient N represented by the following formula (1) satisfying a relationship of the following formula (2).
N = n × (0.125D / ρ) ^1/2 × 10 ⁻³ (1)
0.34 ≦ N (2)
[In the formula, n represents the number of upper twists (times / 10 cm), D represents the total display decitex, and ρ represents the density (g / cm ³ ) of the fiber containing at least 50% by mass of the polyketone fiber. ] The twist coefficient N is the following formula (2-a)
0.6 ≦ N ≦ 0.9 (2-a)
The pneumatic tire according to claim 4, satisfying the relationship:   The pneumatic tire according to any one of claims 1 to 5, wherein the number of reinforcing fiber cords constituting the carcass ply is 30 to 60/50 mm.   The pneumatic tire according to any one of claims 1 to 6, wherein the reinforcing fiber cord constituting the carcass ply is formed by twisting a filament bundle having a fineness of 500 to 2000 dtex. The polyketone constituting the polyketone fiber is represented by the following general formula (I)

[In formula, A shows the residue derived from the unsaturated compound superposed | polymerized by the unsaturated bond, and may be same or different in a repeating unit. ]
The pneumatic tire according to claim 1, having a repeating unit represented by:   The pneumatic tire according to claim 8, wherein A in the general formula (I) is an ethylene group.   (A) The rubber component and 100 parts by mass of the rubber component (B) include 55 parts by mass or more of carbon black, and in the physical properties of vulcanized rubber, the elastic modulus at 100% elongation (M100) is 10 MPa or more, and the loss tangent ( The pneumatic tire according to any one of claims 1 to 9, wherein a rubber composition (1) having a tan value of tan δ at 28 to 150 ° C of 6.0 or less is used for at least one of the tire members.   The air according to claim 10, wherein in the rubber composition (1), (B) carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade. Enter tire.   The pneumatic tire according to claim 11, wherein (B) carbon black is FEF grade grade.   The pneumatic tire according to any one of claims 10 to 12, wherein in the rubber composition (1), the rubber component (A) contains an amine-modified conjugated diene polymer.   The pneumatic tire according to claim 13, wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer.   The pneumatic tire according to claim 13 or 14, wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.   The pneumatic tire according to claim 15, 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.   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. The described pneumatic tire.   The pneumatic tire according to claim 17, wherein the conjugated diene polymer is polybutadiene.   The pneumatic tire according to any one of claims 16 to 18, wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane.   The pneumatic tire according to any one of claims 10 to 19, wherein the rubber composition (1) is used for a side reinforcing layer.   The pneumatic tire according to any one of claims 10 to 19, wherein the rubber composition (1) is used as a bead filler.   The pneumatic tire according to any one of claims 10 to 19, wherein the rubber composition (1) is used for a side reinforcing layer and a bead filler.   (A) Rubber component and 100 parts by mass of (B) 50 parts by mass or less of filler, and in the physical properties of vulcanized rubber, dynamic storage elastic modulus (E) at 25% at dynamic strain of 1% The rubber composition (2) in which ') is 10 MPa or less and the loss tangent (tan δ) of Σ value at 28 ° C to 150 ° C is 5.0 or less is used. The described pneumatic tire. In the rubber composition (2), the filler (B) is carbon black, silica and general formula (II)
nM · xSiO _y · zH ₂ O (II)
[Wherein, M is at least selected from metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of the metals. N, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. ]
The pneumatic tire according to claim 23, wherein the pneumatic tire is at least one selected from the group consisting of inorganic fillers.   (B) The pneumatic tire according to claim 23 or 24, wherein the filler is carbon black.   26. The pneumatic tire according to claim 25, wherein 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 25, wherein the carbon black is FEF grade.   The pneumatic tire according to any one of claims 23 to 27, wherein in the rubber composition (2), the rubber component (A) contains a modified conjugated diene polymer.   The pneumatic tire according to claim 28, wherein the modified conjugated diene polymer is an amine-modified conjugated diene polymer.   The pneumatic tire according to claim 29, wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer.   The pneumatic tire according to claim 29 or 30, wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.   32. The pneumatic tire according to claim 31, wherein the primary amine-modified conjugated diene polymer is obtained by reacting a protected primary amine compound with the active terminal of the conjugated diene polymer.   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. The described pneumatic tire.   The pneumatic tire according to claim 33, wherein the conjugated diene polymer is polybutadiene.   The pneumatic tire according to any one of claims 32 to 34, wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropyltriethoxysilane.   The pneumatic tire according to any one of claims 23 to 35, wherein the rubber composition (2) is used for a side reinforcing layer.   The pneumatic tire according to any one of claims 23 to 35, wherein the rubber composition (2) is used as a bead filler.   The pneumatic tire according to any one of claims 23 to 35, wherein the rubber composition (2) is used for a side reinforcing layer and a bead filler.

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