JP2010132168A - Pneumatic tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pneumatic tire exhibiting enhanced run-flat durability while maintaining riding comfort during normal running. <P>SOLUTION: The pneumatic tire comprises a bead core, a carcass layer, a tread rubber layer, an inner liner, a side reinforcing layer and a bead filler, and adopts a rubber composition containing (A) rubber component and (B) carbon black of at least 55 pts.mass with respect to 100 pts.mass of the rubber component, and being formed by mixing (C) short fibers to a reinforcing rubber component of which the elastic modulus (M100) at 100% elongation elasticity is 10 MPa or more and the Σ value of tangent loss tan δ at 28-150°C is 6.0 or less in the physical properties of vulcanized rubber. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pneumatic tire. More specifically, by using a rubber composition having a specific property for the side reinforcing layer and / or the bead filler, air that has greatly improved run-flat durability without impairing riding comfort during normal driving. This relates to the tires inside.

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, the temperature 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 of prolonging the time until such a failure, the rubber composition used for the side reinforcing layer and the bead filler is highly compounded with sulfur, and the rubber composition is made highly elastic so that the tire sidewall portion and Although there is a technique for suppressing the deformation amount of the bead filler, there is a problem that the rolling resistance during normal running of the tire becomes high and the fuel efficiency is lowered.

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.
Furthermore, 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.

On the other hand, as a means of earning time to the failure, there is something that increases the volume of rubber, such as increasing the maximum thickness of the arranged side reinforcing layer and the bead filler, but when taking such a method, Undesirable situations such as deterioration of riding comfort during normal driving, increase in weight, and 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.

  On the other hand, a pneumatic tire is disclosed in which run-flat durability is improved without impairing riding comfort during normal running by using a rubber composition in which short fibers are blended in the side reinforcing rubber layer (for example, Patent Documents 4, 5 and 6). However, none of these techniques defines the physical properties of the reinforcing rubber component before blending the short fibers.

JP 11-310019 A WO02 / 02356 brochure JP 2004-74960 A JP 2007-276569 A JP 2007-284022 A JP 2007-284490 A

  An object of the present invention is to provide a pneumatic tire in which run-flat durability is greatly improved without impairing riding comfort during normal driving under such circumstances.

  As a result of intensive studies to develop a pneumatic tire having the above-mentioned preferable properties, the present inventors have obtained a rubber composition obtained by blending short fibers in a reinforcing rubber component having specific properties. In particular, it has been found that a pneumatic tire suitable for the purpose can be obtained by using it as a side reinforcing layer and / or a bead filler. 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 layer, a tread rubber layer, an inner liner, a side reinforcing layer, and a bead filler, wherein (A) the rubber component and 100 parts by mass of (B) carbon black A reinforced rubber component containing 55 parts by mass or more and having a vulcanized rubber physical property 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. And (C) a pneumatic tire characterized by using a rubber composition containing short fibers,
(2) The pneumatic tire according to (1), wherein the blending amount of (C) short fibers is 1 to 20 parts by mass with respect to 100 parts by mass of the (A) rubber component,
(3) The pneumatic tire according to (1) or (2), wherein the average fiber length of (C) short fibers is 0.01 to 15 mm,
(4) (C) The pneumatic tire according to any one of (1) to (3), wherein an average diameter of the short fibers is 0.1 μm to 0.2 mm,
(5) The pneumatic tire according to any one of the above (1) to (4), wherein the melting point of (C) short fibers is 200 ° C. or higher.
(6) The pneumatic tire according to any one of (1) to (5), wherein (C) the short fiber is a polyketone short fiber,
(7) The pneumatic tire according to any one of (1) to (6), wherein (C) the short fibers are oriented in the circumferential direction of the tire,
(8) (C) When the short fibers are oriented in the tire circumferential direction, the dynamic elastic modulus in the tire circumferential direction when measured at a temperature of 150 ° C. and a strain of 1% is E ₁ , Assuming that the elastic modulus is E ₂ , the pneumatic tire according to (7) above, wherein E ₁ is 5 MPa or more and E ₁ / E ₂ is 1.2 or more,

(9) The rubber composition, wherein (B) carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade, ) The pneumatic tire according to any one of
(10) The pneumatic tire according to (9), wherein (B) carbon black is FEF grade grade,
(11) The pneumatic tire according to any one of (1) to (10), wherein in the rubber composition, (A) the rubber component contains an amine-modified conjugated diene polymer.
(12) The pneumatic tire according to (11), wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer,
(13) The pneumatic tire according to (11) or (12), wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.
(14) The pneumatic tire according to (13), 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.
(15) 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. (14) the pneumatic tire according to
(16) The pneumatic tire according to (15), wherein the conjugated diene polymer is polybutadiene,
(17) The pneumatic tire according to any one of (14) to (16), wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane,
(18) The pneumatic tire according to any one of (1) to (17), wherein the rubber composition is used for a side reinforcing layer,
(19) The pneumatic tire according to any one of (1) to (17), wherein the rubber composition is used for the bead filler, and (20) the rubber composition for the side reinforcing layer and the bead filler. The pneumatic tire according to any one of the above (1) to (17),
Is to provide.

  According to the present invention, by using a rubber composition having a specific property, particularly for the side reinforcing layer and / or the bead filler, run-flat durability can be greatly improved without impairing riding comfort during normal driving. A pneumatic tire can be provided.

[Pneumatic tire]
First, the pneumatic tire of the present invention will be described below with reference to the drawings. Drawing 1 is a mimetic diagram showing the section of one embodiment of the pneumatic tire of the present invention.
In FIG. 1, a preferred embodiment of the pneumatic tire according to the present invention is toroidally connected between a pair of beadcos 1, 1 ′ (1 ′ is not shown), and both ends of the bead core 1 are connected to the outside from the inside of the tire. 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 carcass layer 2 to form an airtight film, and the carcass extending from one bead core 1 to the other bead core 1 ′. The bead filler 7 disposed between the body layer 2 main body portion and the winding portion wound up on the bead core 1, and the carcass layer 2 extending from the side portion of the bead filler 7 to the shoulder region 10 in the side region of the carcass layer. 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 according to the present invention for the side reinforcing layer 8 and / or the bead filler 7 of the pneumatic tire, the pneumatic tire of the present invention can exhibit the above-described effects.

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

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

Examples of the protic amino group include at least one selected from a primary amino group, a secondary amino group, and salts thereof.
On the other hand, examples of the amino group protected with a detachable group include N, N-bis (trihydrocarbylsilyl) amino group and N- (trihydrocarbylsilyl) imino group. Preferably, the hydrocarbyl group is carbon. The trialkylsilyl group which is a C1-C10 alkyl group can be mentioned, Especially preferably, a trimethylsilyl group can be mentioned.
An example of a primary amino group protected with a detachable group (also referred to as a protected primary amino group) is N, N-bis (trimethylsilyl) amino group, which is protected with a detachable group. Examples of the secondary amino group include N- (trimethylsilyl) imino group. The N- (trimethylsilyl) imino group-containing group may be an acyclic imine residue or a cyclic imine residue.

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

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

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

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

  As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl. Examples include lithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, and reactive organisms of diisopropenylbenzene and butyllithium. Of these, n-butyllithium is particularly preferred.

On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, and lithium disulfide. Heptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, from the viewpoint of the interaction effect on carbon black and the ability to initiate polymerization, cyclic hexaamides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable, In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.
In general, these lithium amide compounds prepared from a secondary amine and a lithium compound can be used for polymerization, but can also be prepared in a polymerization system (in-situ). The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

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

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, 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, oxolanylpropane oligomers [especially those containing 2,2-bis (2-tetrahydrofuryl) -propane, etc.], triethylamine, pyridine N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, ethers such as 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium tert-amylate and potassium tert-butoxide, and sodium salts such as sodium tert-amylate can also be used.

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

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

Moreover, as a modifier, N-methyl-N-trimethylsilylaminopropyl (methyl) dimethoxysilane, N-methyl-N-trimethylsilylaminopropyl (methyl) diethoxysilane, N-trimethylsilyl (hexamethyleneimin-2-yl) Propyl (methyl) dimethoxysilane, N-trimethylsilyl (hexamethyleneimin-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (pyrrolidin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (pyrrolidine- 2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) diethoxysila N-trimethylsilyl (imidazol-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (imidazol-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) ) Alkoxysilane compounds having protected secondary amino groups such as propyl (methyl) dimethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) propyl (methyl) diethoxysilane; N- (1,3 -Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxy Silyl) -1-propanamine, N- (1-methylpropiyl) Den) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) Alkoxysilane compounds having an imino group such as -3- (triethoxysilyl) -1-propanamine; 3-dimethylaminopropyl (triethoxy) silane, 3-dimethylaminopropyl (trimethoxy) silane, 3-diethylaminopropyl (triethoxy) Silane, 3-diethylaminopropyl (trimethoxy) silane, 2-dimethylaminoethyl (triethoxy) silane, 2-dimethylaminoethyl (trimethoxy) silane, 3-dimethylaminopropyl (diethoxy) methylsilane, 3-dibutylaminopropyl (triethoxy) silane Examples thereof include alkoxysilane compounds having an amino group such as lan.
These modifiers may be used individually by 1 type, and may be used in combination of 2 or more types. The modifier may be a partial condensate.
Here, the partial condensate means a product in which a part (not all) of the modifier SiOR is SiOSi bonded by condensation.

In the modification reaction with the modifying agent, the amount of the modifying agent used 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) Titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titaniumpropoxyacetylacetonatebis (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 (naphthe Nate) 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-pentandionate), Titanium oxide bis (stearate), Titanium oxide bis (tetramethyl) Heptane dionate), titanium oxide bis (pentanedionate), titanium tetra (lactate) and the like.
Of 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-ethylhexyl) zirconium, zirconium tributoxy Stearate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate Zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium tetrakis (acetylacetonate), zirconium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, Bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexanoate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) Zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, Tetrakis (linolate) zirconium and the like.

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

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

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

The condensation reaction time is usually about 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly.
In addition, the pressure of the reaction system at the time of condensation reaction is 0.01-20 Mpa normally, Preferably it is 0.05-10 Mpa.
There is no restriction | limiting in particular about the format in the case of performing a condensation reaction in aqueous solution, You may carry out by a continuous type using apparatuses, such as a batch type reactor and a multistage continuous type reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.
The primary amino group derived from the modifying agent of the modified conjugated diene polymer of the present invention is generated by performing the deprotection treatment as described above. Specific examples of suitable deprotection treatments other than the solvent removal treatment using steam such as steam stripping described above will be described in detail below.
That is, the protecting group on the primary amino group is converted to a free primary amino group by hydrolysis. By removing the solvent, a modified conjugated diene polymer having a primary amino group can be obtained. In addition, the deprotection treatment of the protected primary amino group derived from the modifier can be performed as necessary in any stage from the step including the condensation treatment to the solvent removal to the dry polymer.

<Modified conjugated diene polymer>
The modified conjugated diene polymer thus obtained has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of preferably 10 to 150, more preferably _{15 to} 100. When the Mooney viscosity is less than 10, sufficient rubber physical properties such as fracture resistance characteristics cannot be obtained.
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 physical properties of the resulting reinforced rubber component, 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 obtained reinforcing rubber component. Therefore, the preferable amount of the carbon black is 55 to 70 parts by mass, and more preferably 60 to 70 parts by mass.
As the carbon black, in order for the vulcanized rubber properties of the obtained reinforcing rubber component to satisfy the above vulcanized rubber properties, the FEF grade, FF grade, HAF grade grade, ISAF grade grade and SAF grade grade can be used. It is preferable to use at least one selected from among them, and the FEF grade grade is particularly preferable.

(Properties of reinforced rubber component)
In the rubber composition according to the present invention, the reinforcing rubber component containing the rubber component (A) and the carbon black (B) has a vulcanized rubber physical property and an elastic modulus at 100% elongation (M100) of 10 MPa or more. Is required. 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 reinforced rubber component at 160 ° C. for 12 minutes.

Further, as the physical properties of the vulcanized rubber, the Σ value [Σ tan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of the loss tangent tan δ needs to be 6.0 or less. When the sigma value of tan δ exceeds 6.0, the heat generation of the tire during run-flat running is large, and the run-flat running durability of the tire is lowered. The lower limit of Σtan δ (28 to 150 ° C.) is not particularly limited, but is usually about 5.
The Σtanδ (28 to 150 ° C.) is a value measured by the following method.
<Measuring method of Σtan δ (28 to 150 ° C.)>
A sheet having a width of 5 mm and a length of 40 mm was cut out from a slab sheet having a thickness of 2 mm obtained by vulcanizing the reinforcing rubber component at 160 ° C. for 12 minutes to prepare a sample. About this sample, the loss tangent tan δ is measured under the measurement conditions of a distance between chucks of 10 mm, an initial strain of 200 μm, a dynamic strain of 1%, a frequency of 52 Hz, and a measurement start temperature of 25 to 200 ° C. using a spectrometer manufactured by Ueshima Seisakusho. As shown in FIG. 2, the relationship between 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.).

((C) Short fiber)
In the rubber composition according to the present invention, short fibers are blended as the component (C) with respect to the above-described reinforcing rubber component. The short fiber of the component (C) is used in order to further improve the run flat durability without impairing the riding comfort during normal running.

(1) Material of short fiber The material of the short fiber may be either an organic fiber or an inorganic fiber. However, a material having a melting point of 200 ° C. or higher and a higher melting point is preferable, and a material that does not melt is particularly preferable. In general, during run-flat running, the side reinforcing rubber layer is one of the parts where the temperature rises the most. When a low melting point material is used, the side reinforcing rubber layer melts and becomes a fracture nucleus in the side reinforcing rubber layer. Although it may be lowered, the use of fibers having a melting point of 200 ° C. or higher can suppress the generation of such fracture nuclei and improve the run-flat durability.
The short fiber is, for example, a natural polymer fiber such as cotton, rayon, or cellulose; a synthetic organic polymer fiber such as aliphatic polyamide, Yoshiharu polyamide, polyester, polyvinyl alcohol, polyimide, aliphatic polyketone, or carbon fiber; glass fiber or the like. Inorganic fibers and the like can be mentioned, and one or more kinds of fibers selected from these can be mixed and used. Among these, aromatic polyamide (melting point: 400 to 570 ° C.) is preferable because it has a high elastic modulus at a high temperature and has a large effect of improving the run-flat durability of the tire.
In addition, by using a rubber composition containing polyketone short fibers having specific heat shrinkage stress and elastic modulus for the side reinforcing rubber layer, the normal running performance at the time of filling with internal pressure is high, so that the conventional side reinforcing type safety tire can be used. To provide a pneumatic safety tire that is lighter in weight, generates less heat from the side reinforcing rubber layer, and can sufficiently maintain the rigidity of the side wall during run-flat running, thus greatly improving run-flat running performance. Can do.
In addition, the measuring method of melting | fusing point is based on the melting temperature measuring method by DSC described in JISK7121-1987.

<Polyketone short fiber>
In the present invention, polyketone short fibers are represented by the following formulas (I) and (II):
σ ≧ −0.01 × E + 1.2 (I)
σ ≧ 0.02 (II)
[Wherein σ is heat shrinkage stress (cN / dtex) at 177 ° C .; E is elastic modulus (cN / dtex) at 49 N load at 25 ° C.] It is preferable to use a rubber composition. Since the polyketone short fibers have a high heat shrinkage stress at high temperature, that is, at 177 ° C., the side reinforcing rubber layer can sufficiently retain the rigidity during run flat running. Therefore, the run flat durability of the safety tire can be greatly improved by applying a rubber composition containing polyketone short fibers satisfying the above formulas (I) and (II) to the side reinforcing rubber layer. In addition, by applying the polyketone short fiber-containing rubber composition to the side reinforcing rubber layer, the run flat durability can be greatly improved, so the side reinforcing rubber layer is made thin while ensuring sufficient run flat durability. As a result, the weight of the safety tire can be reduced, and the heat generation of the side reinforcing rubber layer can be suppressed.

  If the heat shrinkage stress σ at 177 ° C. of the polyketone short fiber is less than 0.02 cN / dtex, the rigidity of the side reinforcing rubber layer 6 during run flat running (at high temperature) cannot be secured. Sex is reduced. Moreover, when the polyketone short fiber which does not satisfy | fill the relationship of Formula (I) will be used, since the rigidity of a side wall part at the time of normal temperature will also become low, it will become difficult to reduce the weight of side reinforcement rubber.

［式中、Ａは不飽和結合によって重合された不飽和化合物由来の部分であり、各繰り返し単位において同一でも異なっていてもよい］で表される繰り返し単位から実質的になるポリケトンの短繊維であることが好ましい。
また、該短繊維の原料のポリケトンの中でも、繰り返し単位の９７モル％以上が１−オキソトリメチレン［−ＣＨ₂−ＣＨ₂−ＣＯ−］であるポリケトンが好ましく、９９モル％以上が１−オキソトリメチレンであるポリケトンが更に好ましく、１００モル％が１−オキソトリメチレンであるポリケトンが最も好ましい。 This polyketone short fiber has the following general formula (III)

[In the formula, A is a portion derived from an unsaturated compound polymerized by an unsaturated bond, and may be the same or different in each repeating unit]. Preferably there is.
Further, among the polyketone as the raw material of the short fiber, a polyketone in which 97 mol% or more of the repeating unit is 1-oxotrimethylene [—CH ₂ —CH ₂ —CO—] is preferable, and 99 mol% or more is 1-oxo. A polyketone that is trimethylene is more preferred, and a polyketone in which 100 mol% is 1-oxotrimethylene is most preferred.

The polyketone as the raw material of the above polyketone short fiber may be partially bonded with ketone groups or with portions derived from unsaturated compounds, but with portions derived from unsaturated compounds and ketone groups alternately arranged. Is preferably 90% by mass or more, more preferably 97% by mass or more, and most preferably 100% by mass.
As the degree of polymerization of this polyketone, the intrinsic viscosity using hexafluoroisopropanol as a solvent is preferably in the range of 1 to 20 dL / g, and more preferably in the range of 2 to 10 dL / g.

  In the formula (III), the unsaturated compound forming 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, methyl methacrylate, vinyl acetate, acrylamide, hydroxyethyl methacrylate, undecenoic acid, undecenol, 6-chlorohexene, N-vinylpyrrolidone, diethyl ester of sulphonylphosphonic acid , A compound containing an unsaturated bond, such as sodium styrenesulfonate, sodium allylsulfonate, vinylpyrrolidone, and vinyl chloride.

(2) Shape of short fiber In this invention, it is preferable that the average fiber length of the said short fiber is 0.01-15 mm. If this average fiber length is in the above range, the yield at the time of cutting is good, the dispersibility of the short fibers in the rubber composition is good, and the short fibers serve as the fracture nuclei, resulting in the fracture characteristics of rubber. It can suppress that it falls. A more preferable average fiber length is in the range of 0.5 to 5 mm.
Moreover, it is preferable that the average diameter of the said short fiber exists in the range of 0.1 micrometer-0.2 mm. If this average diameter is in the above range, both the spinnability and the strength of the vulcanized rubber are good. A more preferable average diameter is in the range of 0.1 μm to 0.025 mm.
In addition, the average length and average diameter of the short fiber are values measured by the following method.
<Measuring method of average length and average diameter of short fiber>
In the short fiber group to be measured, 200 places are selected at random, the diameter and length are measured with an optical microscope, and the respective layered average values are obtained.

(3) Orientation of short fibers in the rubber composition In the rubber composition according to the present invention, the short fibers are preferably oriented in the circumferential direction of the tire. With such an orientation, run-flat durability can be improved without impairing riding comfort during normal driving. Here, assuming that the dynamic elastic modulus in the tire circumferential direction when measured at a temperature of 150 ° C. and a strain of 1% is E ₁ , and the dynamic elastic modulus in the tire radial direction is E ₂ , “the short fiber is in the circumferential direction of the tire. “Oriented” means that E ₁ is higher than E ₂ .
In addition, when the short fibers are oriented in the circumferential direction of the tire as described above, E ₁ is 5 MPa or more and E ₁ / E from the viewpoint of improving the run-flat durability without impairing the ride comfort. ₂ is preferably 1.2 or more.
The E ₁ is more preferably 7 MPa or more, and the upper limit thereof is not particularly limited, but is preferably 20 MPa or less. On the other hand, E ₁ / E ₂ is more preferably 1.5 or more, and the upper limit thereof is not particularly limited, but is preferably 3 or less, more preferably 2 or less.
Incidentally, the E ₁ and E ₂ is a value measured by the following method.
<Measurement method of E ₁ and E _2>
For example, a side reinforcing rubber layer is cut out from the test tire and made into a thickness of about 1 mm with a slicer, and then the dynamic elastic modulus E ₁ in the tire circumferential direction and the tire radial direction (radial direction) is measured with a dynamic viscoelasticity measuring device. And E ₂ are measured respectively. Measurement conditions are strain: 1%, frequency: 50 Hz, temperature: 150 ° C.
When preparing the rubber composition, the short fibers are usually oriented in the direction along the extrusion direction. Therefore, by appropriately adjusting the extrusion conditions of the rubber member such as the side reinforcing rubber layer and the bead filler, a desired E _{A 1} / E ₂ value can be obtained. Further, the E ₁ / E ₂ value can be lowered by stretching the extruded rubber member at right angles to the extrusion direction.

  In the rubber composition according to the present invention, the amount of the short fiber of the component (C) is the above-mentioned (A) from the viewpoint of further improving the run flat durability without impairing the riding comfort during normal running. The amount is preferably 1 to 20 parts by mass and more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the rubber component.

(Optional component)
In the rubber composition according to the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an anti-aging agent, as long as the effects of the present invention are not impaired. Further, a scorch inhibitor, zinc white, stearic acid, and the like can be contained.
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.

(Preparation of rubber composition, production of pneumatic tire)
The rubber composition according to the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer or the like according to the above compounding prescription, vulcanized after molding, and in FIG. Used as a side reinforcing layer 8 and / or a bead filler 7 of a pneumatic tire.
The tire of the present invention is manufactured by a normal method for manufacturing a run-flat tire using the rubber composition according to the present invention for the side reinforcing layer 8 and / or the bead filler 7. That is, as described above, the rubber composition according to the present invention containing various chemicals is processed into each member at an unvulcanized stage, and pasted and molded by a normal method on a tire molding machine, and a raw tire is molded. Is done. The green tire is heated and pressed in a vulcanizer to obtain a tire.
The pneumatic tire of the present invention thus obtained has improved run flat durability without impairing riding comfort during normal running.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various characteristics were measured according to the following methods.
<< Physical Properties of Unmodified or Modified Conjugated Diene Polymer >>
<Microstructure analysis method>
The vinyl bond content (%) was measured by an infrared method (Morero method).
<Measurement of Number Average Molecular Weight (Mn), Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw / Mn)>
It measured using GPC [the Tosoh make, HLC-8020] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as the standard. The column is GMHXL [manufactured by Tosoh], and the eluent is tetrahydrofuran.

<Measurement of primary amino group content (mmol / kg)>
First, the polymer was dissolved in toluene, and then the amino group-containing compound not bound to the polymer was separated from the rubber by precipitation in a large amount of methanol, followed by drying. Using this treated polymer as a sample, the total amino group content was quantified by the “total amine value test method” described in JIS K7237. Subsequently, the contents of secondary amino groups and tertiary amino groups were quantified by the “acetylacetone blocked method” using the polymer subjected to the above treatment as a sample. As a solvent for dissolving the sample, o-nitrotoluene was used, acetylacetone was added, and potentiometric titration was performed with a perchloracetic acid solution. The primary amino group bound to the polymer by subtracting the secondary amino group content and tertiary amino group content from the total amino group content to determine the primary amino group content (mmol) and dividing by the polymer mass used in the analysis. The content (mmol / kg) was determined.

<Physical properties of vulcanized rubber for reinforcing rubber components>
The Σ value [Σ tan δ (28 to 150 ° C.)] at 28 ° C. to 150 ° C. of the 100% stretch modulus (M100) and loss tangent tan δ was measured according to the method described in the specification.
<< Evaluation of pneumatic tire >>
<Runflat durability>
Each test tire (passenger car radial tire with tire size 215 / 45ZR17) is assembled with rims at normal pressure, filled with 230 kPa of internal pressure, left in a room at 38 ° C. for 24 hours, then the valve core is removed to increase the internal pressure. The drum running test was performed under the conditions of a pressure of 4.17 kN (425 kg), a speed of 89 km / h, and an indoor temperature of 38 ° C. as atmospheric pressure. 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
<Longitudinal spring constant of tire during internal pressure filling (riding comfort)>
The rim was assembled with a rim conforming to JATMA, adjusted to a compliant air pressure, and then the tire was mounted on a load device (static characteristic testing machine Amsler). A vertical load is applied at a speed where the amount of change in the diameter direction of the tire is 50 mm / min, the vertical deflection with respect to the load is measured, and the vertical spring constant (N / mm) is determined by differentiation at a certain load value in the regression equation. Asked. The longitudinal spring constant of the tire was indicated as an index with the tire of Comparative Example 1 as 100. The smaller the index value, the smaller the vertical spring of the tire, and the better the ride comfort.
<E ₁ and E _2>
The dynamic elastic modulus E _{1 in} the tire circumferential direction and the dynamic elastic modulus E ₂ in the tire radial direction were measured according to the methods described in the specification.

Production Example 1 Production of primary amine-modified polybutadiene (1) Polybutadiene In a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, 2,2-ditetrahydrofurylpropane (0.0285 mmol) cyclohexane under nitrogen. The solution was injected as a solution, and 2.85 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. The polymer solution was drawn into a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping and dried with a roll at 110 ° C. Thus, polybutadiene was obtained. The resulting polybutadiene was measured for microstructure (vinyl bond amount), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn). As a result, the vinyl bond content was 14%, Mw was 150,000, and Mw / Mn was 1.1.
(2) Production of primary amine-modified polybutadiene The polymer solution obtained in (1) above is maintained at a temperature of 50 ° C. without deactivating the polymerization catalyst, and the primary amino group protected N, N-bis ( 1129 mg (3.364 mmol) of trimethylsilyl) aminopropylmethyldiethoxysilane was added and the modification reaction was carried out for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the primary amino group, which was desolvated and protected by steam stripping, was removed, and the rubber was dried with a ripening roll adjusted to 110 ° C. to obtain primary amine-modified polybutadiene. The resulting modified polybutadiene was measured for microstructure (vinyl bond amount), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and primary amino group content. As a result, the vinyl bond content was 14%, Mw was 150,000, Mw / Mn was 1.2, and the primary amino group content was 4.0 mmol / kg.

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

Examples 1-8 and Comparative Examples 1-4
Twelve types of rubber compositions having the composition shown in Table 1 were prepared, and the vulcanized rubber properties of the reinforcing rubber component, that is, M100 and Σtan δ (28 to 150 ° C.) were determined.
Next, these 12 kinds of rubber compositions are disposed on the side reinforcing layer 8 and the bead filler 7 shown in FIG. 1, and radial tires for passenger cars having tire sizes of 215 / 45ZR17 are manufactured according to a standard method. The run-flat durability and the longitudinal spring constant (riding comfort) during internal pressure filling were evaluated. The results are shown in Table 1. The elastic modulus at 100% elongation (M100) in Table 1 is the value in the rubber composition before blending the short fibers (that is, the rubber composition containing no short fibers).
The ratio between the dynamic elastic modulus E _{1 in the} tire circumferential direction and the dynamic elastic modulus E _{2 in the} tire radial direction by stretching the side reinforcing layer and the bead filler rubber member after extrusion at right angles to the extrusion direction. The E ₁ / E ₂ value was set to 1.

［注］
１）天然ゴム：ＴＳＲ２０
２）未変性ポリブタジエン：ＪＳＲ社製ＢＲ０１
３）一級アミン変性ポリブタジエン：製造例１で得られたもの
４）カーボンブラック：ＦＥＦ（Ｎ５５０）、旭カーボン社製「旭＃６０」
５）短繊維
（Ｉ）；アラミド短繊維、平均長さ：１．０ｍｍ、平均直径：１７μｍ、分解温度：５００℃、１７７℃熱収縮応力：０ｃＮ／ｄｔｅｘ、ディップ処理：有
（II）；ポリケトン短繊維、平均長さ：２．０ｍｍ、平均直径：１０μｍ、融点：２５０℃、１７７℃熱収縮応力：０．７ｃＮ／ｄｔｅｘ、ディップ処理：有
６）プロセスオイル：アロマティックオイル、富士興産社製「アロマックス＃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「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「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「ノクセラーＴＯＴ−Ｎ」
１０）ＤＭＢＴＥＳＰＡ変性ポリブタジエン：製造例２で得られたもの
第１表から分かるように、本発明の空気入りタイヤ（実施例１〜８）は、比較例１〜４の空気入りタイヤにほぼ匹敵する乗り心地性を有すると共に、ランフラット耐久性が、比較例１〜４のものに比べて、大幅に向上している。

[note]
1) Natural rubber: TSR20
2) Unmodified polybutadiene: BR01 manufactured by JSR
3) Primary amine-modified polybutadiene: obtained in Production Example 1 4) Carbon black: FEF (N550), “Asahi # 60” manufactured by Asahi Carbon Co., Ltd.
5) Short fiber (I); aramid short fiber, average length: 1.0 mm, average diameter: 17 μm, decomposition temperature: 500 ° C., 177 ° C. heat shrinkage stress: 0 cN / dtex, dip treatment: yes (II); polyketone Short fiber, average length: 2.0 mm, average diameter: 10 μm, melting point: 250 ° C., 177 ° C. heat shrinkage stress: 0.7 cN / dtex, dip treatment: yes 6) Process oil: aromatic oil, manufactured by Fuji Kosan Co., Ltd. "Aromax # 3"
7) Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
8) Vulcanization accelerator DZ: N, N′-dicyclohexyl-2-benzothiazylsulfenamide, “Noxeller DZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
9) Vulcanization accelerator TOT: Tetrakis (2-ethylhexyl) thiuram disulfide, “Noxeller TOT-N” manufactured by Ouchi Shinsei Chemical Co., Ltd.
10) DMBTESPA modified polybutadiene: obtained in Production Example 2 As can be seen from Table 1, the pneumatic tires (Examples 1 to 8) of the present invention are almost equivalent to the pneumatic tires of Comparative Examples 1 to 4. While having ride comfort, the run-flat durability is significantly improved as compared with those of Comparative Examples 1 to 4.

Examples 9-16
Eight types of rubber compositions having the compounding compositions shown in Table 2 were prepared, and the vulcanized rubber properties of the reinforcing rubber component, that is, M100 and tan δ (28 to 150 ° C.) were determined.
Next, these eight kinds of rubber compositions are disposed on the side reinforcing layer 8 and the bead filler 7 shown in FIG. 1, and radial tires for passenger cars having tire sizes 215 / 45ZR17 are manufactured according to a standard method. The run-flat durability and the longitudinal spring constant (riding comfort) during internal pressure filling were evaluated.
Further, to measure the dynamic modulus of elasticity E ₂ of the tire circumferential direction of the dynamic elastic modulus E ₁ and the tire radial direction, it was determined E ₁ / E _2. In the production of the radial tire, when the rubber composition was attached to the raw tire, it was attached so that the orientation direction of the short fibers in the rubber composition was the tire circumferential direction (preparing the rubber composition). In this case, since the short fibers are usually oriented in the direction along the extrusion direction, it is possible to apply the short fibers in the tire circumferential direction). In each example, the extrusion conditions were adjusted, and the rubber member after extrusion was further stretched in the tire circumferential direction as necessary to obtain the desired E ₁ / E ₂ .
These results are shown in Table 2. The elastic modulus at 100% elongation (M100) in Table 2 is a value in the rubber composition before blending the short fibers (that is, the rubber composition containing no short fibers).

［注］
１）〜１０）は、前記第１表の脚注と同じである。
第１表の実施例１〜８と、第２表の実施例９〜１６とを比較して分かるように、実施例９〜１６は、Ｅ₁／Ｅ₂が１．５を超え、周方向配向で高い異方性を有し、通常走行時の乗り心地性を損なうことなく、ランフラット耐久性が、さらに向上している。

[note]
1) to 10) are the same as the footnotes in Table 1 above.
As can be seen by comparing Examples 1 to 8 in Table 1 and Examples 9 to 16 in Table 2, Examples 9 to 16 have an E ₁ / E ₂ exceeding 1.5, and the circumferential direction The run flat durability is further improved without losing the riding comfort during normal running, having high anisotropy in orientation.

  The pneumatic tire of the present invention significantly improves run-flat durability without impairing riding comfort during normal running by using a rubber composition having specific properties for the side reinforcing layer and the bead filler. be able to.

It is a mimetic diagram showing the section of one 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.

Explanation 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 reinforcing layer 10 shoulder area

Claims (20)

  A pneumatic tire comprising a bead core, a carcass layer, a tread rubber layer, an inner liner, a side reinforcing layer, and a bead filler, wherein (A) rubber component and 100 parts by mass thereof, (B) 55 parts by mass of carbon black In addition to the above, and in the vulcanized rubber properties, a reinforced rubber component having an elastic modulus at 100% elongation (M100) of 10 MPa or more and a loss tangent tan δ of 28 ° C. to 150 ° C. having a Σ value of 6.0 or less, C) A pneumatic tire using a rubber composition containing short fibers.   The pneumatic tire according to claim 1, wherein the blending amount of (C) short fibers is 1 to 20 parts by mass with respect to 100 parts by mass of (A) rubber component.   (C) The pneumatic tire according to claim 1 or 2, wherein an average fiber length of the short fibers is 0.01 to 15 mm.   (C) The pneumatic tire according to any one of claims 1 to 3, wherein the short fibers have an average diameter of 0.1 µm to 0.2 mm.   (C) Melting | fusing point of a short fiber is 200 degreeC or more, The pneumatic tire in any one of Claims 1-4.   (C) The short fiber is a polyketone short fiber, The pneumatic tire according to any one of claims 1 to 5.   (C) The pneumatic tire according to any one of claims 1 to 6, wherein the short fibers are oriented in a circumferential direction of the tire. (C) When short fibers are oriented in the circumferential direction of the tire, the dynamic elastic modulus in the tire circumferential direction when measured at a temperature of 150 ° C. and a strain of 1% is E ₁ , and the dynamic elastic modulus in the radial direction of the tire When the the E _2, pneumatic tire according to claim 7 E ₁ together with at 5MPa or more, E ₁ / E ₂ 1.2 or more.   9. The rubber composition according to claim 1, wherein (B) carbon black is at least one selected from FEF grade, FF grade, HAF grade, ISAF grade and SAF grade. Pneumatic tires.   The pneumatic tire according to claim 9, wherein (B) carbon black is FEF grade grade.   The pneumatic tire according to any one of claims 1 to 10, wherein (A) the rubber component contains an amine-modified conjugated diene polymer in the rubber composition.   The pneumatic tire according to claim 11, wherein the amine-modified conjugated diene polymer is a protic amine-modified conjugated diene polymer.   The pneumatic tire according to claim 11 or 12, wherein the amine-modified conjugated diene polymer is a primary amine-modified conjugated diene polymer.   The pneumatic tire according to claim 13, 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 15, wherein the conjugated diene polymer is polybutadiene.   The pneumatic tire according to any one of claims 14 to 16, wherein the protected primary amine compound is N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane.   The pneumatic tire according to claim 1, wherein the rubber composition is used for a side reinforcing layer.   The pneumatic tire according to claim 1, wherein the rubber composition is used for a bead filler.   The pneumatic tire according to any one of claims 1 to 17, wherein the rubber composition is used for a side reinforcing layer and a bead filler.

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