JP5756248B2 - tire - Google Patents

Description

  The present invention relates to a tire, particularly a pneumatic tire, which is excellent in handling stability on a wet road surface and has good fuel efficiency, ice / snow performance and wear resistance by using a specific rubber composition as a tread.

In recent years, due to social demands for energy saving, demands for lower fuel consumption of automobiles are becoming more severe. In order to meet such demands, a reduction in rolling resistance has also been demanded for tire performance. As a technique for reducing the rolling resistance of a tire, a technique by optimizing the tire structure has been studied, but the most common technique is to use a material with less heat generation as a rubber composition.
In order to obtain such a rubber composition with low heat generation, many technical developments have been made so far to improve the dispersibility of the filler used in the rubber composition. Among them, a method of modifying a polymerization active site of a diene polymer obtained by anionic polymerization using a lithium compound with a functional group that interacts with a filler is the most common.
The most representative of such methods is a method in which carbon black is used as a filler and a polymerization active site is modified with a tin compound (see, for example, Patent Document 1). Similarly, carbon black is used in an active terminal. For example, a method of introducing an amino group into the lignin (see, for example, Patent Document 2) is known.

  Further, in order to improve the performance of snow and snow, a technique for lowering the rigidity in a low temperature region (here, the low temperature region is a temperature during running on ice and snow, which is about −20 to 0 ° C.) is adopted. As the rubber component to be used, natural rubber having a glass transition temperature of −60 ° C. or less, high cis polybutadiene, and the like are used. In particular, high cis polybutadiene has a low glass transition temperature, and by increasing the ratio of high cis polybutadiene in the rubber component, the snow and snow performance improves, but the handling stability on wet road surfaces, especially the braking performance on wet road surfaces, decreases. There is a problem of doing.

However, in recent years, with increasing interest in safety of automobiles, there has been an increasing demand for wet performance. For this reason, the performance requirements for the rubber composition of the tire tread are not limited to the improvement of fuel efficiency and ice / snow performance, but are required to satisfy the high driving stability on wet road surfaces.
In addition, there is still a need for ensuring wear resistance.
As a method for obtaining such a rubber composition that imparts good fuel efficiency, ice and snow performance and abrasion resistance, and good wet performance to the tire at the same time, it is obtained by anionic polymerization using alkyl lithium or lithium amide as a polymerization initiator. A modified polymer in which an alkoxysilane having a dialkylamino group is introduced into the active terminal of the obtained polymer is disclosed (for example, see Patent Document 3). When this modified polymer is used, it interacts with both the filler carbon black and silica, so that although a certain improvement effect is obtained, it cannot always be said that it is sufficiently satisfactory.
Furthermore, unvulcanized rubber compositions for tire treads tend to shrink during the extrusion process at the time of tire manufacture. When shrinking, the hot workability in the heating process is reduced and the dimensions of the extruded product are likely to become unstable. Therefore, it is also desired to improve the workability by suppressing the shrinkage.

Japanese Patent Publication No. 5-87630 JP 62-207342 A Japanese Examined Patent Publication No. 6-57767

  Under such circumstances, the present invention provides a tire, particularly a pneumatic tire, which has excellent fuel economy, ice and snow performance, wear resistance, excellent driving stability on wet road surfaces, and good workability. It is intended to do.

As a result of intensive studies to achieve the above object, the present inventor has a rubber component, a thermoplastic resin and a filler, and the rubber component contains a specific modified conjugated diene-aromatic vinyl copolymer and a specific conjugate. A hydrocarbyloxysilane compound containing a diene polymer, wherein the polymerization initiator used in the copolymer is specific, or the modifier used in the copolymer contains a specific nitrogen atom and silicon atom, or It has been found that a hydrocarbyloxysilane compound containing a specific silicon atom can achieve its purpose by combining a conjugated diene-aromatic vinyl copolymer before modification with each modifier. The present invention has been completed based on such findings.
That is, the present invention
[1] A rubber composition containing a rubber component, a thermoplastic resin and a filler, wherein (A) 10 to 60% by mass of a modified conjugated diene-aromatic vinyl copolymer and (B) in the rubber component The conjugated diene polymer is contained in an amount of 90% by mass or less, and the polymerization initiator of the component (A) is a lithium amide compound, or the modifier used at the active terminal of the component (A) contains (C) a nitrogen atom and a silicon atom. A tire comprising a rubber composition which is a hydrocarbyloxysilane compound or (D) a hydrocarbyloxysilane compound containing a silicon atom for a tread;
[2] The conjugated diene compound used as one raw material monomer of the component (A) is 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3. -The tire according to [1], which is at least one selected from butadiene and 2-phenyl-1,3-butadiene,
[3] The tire according to the above [2], wherein the aromatic vinyl compound used as another raw material monomer of the component (A) is styrene.
[4] The tire according to any one of [1] to [3], wherein the glass transition temperature Tg of the modified conjugated diene-aromatic vinyl copolymer of the component (A) is -60 to -20 ° C.
[5] The tire according to [3] or [4] above, wherein the modified conjugated diene-aromatic vinyl copolymer of the component (A) is a modified styrene-butadiene rubber.
[6] The tire according to any one of [1] to [5], wherein the rubber component includes 10 to 90% by mass of the component (B).
[7] The tire according to any one of [1] to [6], wherein a glass transition temperature Tg of the conjugated diene polymer of the component (B) is −110 to −50 ° C.
[8] The tire according to [7], wherein the conjugated diene polymer of the component (B) has a glass transition temperature Tg of -80 to -50 ° C.
[9] The tire according to [7] or [8] above, wherein the conjugated diene polymer of the component (B) is natural rubber and / or polyisoprene rubber.
[10] The conjugated diene compound used as a raw material monomer for the component (B) is 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethyl-1,3-butadiene. The tire according to any one of the above [1] to [8], which is at least one selected from
[11] The tire according to [7] or [10] above, wherein the conjugated diene polymer of the component (B) has a glass transition temperature Tg of −110 ° C. or more and less than −80 ° C.
[12] The conjugated diene polymer of the component (B) is a modified conjugated diene polymer, and a conjugated diene compound alone or other conjugated diene compound in an organic solvent using a catalyst containing a lanthanum series rare earth element-containing compound Is obtained by coordinating anionic polymerization of a conjugated diene polymer having an active terminal and having a cis-1,4 bond content in the conjugated diene moiety of the main chain of 90 mol% or more. The tire according to the above [11], which is obtained by reacting a hydrocarbyloxysilane compound of a certain component (C) or component (D),
[13] The tire according to [7], [10], [11] or [12], wherein the modified conjugated diene polymer is a modified polybutadiene rubber.
[14] The tire according to any one of [1] to [13], wherein the rubber component includes 40% by mass or less of the component (B).
[15] The hydrocarbyloxysilane compound of the component (C) is represented by the following general formula (I)
[In the formula, A ¹ is a monovalent group having at least one functional group selected from a cyclic tertiary amino group, an acyclic tertiary amino group, an isocyanate group, a thioisocyanate group, an imine residue, and a pyridine residue; ¹ is a single bond or a divalent inert hydrocarbon group, R ² and R ³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aliphatic group having 6 to 18 carbon atoms. an aromatic hydrocarbon group, n is an integer from 0 to 2, if the oR ³ there are a plurality, the plurality of oR ³ may be the same or different and active proton and onium salt in the molecule include I can't. ]
The tire according to any one of the above [1] to [14], which is at least one selected from a hydrocarbyloxysilane compound represented by formula (1) and a partial condensate thereof,
[16] The hydrocarbyloxysilane compound of the component (D) is represented by the following general formula (II)
[Wherein, R ⁴ and R ⁵ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; an integer 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ may be the same as or different from each other, also in the molecule does not include an active proton and an onium salt. And a partial condensate thereof, and the following general formula (III)
[In the formula, A ² represents an epoxy group, a thioepoxy group, a ketone group, a thioketone group, an aldehyde group, a thioaldehyde group, an isocyanuric acid trihydrocarbyl ester residue, a carboxylic acid ester residue, a thiocarboxylic acid ester residue, a carboxylic acid anhydride. residues, monovalent group having at least one functional group selected from carboxylic acid halide residue and carbonate dihydrocarbyl ester residue, R ⁶ is a single bond or a divalent inactive hydrocarbon group, R ⁷ And R ⁸ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, m is an integer of 0 to 2, If oR ⁸ there are a plurality, the plurality of oR ⁸ may be the same or different, and in the molecule does not include an active proton and an onium salt. The tire according to any one of the above [1] to [14], which is at least one selected from a hydrocarbyloxysilane compound represented by the above and a partial condensate thereof,
[17] The hydrocarbyloxysilane compound of the component (C) is a bifunctional compound in which a primary amino group is protected in the molecule and one hydrocarbyloxy group and one reactive group are bonded to the same silicon atom. The tire according to any one of the above [1] to [14], which is a compound containing a silicon atom,
[18] The compound containing a bifunctional silicon atom is represented by the general formula (IV)
Wherein R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1 A silicon compound represented by formula (V): an alkylene group of -12, A is a reactive group, and f is an integer of 1-10.
(Wherein R ^{15 to} R ¹⁹ each independently represents a hydrocarbon group having 1 to ²⁰ carbon atoms, and R ²⁰ represents an alkylene group having 1 to 12 carbon atoms) and a general formula ( VI)
Wherein R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1 -12 alkylene group, R ²¹ is an alkylene group having 1 to 12 carbon atoms, A is a reactive group, and f is an integer of 1 to 10). A tire according to [17] above,
[19] The tire according to the above [18], wherein the reactive group A in the general formula (IV) or the general formula (VI) is a halogen atom or an alkoxy group having 1 to 20 carbon atoms.
[20] The tire according to any one of [1] to [19], containing 5 to 20 parts by mass of the thermoplastic resin and 50 to 100 parts by mass of the filler, with respect to 100 parts by mass of the rubber component.
[21] The tire according to any one of [1] to [20], wherein a softening point of the thermoplastic resin is 50 to 150 ° C.
[22] Any of the above [1] to [21], wherein the thermoplastic resin is at least one selected from an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, a terpene resin, and a terpene phenol resin. Tires described in the
[23] The tire according to any one of [1] to [22], wherein the filler is carbon black and / or silica, and [24] the filler is carbon black and silica, and carbon. The tire according to any one of [1] to [23], wherein the content ratio of black and silica is (10:90) to (50:50) in terms of mass ratio.

  According to the present invention, a rubber composition obtained by blending a specific modified conjugated diene-aromatic vinyl copolymer, a specific conjugated diene polymer, carbon black, and a specific thermoplastic resin in a predetermined ratio is used as a tread. By using the tire, the fuel efficiency, the snow and snow performance and the wear resistance are good, the driving stability on a wet road surface (hereinafter referred to as “wet performance”) is excellent, and the workability is good, particularly a pneumatic tire. Can be provided.

[tire]
The tire of the present invention is a rubber composition containing a rubber component, a thermoplastic resin, and a filler, and the rubber component contains (A) a modified conjugated diene-aromatic vinyl copolymer in an amount of 10 to 60% by mass and (B) The conjugated diene polymer is contained in 90% by mass or less, and the polymerization initiator of the component (A) is a lithium amide compound, or the modifier used at the active terminal of the component (A) is (C) a nitrogen atom and silicon. A rubber composition which is a hydrocarbyloxysilane compound containing an atom or (D) a hydrocarbyloxysilane compound containing a silicon atom is used for a tread.

[Rubber composition]
The rubber composition used in the tread of the tire of the present invention contains the component (A) in the rubber component, so that the fuel efficiency is greatly improved and the wet performance is improved. Moreover, by including the said (B) component, snow and ice performance, low fuel consumption, and abrasion resistance are improved significantly.
In addition, the polymerization initiator of component (A) is a lithium amide compound, or the modifier used at the active terminal of component (A) is (C) a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom. Further, the dispersibility of the filler such as carbon black and / or silica in the rubber component is improved, and the reinforcing property of the rubber composition is improved. On the other hand, when the modifier used at the active terminal of the component (A) is a hydrocarbyloxysilane compound containing a silicon atom (D), the dispersibility of the filler, particularly silica, in the rubber component is improved. The reinforcing property of the rubber composition is improved.

[Rubber component]
In the rubber component of the rubber composition used for the tread of the tire of the present invention, it is necessary to include 10 to 60% by mass of the component (A), and if it is less than 10% by mass, it becomes difficult to achieve an effect of improving fuel economy. This is because if it exceeds 60% by mass, it is difficult to improve the ice and snow performance.
The glass transition temperature Tg of the modified conjugated diene-aromatic vinyl copolymer that is the component (A) is preferably −60 to −20 ° C. This is because within this range, the fuel economy improvement effect can be suitably enjoyed.
The glass transition temperature Tg of the conjugated diene polymer as the component (B) is preferably −110 to −50 ° C. If it is −110 ° C. or higher, it is easy to produce, and if it is −50 ° C. or lower, the effect of improving snow and snow performance can be more suitably achieved. It is preferable that 10-90 mass% of (B) component is included in a rubber component. This is because the wet performance can be more suitably improved when the content is 90% by mass or less. If it is 10 mass% or more, snow and ice performance, low fuel consumption, and wear resistance can be further improved.
By using such a rubber component, it is possible to obtain a rubber composition for a tire tread that can provide a tire having good wet performance, low fuel consumption, ice / snow performance and wear resistance, particularly a pneumatic tire.

[Component A]
As the conjugated diene compound used as one raw material monomer of the component (A), 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, Examples include 2-phenyl-1,3-butadiene. 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 as another raw material monomer of the component (A) include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexane. Hexylstyrene, 2,4,6-trimethylstyrene and the like can be mentioned. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.
As the modified conjugated diene-aromatic vinyl copolymer as component (A), modified styrene-butadiene rubber (modified SBR) is preferable.

[B component]
The glass transition temperature Tg of the conjugated diene polymer as the component (B) is preferably −80 to −50 ° C. Hereinafter, the component (B) in the range of the glass transition temperature Tg is referred to as “component (B1)”. This is because if the glass transition temperature Tg is within this range, the effect of improving the snow and snow performance is improved. More preferably, the rubber component contains 20 to 90% by mass of the component (B1). This is because if it is 20% by mass or more, the effect of improving ice and snow performance, fuel efficiency and wear resistance is further improved, and if it is 90% by mass or less, the effect of improving wet performance is further improved.
Suitable examples of the conjugated diene polymer as component (B1) include natural rubber and / or polyisoprene rubber (synthetic polyisoprene rubber). For example, the glass transition temperature Tg of natural rubber is −75 ° C., and the glass transition temperature Tg of polyisoprene rubber is −75 ° C. However, the conjugated diene polymer as the component (B1) may be a polybutadiene rubber having a high vinyl bond content obtained by anionic polymerization.

Moreover, it is preferable that the glass transition temperature Tg of the conjugated diene polymer which is (B) component is -110 degreeC or more and less than -80 degreeC. Hereinafter, the component (B) in the range of the glass transition temperature Tg is referred to as “component (B2)”. This is because if the glass transition temperature Tg is within this range, the effect of improving snow and snow performance is further improved. The rubber component preferably contains 40% by mass or less of the component (B2). It is because the improvement effect of wet performance will improve more if (B2) component is 40 mass% or less. In order to enjoy the effects of improving the snow and snow performance, fuel efficiency and wear resistance of the component (B2), the rubber component preferably contains 5% by mass or more of the component (B2), and 10% by mass or more. Is more preferable.
In the rubber composition used for the tread of the tire of the present invention, the rubber component preferably includes both the component (B1) and the component (B2) in order to achieve the effect of the component (B).
As the conjugated diene polymer as the component (B2), polybutadiene rubber is preferably exemplified.

The conjugated diene polymer of the component (B) according to the present invention, particularly the conjugated diene polymer of the component (B2) uses a catalyst containing a lanthanum series rare earth element-containing compound, and the conjugated diene compound alone or other in an organic solvent It is particularly preferred to obtain it by coordination anionic polymerization with a conjugated diene compound. As a result, a conjugated diene polymer having a low glass transition temperature Tg and a cis-1,4 bond content of 90 mol% or more in the conjugated diene portion of the main chain is obtained.
The conjugated diene compound used as a raw material monomer for the component (B) is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethyl-1,3-butadiene. It is preferable that there is at least one.
In addition, the conjugated diene polymer of component (B) according to the present invention, particularly the conjugated diene polymer of component (B2) is the active terminal of the conjugated diene polymer having an active terminal obtained by the coordination anionic polymerization. And a modified conjugated diene polymer obtained by reacting the hydrocarbyloxysilane compound of component (C) or component (D), which is a modifier.
The modified conjugated diene polymer is preferably a modified polybutadiene rubber.

[Polymerization of component (A)]
In the present invention, the active terminal of the conjugated diene-aromatic vinyl copolymer is modified by reacting (C) a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom or (D) a hydrocarbyloxysilane compound containing a silicon atom. For the conjugated diene-aromatic vinyl copolymer, it is preferable that at least 10% of the polymer chains have living property or pseudo-living property. As the polymerization reaction having such living properties, a reaction in which an organic alkali metal compound is used as an initiator and an conjugated diene compound and an aromatic vinyl compound are subjected to anionic polymerization in an organic solvent is preferable. By anionic polymerization, a high conjugated diene moiety vinyl bond content can be obtained, and the glass transition temperature Tg can be adjusted to a desired temperature. Heat resistance can be improved by increasing the vinyl bond content, and fuel efficiency and ice / snow performance can be improved by increasing the cis-1,4 bond content.

  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 or lithium amide compound is 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-aromatic vinyl copolymer as a site is obtained, and (C) the hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom or (D) a hydrocarbyl containing a silicon atom at the active terminal as a polymerization active site The oxysilane compound is reacted and modified.

  When the latter lithium amide compound is used, a conjugated diene-aromatic vinyl copolymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained. In the case of a lithium amide compound, the modified conjugated diene-aromatic vinyl copolymer which is the component (A) according to the present invention can be obtained without modification with the above-described hydrocarbyloxysilane compound, but it is a polymerization active site. When (C) a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom at the active terminal or (D) a hydrocarbyloxysilane compound containing a silicon atom is reacted and modified, so-called double-end modified conjugated diene-aromatic vinyl copolymer It is more preferable because a coalescence is obtained and the dispersibility and reinforcement of the filler such as carbon black and silica can be further enhanced.

  As the hydrocarbyl lithium which is a polymerization initiator, 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-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, reactive organisms of diisopropenylbenzene and butyllithium, etc. Among them, n-butyllithium is particularly preferable among these.

Examples of the lithium amide compound as a polymerization initiator include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium Dipropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, Examples include lithium methylphenethylamide. 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 the polymerization, but they can also be prepared in-polymerization 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-aromatic vinyl copolymer by anionic polymerization using the organolithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, the lithium compound is polymerized with a conjugated diene compound and an aromatic vinyl compound in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound. A conjugated diene-aromatic vinyl copolymer having a target active end can be obtained by anionic polymerization in the presence of a randomizer used as an initiator, if desired.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.
The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. In addition, when copolymerizing using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably 5 to 55% by mass, and more preferably 6 to 45% by mass. .

  The randomizer used as desired is the control of the microstructure of the conjugated diene-aromatic vinyl copolymer, such as 1,2-bond of the butadiene moiety in the butadiene-styrene copolymer, and 3,4-bond in the isoprene polymer. It is a compound having an action such as increase or control of composition distribution of monomer units in a conjugated diene / aromatic vinyl copolymer, such as randomization of butadiene units or 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, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, Examples thereof include ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium t-amylate and potassium t-butoxide, and sodium salts such as sodium t-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.

[Polymerization of component (B)]
The case where the conjugated diene polymer of the component (B) according to the present invention, particularly the conjugated diene polymer of the component (B2), is obtained by coordination anion polymerization using a catalyst containing a lanthanum series rare earth element-containing compound will be described.
The polymerization catalyst containing the lanthanum series rare earth element compound is preferably a combination of at least one compound selected from the following components (x), (y) and (z).

[(X) component]
The rare earth compound selected from the following (x1) to (x4) may be used as it is as an inert organic solvent solution or may be supported on an inert solid.
(X1) a rare earth compound having an oxidation number of 3, a carboxyl group having 2 to 30 carbon atoms, an alkoxy group having 2 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and 1,3-di having 5 to 30 carbon atoms One having a total of three ligands freely selected from carbonyl-containing groups, or a Lewis base compound (in particular, free carboxylic acid, free alcohol, 1,3-diketone, cyclic ether, linear ether, Selected from trihydrocarbyl phosphine, trihydrocarbyl phosphite, and the like. Specific examples include neodymium tri-2-ethylhexanoate, complex compounds thereof with acetylacetone, neodymium trineodecanoate, complex compounds thereof with acetylacetone, neodymium tri-n-butoxide, and the like.
(X2) A complex compound of a rare earth trihalide and a Lewis base. For example, there is a THF complex of neodymium trichloride.
(X3) An organic rare earth compound having an oxidation number of 3 in which at least one (substituted) allyl group is directly bonded to a rare earth atom. For example, there is a salt of tetraallyl neodymium and lithium.
(X4) An organic rare earth compound having an oxidation number of 2 or 3 in which at least one (substituted) cyclopentadienyl group is directly bonded to a rare earth atom, or this compound, a trialkylaluminum or a non-coordinating anion and a counter cation It is a reaction product with an ionic compound. An example is dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) samarium.
As the rare earth element of the rare earth compound, lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and lanthanum, neodymium and samarium are more preferable.
Among the above components (x), neodymium carboxylates and samarium substituted cyclopentadienyl compounds are preferred.

[(Y) component]
A plurality of organoaluminum compounds selected from the following one can be used at the same time.
(Y1) A trihydrocarbylaluminum compound represented by the formula R ²² ₃ A1 (wherein R ²² is a hydrocarbon group having 1 to 30 carbon atoms, which may be the same as or different from each other).
(Y2) Hydrocarbyl aluminum hydride represented by the formula R ²³ ₂ A1H or R ²³ A1H ₂ (wherein R ²³ is a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different from each other).
(Y3) A hydrocarbylaluminoxane compound having a hydrocarbon group having 1 to 30 carbon atoms.
Examples of the component (y) include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used as a mixture. Among the components (y), a combination of an aluminoxane and another organoaluminum compound is preferable.

[(Z) component]
Although it is a compound selected from the following ones, it is not always necessary when (x) contains a halogen or a non-coordinating anion and (y) contains an aluminoxane.
(Z1) An inorganic or organic compound of an element belonging to Group 2 or Group 12-14 of the periodic table (long-period type) having a hydrolyzable halogen, or a complex compound of these with a Lewis base. For example, alkyl aluminum dichloride, dialkyl aluminum chloride, silicon tetrachloride, tin tetrachloride, a complex of zinc chloride and a Lewis base such as alcohol, a complex of magnesium chloride and a Lewis base such as alcohol, and the like.
(Z2) An organic halide having a structure selected from at least one tertiary alkyl halide, benzyl halide, and aryl halide. For example, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide and the like.
(Z3) A zinc halide or a complex compound of this with a Lewis base.
(Z4) An ionic compound comprising a non-coordinating anion and a counter cation. For example, triphenylcarbonium tetrakis (pentafluorophenyl) borate is preferably used.

For the preparation of the catalyst, in addition to the components (x), (y), and (z), the same conjugated diene compound and / or non-conjugated diene monomer as the polymerization monomer is used in combination as necessary. May be.
Further, a part or all of the component (x) or the component (z) may be supported on an inert solid, and in this case, it can be carried out by so-called gas phase polymerization.
Although the usage-amount of the said catalyst can be set suitably, normally (x) component is about 0.001-0.5 millimoles per 100g of monomers. Moreover, (y) component / (x) component is about 5-1000 and (z) component / (x) component is about 0.5-10 by molar ratio.
Examples of the solvent used in the solution polymerization include organic solvents inert to the reaction, for example, hydrocarbon solvents such as aliphatic, alicyclic, and aromatic hydrocarbon compounds. Specifically, those having 3 to 8 carbon atoms are preferred, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2-butene, Examples thereof include cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene. These may be used alone or in combination of two or more.

The temperature in this polymerization reaction is preferably selected in the range of −80 to 150 ° C., more preferably −20 to 120 ° 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 will depend on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, and such a pressure can be used with a gas inert to the polymerization reaction. It can be obtained by an appropriate method such as pressurization.
In this polymerization, it is desirable to use a material from which reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds are substantially removed as all raw materials involved in the polymerization, such as a catalyst, a solvent, and a monomer.

[Modifier]
In the present invention, the active terminal of the conjugated diene-aromatic vinyl copolymer having an active terminal and the conjugated diene polymer obtained as described above contains (C) a nitrogen atom and a silicon atom as a modifier. The (A) modified conjugated diene-aromatic vinyl copolymer and (B) modified conjugated diene polymer can be produced by reacting a hydrocarbyloxysilane compound or (D) a hydrocarbyloxysilane compound containing a silicon atom.
As the modifier, a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom in one molecule as the component (C) is preferable. In particular, the primary amino group is protected in the molecule and one hydrocarbyloxy group is present. And a compound containing a bifunctional silicon atom in which one reactive group is bonded to the same silicon atom.

[(C) Hydrocarbyloxysilane compound-1 containing nitrogen atom and silicon atom]
Component (C) is a hydrocarbyloxysilane compound represented by the following general formula (I)

[In the formula, A ¹ is a monovalent group having at least one functional group selected from a cyclic tertiary amino group, an acyclic tertiary amino group, an isocyanate group, a thioisocyanate group, an imine residue, and a pyridine residue; ¹ is a single bond or a divalent inert hydrocarbon group, R ² and R ³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aliphatic group having 6 to 18 carbon atoms. an aromatic hydrocarbon group, n is an integer from 0 to 2, if the oR ³ there are a plurality, the plurality of oR ³ may be the same or different and active proton and onium salt in the molecule include I can't. Here, the single bond means that A ¹ and Si are directly bonded by a single bond. ]
And a partial condensate thereof can be used. Here, the partial condensate refers to a product in which a part (not all) of SiOR of the hydrocarbyloxysilane compound is bonded to SiOSi by condensation.

In the general formula (I), among the functional groups in A ¹ , the imine residue includes a ketimine group, an aldimine group, and an amidine group.
Preferred examples of the divalent inert hydrocarbon group in R ¹ include an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched, or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.

Examples of R ² and R ³ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. Here, the alkyl group and alkenyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl, hexenyl, octenyl , Cyclopentenyl group, cyclohexenyl group and the like.
The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Further, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
n is an integer of 0 to 2, but 0 is preferable, and it is necessary that this molecule does not have an active proton or onium salt.

  Among the compounds represented by the general formula (I), 3-dimethylaminopropyl (triethoxy) silane, 3-dimethylaminopropyl (trimethoxy) silane, 3-diethylamino are used as the acyclic tertiary amino group-containing hydrocarbyloxysilane compounds. Propyl (triethoxy) silane, 3-diethylaminopropyl (trimethoxy) silane, 2-dimethylaminoethyl (triethoxy) silane, 2-dimethylaminoethyl (trimethoxy) silane, 3-dimethylaminopropyl (diethoxy) methylsilane, 3-dibutylaminopropyl (Triethoxy) silane and the like can be mentioned, among which 3-diethylaminopropyl (triethoxy) silane and 3-dimethylaminopropyl (triethoxy) silane are preferable.

  Further, as the cyclic tertiary amino group-containing hydrocarbyloxysilane compound, 3- (1-hexamethyleneimino) propyl (triethoxy) silane, 3- (1-hexamethyleneimino) propyl (trimethoxy) silane, (1-hexamethyleneimino ) Methyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (trimethoxy) silane, 3- (1-pyrrolidinyl) propyl (triethoxy) silane, 3- (1-pyrrolidinyl) propyl (trimethoxy) silane, 3- (1-heptamethyleneimino) propyl (triethoxy) silane, 3- (1-dodecamethyleneimino) Propyl (triethoxy) Run, 3- (1-hexamethyleneimino) propyl (diethoxy) methylsilane, 3- (1-hexamethyleneimino) can be preferably exemplified propyl (diethoxy) ethylsilane. In particular, 3- (1-hexamethyleneimino) propyl (triethoxy) silane is preferred. Furthermore, examples of other hydrocarbyloxysilane compounds include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 4-ethylpyridine and the like.

  As an imine residue-containing hydrocarbyloxysilane compound, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) ) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- ( 4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their triethoxysilyl Trimethoxysilyl compound, methyldiethoxysilyl compound, ethyldiethoxysilyl compound, methyl corresponding to the compound Preferred examples include dimethoxysilyl compounds and ethyldimethoxysilyl compounds. Among these, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1 , 3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is preferred.

  Furthermore, the following can be mentioned as another hydrocarbyloxy compound. That is, as imino (amidine) group-containing compounds, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5-dihydro Examples include imidazole and 3- [10- (triethoxysilyl) decyl] -4-oxazoline. Among them, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole can be mentioned. And 1- [3- (trimethoxysilyl) propyl] -4,5-dihydroimidazole can be preferably mentioned. Moreover, 1- [3- (triisopropoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (methyldiethoxysilyl) propyl] -4,5-dihydroimidazole, and the like can be given.

Examples of the isocyanate group-containing compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.
One of these hydrocarbyloxysilane compounds may be used alone, or two or more thereof may be used in combination. Moreover, the partial condensate of the said hydrocarbyl oxysilane compound can also be used.

[(D) Hydrocarbyloxysilane compound containing silicon atom]
The component (D) is a hydrocarbyloxysilane compound represented by the following general formula (II)

[Wherein, R ⁴ and R ⁵ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; an integer 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ may be the same as or different from each other, also in the molecule does not include an active proton and an onium salt. And a partial condensate thereof, and the following general formula (III)

[In the formula, A ² represents an epoxy group, a thioepoxy group, a ketone group, a thioketone group, an aldehyde group, a thioaldehyde group, an isocyanuric acid trihydrocarbyl ester residue, a carboxylic acid ester residue, a thiocarboxylic acid ester residue, a carboxylic acid anhydride. residues, monovalent group having at least one functional group selected from carboxylic acid halide residue and carbonate dihydrocarbyl ester residue, R ⁶ is a single bond or a divalent inactive hydrocarbon group, R ⁷ And R ⁸ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, m is an integer of 0 to 2, If oR ⁸ there are a plurality, the plurality of oR ⁸ may be the same or different, and in the molecule does not include an active proton and an onium salt. ] The hydrocarbyl oxysilane compound represented by these, and its partial condensate can be used.

Examples of the hydrocarbyloxysilane compound represented by the general formula (II) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, Tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, Butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltrie Kishishiran, divinyl dimethoxysilane, may be mentioned divinyl diethoxy silane, among these, in particular tetraethoxysilane are preferred.
This hydrocarbyloxysilane compound (II) may be used alone or in combination of two or more.

Examples of the hydrocarbyloxysilane compound represented by the general formula (III) include, for example, thioepoxy group and epoxy group-containing hydrocarbyloxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethyltriethoxy. Silane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane (GPMOS), 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and these compounds Epoch There may be mentioned preferably those obtained by replacing the group to thioepoxy groups, among these, in particular 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl trimethoxysilane is preferred.
One of these hydrocarbyloxysilane compounds may be used alone, or two or more thereof may be used in combination. Moreover, the partial condensate of the said hydrocarbyl oxysilane compound can also be used.

[(C) Hydrocarbyloxysilane compound-2 containing nitrogen atom and silicon atom]
As the modifier, a compound containing a bifunctional silicon atom in which a primary amino group is protected in the molecule and one hydrocarbyloxy group and one reactive group are bonded to the same silicon atom is preferable.
The compound containing a bifunctional silicon atom is represented by the general formula (IV)

Wherein R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1 A silicon compound represented by formula (V): an alkylene group of -12, A is a reactive group, and f is an integer of 1-10.

(Wherein R ^{15 to} R ¹⁹ each independently represents a hydrocarbon group having 1 to ²⁰ carbon atoms, and R ²⁰ represents an alkylene group having 1 to 12 carbon atoms) and a general formula ( VI)

Wherein R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1 -12 alkylene group, R ²¹ is an alkylene group having 1 to 12 carbon atoms, A is a reactive group, and f is an integer of 1 to 10.)

In the above formulas (IV) to (VI), preferred examples of the alkylene group having 1 to 12 carbon atoms of R ¹⁴ or R ²⁰ include a methylene group, an ethylene group, and a propylene group. Examples of the hydrocarbon group having 1 to 20 carbon atoms include aryl groups such as alkyl groups such as methyl group, ethyl group and propyl group, and aralkyl groups such as phenyl group, toluyl group, naphthyl group and benzyl group. .
Further, two of R ¹¹ , R ¹² and R ^{13 in} the formula (IV) may be bonded to form a 4- to 7-membered ring together with the silicon atom to which they are bonded. Two of R ¹⁷ , R ¹⁸ and R ¹⁹ in (V) may be bonded to form a 4- to 7-membered ring together with the silicon atom to which they are bonded. R ²¹ is an alkylene group having 1 to 12 carbon atoms.
In consideration of the reactivity with the polymerization active terminal, the reactive group A in the above formula (IV) or the above formula (VI) is preferably a halogen atom or an alkoxy group having 1 to 20 carbon atoms.

  Examples of the compound containing a protected primary amino group and a bifunctional silicon atom having at least an alkoxy group bonded to a silicon atom include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis ( Trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, and 1-trimethylsilyl-2,2-diethoxymethyl Examples thereof include -1-aza-2-silacyclopentane.

Examples of the compound in which the reactive group A is a halogen atom include N, N-bis (trimethylsilyl) aminopropylmethylmethoxychlorosilane, N, N-bis (trimethylsilyl) aminopropylmethylethoxychlorosilane, N, N-bis ( And trimethylsilyl) aminoethylmethylmethoxychlorosilane and N, N-bis (trimethylsilyl) aminoethylmethylethoxychlorosilane.
Preferably, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, 1-trimethylsilyl-2,2-diethoxymethyl-1-aza-2- Silacyclopentane.

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 above modification reaction, it is preferable that the polymer to be used has at least 10% of the polymer chain having a living property.

  In the modification reaction with the modifying agent, the amount of the modifying agent is preferably 0.5 to 200 mmol / kg · conjugated diene-aromatic vinyl copolymer or conjugated diene polymer. The content is more preferably 1 to 100 mmol / kg · conjugated diene-aromatic vinyl copolymer or conjugated diene polymer, particularly preferably 2 to 50 mmol / kg · conjugated diene-aromatic vinyl copolymer or It is a conjugated diene polymer. Here, the conjugated diene-aromatic vinyl copolymer or 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 production. By making the usage-amount of a modifier into the said range, it is excellent in the dispersibility of a filler, and the mechanical property after abrasion, abrasion resistance, and low fuel consumption are improved.

The method for adding the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, and a continuous addition method. preferable.
In addition, the modifier may be bonded to any of the polymerization initiation terminal, polymerization termination terminal, polymer main chain, and side chain, but it can improve fuel economy by suppressing energy loss from the polymer terminal. Therefore, it is preferably introduced at the polymerization initiation terminal or the polymerization termination terminal.

[Condensation accelerator]
In the present invention, it is preferable to use a condensation accelerator in order to accelerate the condensation reaction involving the alkoxysilane compounds (C) and (D) 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. Further, 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 occurs, and for example, a hydrocarboxy group having a protected primary amino group at the active end may not be introduced.
The addition time of the condensation accelerator is usually 5 minutes to 5 hours after the start of the modification reaction, preferably 15 minutes to 1 hour after the start of the modification reaction.

  Specific examples of the titanium 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) -1,3-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-butoxytitanium, tetra-tert-butoxytitanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolaminine) G), titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titaniumpropoxyacetylacetonatebis (ethylacetate) Acetate), titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate), titanium tributoxyethylacetoacetate, titaniumbutoxyacetylacetonatebis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetate Bis (ethyl acetoacetate), bis (2-ethylhexanoate) titanium oxide, bis (laurate) titanium oxide, bis ( Naphthenate) 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. Among these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.

  As the tin-based condensation accelerator, divalent tin dicarboxylic acid {particularly, bis (hydrocarbylcarboxylic acid) salt, for example, bis (2-ethylhexanoate) tin}, or tetravalent tin dihydrocarbyl. Preferred examples include tin dicarboxylate {including bis (hydrocarbylcarboxylic acid)} salt, bis (β-diketonate), alkoxy halide, monocarboxylate hydroxide and the like. The hydrocarbyl group bonded to tin preferably has 4 or more carbon atoms, and particularly preferably has 4 to 8 carbon atoms.

  Examples of other condensation accelerators include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, tris ( Linoleate) bismuth, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, tetra (2-ethylhexyl) zirconium, zirconium Tributoxy systemate, 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 , It may be mentioned tetrakis (linolate) zirconium.

  Examples of the aluminum condensation accelerator include triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tri (2 -Ethylhexyl) aluminum, aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), Tris (2-ethylhexanoate) aluminum, tris (laurate) aluminum, tris (naphthenate) aluminum, tris It can be mentioned (stearate) aluminum, tris (oleate) aluminum, tris (linolate) aluminum.

  Of the above-mentioned condensation accelerators, titanium-based condensation accelerators are preferred, and titanium metal alkoxides, titanium metal carboxylates, or titanium metal acetylacetonate complex salts are particularly preferred. The amount of the condensation accelerator used is preferably such that the number of moles of the compound is 0.1 to 10 as the molar ratio to the total amount of hydrocarbyloxy groups present in the reaction system, and 0.5 to 5 Particularly preferred. By setting the 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.
Further, the condensation reaction may be performed in an aqueous solution, and the condensation reaction temperature is preferably 10 to 180 ° C, more preferably 20 to 170 ° C, and particularly preferably 30 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 polymer aging reaction due to the change over time of the resulting modified conjugated diene-aromatic vinyl copolymer and conjugated diene polymer. It is possible to suppress deterioration in quality due to the like.

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 modifier of the modified conjugated diene-aromatic vinyl copolymer and the conjugated diene polymer according to 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 this solvent, a modified conjugated diene-aromatic vinyl copolymer and 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 step from the step including the condensation treatment to the solvent removal to the dry polymer.

[(A) Modified Conjugated Diene-Aromatic Vinyl Copolymer or (B) Modified Conjugated Diene Polymer]
Particularly preferred (A) modified conjugated diene-aromatic vinyl copolymer or (B) modified conjugated diene polymer is used at the active end of the conjugated diene polymer or conjugated diene-aromatic vinyl copolymer having a modified active end. Titanium-based condensation is performed by reacting a compound containing a bifunctional silicon atom in which a primary amino group is protected in the molecule and one hydrocarbyloxy group and a reactive group are bonded to the same silicon atom. It can be obtained by performing a condensation reaction involving the bifunctional silicon compound in the presence of an accelerator and deprotecting the protected primary amino group derived from the modifier. These obtained modified polymers enhance the dispersion of carbon black alone or a mixed filler of carbon black and silica in the rubber component, and are the subjects of the present invention, such as low fuel consumption, ice / snow performance and wear resistance. A tire having good wet performance and excellent wet performance, particularly a pneumatic tire can be obtained.
The thus obtained (A) conjugated diene-aromatic vinyl copolymer and (B) modified conjugated diene polymer have a Mooney viscosity (ML _{1 + 4} , 100 ° C.), preferably 10 to 150. Preferably it is 15-100. 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 component (A) and the component (B) is preferably 10 to 150, more preferably 30. ~ 100.

The component (A) and the component (B2) used in the rubber composition according to the present invention are the 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 preferably 1 to 3, and more preferably 1.1 to 2.7.
Even if the component (A) and the component (B2) are blended in the rubber composition by setting the molecular weight distribution (Mw / Mn) of the component (A) and the component (B2) within the above range, the operation of the rubber composition Therefore, kneading is easy and the physical properties of the rubber composition can be sufficiently improved.
On the other hand, natural rubber and polyisoprene rubber suitably used as the component (B1) are not particularly limited, and can be appropriately selected from conventionally known rubbers. More preferably, the polyisoprene rubber has a weight average molecular weight of 100,000 or more and a cis bond content of 95% or more. Although there is no restriction | limiting in particular in this weight average molecular weight, Usually, about 2,500,000 is an upper limit.

  The component (A) and the component (B2) used in the rubber composition according to the present invention preferably have a weight average molecular weight (Mw) before or after modification of 100,000 to 800,000, 150 More preferably, it is from 1,000,000 to 700,000. By making the weight average molecular weights of the component (A) and the component (B2) within the above range, the elastic modulus of the vulcanizate is reduced and the increase in hysteresis loss is suppressed to obtain excellent fracture resistance, and the (A) Excellent kneading workability of the rubber composition containing the component and the component (B2) can be obtained.

[Other rubber components]
The rubber component according to the present invention includes, in addition to (A) a modified conjugated diene-aromatic vinyl copolymer and (B) a conjugated diene polymer, various rubber components, particularly diene, within a range that meets the object of the present invention. System rubber can be included.
For example, an unmodified conjugated diene-aromatic vinyl copolymer such as emulsion-polymerized styrene-butadiene rubber, unmodified solution-polymerized styrene-butadiene rubber, component (A) or component (B) has a glass transition temperature Tg range. Polybutadiene rubber, styrene-butadiene rubber, polyisoprene rubber, styrene-isoprene rubber, etc., ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, chloroprene rubber, halogenated butyl rubber and halogenated Examples include a copolymer of styrene and isobutylene having a methyl group.
It is more preferable that some or all of these diene rubbers are diene rubbers having a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride.

[Thermoplastic resin]

The softening point of the thermoplastic resin used in the rubber composition for a tread according to the tire of the present invention is preferably 50 to 150 ° C. Within this range, the unvulcanized rubber composition is plasticized, the shrinkage in the extrusion process is suppressed, the workability is remarkably improved, and the wet performance of the vulcanized rubber composition is greatly improved. . When the softening point is less than 50 ° C., it is softened at room temperature, so that the handleability is deteriorated and it becomes difficult to add the solid at the time of kneading. On the other hand, when the softening point exceeds 150 ° C., the heat generation of the rubber composition increases, and the rolling resistance of the tire increases.
The rubber composition used for the tread of the tire of the present invention preferably contains 5 to 20 parts by mass of a thermoplastic resin with respect to 100 parts by mass of the rubber component. If it is 5 parts by mass or more, the workability improving effect, particularly the shrinkage improving effect is suitably exhibited, and if it is 20 parts by mass or less, the fuel efficiency is improved.
Suitable thermoplastic resins include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, terpene resins, terpene phenol resins, and the like.

  Examples of the aliphatic hydrocarbon resin include a petroleum resin produced by polymerizing a C5 petroleum fraction. Petroleum resins produced from high-purity 1,3-pentadiene as the main raw material include trade names “Quinton 100” series (A100, B170, K100, M100, R100, N295, U190, S100, manufactured by Nippon Zeon Co., Ltd.). , D100, U185, P195N, etc.). In addition, as petroleum resins produced by polymerizing other C5 petroleum fractions, trade names “Escollets” series (1102, 1202 (U), 1304, 1310, 1315, 1395 etc.) manufactured by Exxon Mobile, Trade name “HI-LET'S” series (G-100X, -T-100X, -C-110X, -R-100X, etc.) manufactured by Mitsui Chemicals, Inc. may be mentioned.

  Cyclopentadiene petroleum resin produced from cyclopentadiene extracted from C5 fraction as the main raw material and dicyclopentadiene series produced from dicyclopentadiene in C5 fraction as the main raw material as alicyclic hydrocarbon resin Petroleum resin is mentioned. For example, as a cyclopentadiene-based petroleum resin produced using high-purity cyclopentadiene as a main raw material, trade name “Quinton 1000” series (1325, 1345, etc.) manufactured by Nippon Zeon Co., Ltd. can be mentioned. Moreover, as a dicyclopentadiene-type petroleum resin, the brand name "Marcaretz M" series (M-890A, M-845A, M-990A etc.) of Maruzen Petrochemical Co., Ltd. is mentioned.

  The terpene resin is a resin produced using natural turpentine oil or orange oil as a main raw material. The product name “YS Resin” series (PX-1250, TR-105, etc.) manufactured by Yashara Chemical Co., Ltd., Hercules Co., Ltd. Product name “Picolite” series (A115, S115, etc.).

  As the terpene phenol resin, for example, YShara Chemical Co., Ltd. trade name “YS Polystar” series (U series such as U-130 and U-115, T-series such as T-115, T-130 and T-145) )), Trade name “Tamanol 901” manufactured by Arakawa Chemical Industries, Ltd., and the like.

[Filler]
The rubber composition used for the tread of the tire of the present invention preferably contains 50 to 100 parts by mass of a filler as a filler with respect to 100 parts by mass of the rubber component. If it is 50 parts by mass or more, the wear resistance is improved, and if it is 100 parts by mass or less, the fuel efficiency is improved. The combined use of carbon black and silica is preferable from the viewpoint of improving wet performance, wear resistance and fracture characteristics.
This filler is preferably carbon black and / or silica. In particular, the filler is preferably carbon black and silica, and the content ratio of carbon black and silica is preferably (10:90) to (50:50) in mass ratio. It is preferable that the compounding quantity of a silica is 30-80 mass parts with respect to 100 mass parts of rubber components. If it is this range, low-fuel-consumption property, ice-snow performance, and abrasion resistance will become more favorable, and wet performance can be improved more.
There is no restriction | limiting in particular as carbon black, For example, HAF, N339, IISAF, 1 SAF, SAF etc. are used.
The nitrogen adsorption method specific surface area (measured in accordance with N ₂ SA, JIS K 6217-2: 2001) of carbon black is preferably 70 to 180 m ² / g, more preferably 80 to 180 m ² / g. Moreover, DBP oil absorption (measured based on JISK6217-4: 2001) becomes like this. Preferably it is 70-160 mL / 100g, More preferably, it is 90-160 mL / 100g. By using carbon black, improvement effects such as fracture resistance and wear resistance are increased. N339, IISAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable.

Examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among them, wet is most effective in achieving both wet performance and wear resistance. Silica is preferred.
The BET specific surface area (measured in accordance with ISO 5794/1) of silica is preferably 80 m ² / g or more, more preferably 120 m ² / g or more, particularly preferably 150 m ² / g or more. Although there is no restriction | limiting in particular in the upper limit of a BET specific surface area, Usually, it is about 450 m < ² > / g. Such a Tosoh Silica Co., Ltd. as silica, trade name "Nipsil AQ" (BET specific surface area = 190m ² / g), "Nipsil KQ", Degussa Corporation, trade name "Ultra Jill VN3" (BET specific surface area = 175m ² / G) and other commercial products can be used.
One type of carbon black and / or silica may be used, or two or more types may be used in combination.

[Silane coupling agent]
In the rubber composition according to the present invention, if desired, when silica is used as one of the reinforcing fillers, a silane coupling agent may be blended for the purpose of further improving the reinforcing property and fuel efficiency. preferable.
Examples of silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxysilyl). Ethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarba Yl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyltetrasulfide, 3-triethoxy Silylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like are mentioned. Among these, bis (3 Triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropyl benzothiazyl tetrasulfide are preferable.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  In the rubber composition according to the present invention, a modified polymer in which a functional group having a high affinity for silica is introduced into a molecular active site is used as a rubber component. It can be reduced from the normal case. Although the compounding quantity of a preferable silane coupling agent changes with kinds etc. of a silane coupling agent, Preferably it selects in the range of 1-20 mass% with respect to a silica. If this amount is less than 1% by mass, the effect as a coupling agent is hardly exhibited, and if it exceeds 20% by mass, the rubber component may be gelled. From the viewpoints of the effect as a coupling agent and the prevention of gelation, the preferable amount of the silane coupling agent is in the range of 5 to 15% by mass with respect to silica.

Further, the rubber composition according to the present invention includes various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an aging, as long as the effects of the present invention are not impaired. An inhibitor, a scorch inhibitor, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of (B) 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 fracture strength, wear resistance, and fuel efficiency 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 (B) rubber component.

  Moreover, as a process oil used as a softening agent which can be used for the rubber composition according to the present invention, for example, naphthenic or paraffinic is used from the viewpoint of emphasizing low temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the (B) rubber component, and if it is 100 parts by mass or less, the tensile strength and low fuel consumption (low heat build-up) of the vulcanized rubber are deteriorated. Can be suppressed. If necessary, a phthalic acid derivative plasticizer such as dibutyl phthalate or di (2-ethylhexyl) phthalate may be used.

  Further, examples of the anti-aging agent that can be used in the rubber composition according to the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N ′). -Phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, etc. (B) 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-mentioned blending prescription, vulcanizing after molding, and a pneumatic tire. Used as a tread.
The tire of the present invention is manufactured by a normal tire manufacturing method using the rubber composition according to the present invention for a tread. 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.
In this way, it is possible to obtain a tire, particularly a pneumatic tire, with good fuel efficiency, ice / snow performance, wet performance and dry performance.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples. Various measurements in the examples were performed by the following methods.
[Physical properties of unmodified or modified conjugated diene polymer and unmodified or modified conjugated diene-aromatic vinyl copolymer]
<Glass transition temperature Tg>
The temperature was measured at 10 ° C./min after cooling to −150 ° C. with a differential scanning calorimeter (DSC).
<Microstructure analysis method>
1-4 cis bond content and vinyl bond content (%) were measured by an infrared method (Morello method). The amount of bound styrene was determined by calculating the integral ratio of the spectrum by ¹ H-NMR.
<Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
It measured using GPC [The Tosoh make, HLC-8020] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.
<Measurement of Mooney viscosity (ML _{1 + 4} , 100 ° C.)>
According to JIS K6300, it was determined at a temperature of 100 ° C., L overnight, preheating 1 minute, rotor operating time 4 minutes.
<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 the secondary amino group and the tertiary amino group were quantified by “acetylacetone blocked method” using the polymer subjected to the above treatment as a sample. As a solvent for dissolving the sample, o-nitrotoluene was used, acetylacetone was added, and potentiometric titration was performed with a perchloracetic acid solution. The primary amino group content (mmol) is obtained by subtracting the secondary amino group content and tertiary amino group content from the total amino group content, and divided by the polymer mass used in the analysis to bind to the first polymer. The amino group content (mmol / kg) was determined.

[Evaluation of characteristic values with unvulcanized rubber]
<Shrinkage of unvulcanized rubber>
The amount of shrinkage of the tread after being extruded at a constant length by a tire tread extruder was measured. The shrinkage length of Comparative Example 1 was taken as 100, and the index was displayed with the following colors. Smaller values are better with less shrinkage.
(Shrinkage of test unvulcanized rubber / shrinkage of unvulcanized rubber of Comparative Example 1) × 100
[Evaluation of characteristic values by vulcanized rubber]
<Wet performance>
A brake test was performed from 80 km / h on a wet road surface, and the reciprocal of the distance (m) until the vehicle stopped was indexed with Comparative Example 1 being 100. A larger value is better.
<Ice and snow performance>
Using a spectrometer (dynamic viscoelasticity tester) manufactured by Toyo Seiki Co., Ltd., the dynamic storage elastic modulus E ′ was measured at a frequency of 52 Hz, an initial strain of 10%, a measurement temperature of −20 ° C., and a dynamic strain of 1%. The reciprocal of the value was expressed as an index with the reciprocal of E ′ in Comparative Example 1 being 100. The larger the index value, the better the snow and snow performance.
<Low fuel consumption>
Using a spectrometer (dynamic viscoelasticity measuring tester) manufactured by Toyo Seiki Co., Ltd., tan δ was measured at a frequency of 52 Hz, an initial strain of 10%, a measurement temperature of 60 ° C., and a dynamic strain of 1%. The reciprocal of tan δ in Comparative Example 1 was taken as 100 and displayed as an index. The larger the index value, the better the fuel economy.
<Abrasion resistance>
After testing at room temperature by JIS K 6264-1993 Lambourne abrasion test, it was calculated by the following formula, and Comparative Example 1 was set as 100.
Abrasion resistance index = (Abrasion amount of Comparative Example 1 / Abrasion amount of test sample) × 100
The larger the wear resistance index, the better the wear resistance.

Production Example 1 Production of primary amine-modified styrene-butadiene rubber <Synthesis of modifier>
Synthesis Example 1: Synthesis of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane 36 g of 3-aminopropylmethyldiethoxy as an aminosilane moiety in 400 mL of dichloromethane solvent in a glass flask equipped with a stirrer under nitrogen atmosphere After adding silane (manufactured by Gelest), 48 mL of trimethylsilane chloride (manufactured by Aldrich) and 53 mL of triethylamine were further added to the solution as protective sites, and the mixture was stirred at room temperature for 17 hours, and then the reaction solution was applied to an evaporator. The solvent was removed to obtain a reaction mixture, and the obtained reaction mixture was distilled under reduced pressure under a pressure of 665 Pa to obtain 40 g of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as a 130-135 ° C. fraction. Obtained.
<Synthesis of primary amine-modified styrene-butadiene rubber>
An autoclave reactor having an internal volume of 5 L (liter) purged with nitrogen was charged with 2,750 g of cyclohexane, 16.8 mmol of tetrahydrofuran, 125 g of styrene, and 375 g of 1,3-butadiene. After adjusting the temperature of the reactor contents to 10 ° C., 1.2 mmol of n-butyllithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C.
When the polymerization conversion rate reached 99%, 10 g of butadiene was added, and polymerization was further performed for 5 minutes. A small amount of the polymer solution from the reactor was sampled in 30 g of a cyclohexane solution added with 1 g of methanol, and then 1.1 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane obtained in Synthesis Example 1 was added to modify the polymer solution. The reaction was run for 15 minutes. Thereafter, 0.6 mmol of tetrakis (2-ethyl-1,3-hexanediolato) titanium was added and further stirred for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the solvent was removed by steam stripping and the protected primary amino group was deprotected, and the rubber was dried with a rip roll adjusted to 110 ° C. to obtain a primary amine-modified styrene-butadiene rubber. The resulting primary amine-modified styrene-butadiene rubber has a glass transition temperature Tg of -38 ° C., a bound styrene content of 24.5% by mass, a vinyl content of the conjugated diene part of 56 mol%, a Mooney viscosity of 32, and before modification. The weight average molecular weight was 158,000, and the molecular weight distribution before modification was 1.05. The primary amino group content was 6.3 mmol / kg.

Production Example 2 Production of Hexamethyleneimine-Modified Styrene-Butadiene Rubber In a 800 mL (milliliter) pressure-resistant glass container that had been dried and purged with nitrogen, 300 g of cyclohexane, 37.5 g of 1,3-butadiene monomer, 12 of styrene monomer 12 0.5 g, 0.03 mmol of potassium tert-amylate and 2 mmol of THF were injected, and 0.41 mmol of hexamethyleneimine was further added as a secondary amine. To this was added 0.45 mmol of n-butyllithium (BuLi), followed by polymerization at 50 ° C. for 2.5 hours. The polymerization system was uniform and transparent from the start to the end of the polymerization without any precipitation. The polymerization conversion was almost 100%. A part of the polymerization solution was sampled, isopropyl alcohol was added, and the solid was dried to obtain a rubbery copolymer. The microstructure, molecular weight, and molecular weight distribution of this copolymer were measured. To this polymerization system, 0.09 mmol of a 1 mol / L cyclohexane solution of tin tetrachloride was further added as a modifier, and then a modification reaction was performed for another 30 minutes. Thereafter, 0.5 mL of a 5 mass% isopropyl alcohol solution of 2,6-di-tert-butylparacresol (BHT) was further added to the polymerization system to stop the reaction, followed by drying according to a conventional method. A styrene-butadiene copolymer rubber (modified SBR) was obtained. The obtained modified SBR has a glass transition temperature Tg of −50 ° C., a bound styrene content of 25% by mass, a vinyl bond content of 28 mol%, a Mooney viscosity of 27, a weight average molecular weight before modification of 180,000, The previous molecular weight distribution was 1.21.

Production Example 3 Production of GPMOS Modified Styrene-Butadiene Rubber In a dry, nitrogen-substituted 800 mL pressure-resistant glass container, 40 g of butadiene monomer was added with a cyclohexane solution of butadiene (16 mol%) and a cyclohexane solution of styrene (21 mol%). Then, 10 g of styrene monomer was injected, 0.44 mmol of 2,2-ditetrahydrofurylpropane was injected, 0.48 mmol of n-butyllithium (BuLi) was added thereto, and then a hot water bath at 50 ° C. Polymerization was carried out for 1.5 hours. The polymerization conversion was almost 100%.
After adding 0.43 mmol of 3-glycidoxypropyltrimethoxysilane (GPMOS) to this polymerization system, a modification reaction was further performed at 50 ° C. for 30 minutes. Thereafter, 1.26 mmol of bis (2-ethylhexanoate) tin and 1.26 mmol of water were added to the polymerization system, and then a condensation reaction was performed at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of a 5 wt% isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) was further added to the polymerization system to stop the reaction. Then, the modified styrene-butadiene rubber was obtained by drying according to a conventional method. The resulting modified styrene-butadiene rubber has a glass transition temperature Tg of -40 ° C., a bound styrene content of 20% by mass, a vinyl content of the conjugated diene part of 52.6 mol%, a Mooney viscosity of 70, and a weight average molecular weight before modification. Was 184,000, and the molecular weight distribution before modification was 1.21.

Production Example 4 Production of Tetraethoxysilane-Modified Styrene-Butadiene Rubber In an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, butadiene in cyclohexane solution (16 mol%) and styrene in cyclohexane solution (21 mol%) 40 g of styrene monomer and 10 g of styrene monomer were injected, 0.44 mmol of 2,2-ditetrahydrofurylpropane was added, 0.48 mmol of n-butyllithium (BuLi) was added thereto, Polymerization was carried out in a warm water bath for 1.5 hours. The polymerization conversion was almost 100%.
After adding 0.43 mmol of tetraethoxysilane to this polymerization system, a modification reaction was further performed at 50 ° C. for 30 minutes. Thereafter, 1.26 mmol of tetrakis (2-ethylhexoxy) titanium and 1.26 mmol of water were added to the polymerization system, followed by a condensation reaction at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of a 5 wt% isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) was further added to the polymerization system to stop the reaction. Then, the modified styrene-butadiene rubber was obtained by drying according to a conventional method. The resulting modified styrene-butadiene rubber has a glass transition temperature Tg of -50 ° C., a bound styrene content of 19.9% by mass, a vinyl content of the conjugated diene part of 52 mol%, a Mooney viscosity of 64, and a weight average molecular weight before modification. Was 186,000, and the molecular weight distribution before modification was 1.07.

Production Example 5 Production of Modified Polybutadiene Rubber <Catalyst Preparation>
In a glass bottle with a rubber capacity of 100 mL, dried and nitrogen-substituted, in the following order, 7.11 g of cyclohexane solution of butadiene (15.2% by mass), cyclohexane solution of neodymium neodecanoate (0.56 mol / mol) L) 0.59 mL, toluene solution of aluminum aluminoxane MAO (PMAO manufactured by Tosoh Akzo Co., Ltd.) (aluminum concentration: 3.23 mol / L) 10.32 ml, hexane solution of diisobutylaluminum hydride (manufactured by Kanto Chemical) (0.90 mol / L) L) 7.77 mL was added, and after aging at room temperature for 2 minutes, 1.45 mL of a hexane solution (0.95 mol / L) of chlorinated diethylaluminum (manufactured by Kanto Chemical) was added, and the mixture was stirred at room temperature for 15 minutes. Aged. The neodymium concentration in the catalyst solution thus obtained was 0.011 mol / L.
<Production of intermediate polymer>
A glass bottle with a rubber stopper having a volume of about 900 mL was dried and purged with nitrogen, and a dry purified cyclohexane solution of butadiene and a dry cyclohexane were added to each, and 400 g of a cyclohexane solution of 12.5% by mass of butadiene was charged. Next, 2.28 mL (0.025 mmol in terms of neodymium) of the catalyst solution prepared in the above (1) was added, and polymerization was performed in a 50 ° C. warm water bath for 1.0 hour to produce an intermediate polymer.
<Modification>
A hexane solution having a 3-glycidoxypropyltrimethoxysilane (GPMOS) concentration of 1.0 mol / L is added to the polymerization solution obtained in (2) so that GPMOS is 23.5 molar equivalents relative to neodymium. It was charged and treated at 50 ° C. for 60 minutes.
Next, 1.2 mL of sorbitan trioleate (manufactured by Kanto Chemical Co., Inc.) was added, and after a further denaturing reaction at 60 ° C. for 1 hour, the antioxidant was added to the polymerization system 2,2′-methylene-bis (4- By adding 2 mL of a 5% by mass solution of ethyl-6-tert-butylphenol) (NS-5) in isopropanol, the reaction is stopped, and reprecipitation is performed in isopropanol containing a small amount of NS-5, followed by drum drying. A modified polybutadiene was obtained. In this modified polybutadiene, no macrogel was observed, the glass transition temperature Tg was −103 ° C., the Mooney viscosity before modification was 22, and the Mooney viscosity after modification was 59.

Examples 1-7 , Reference Examples 1-4 and Comparative Examples 1-6
Seventeen rubber compositions having the compounding compositions shown in Table 1 were prepared, and the shrinkage in the extrusion process of each unvulcanized rubber composition was evaluated, and the physical properties of the vulcanized rubber, that is, wet performance, ice / snow performance, and low fuel consumption. And the wear resistance was evaluated. The evaluation results are shown in Table 1.

[note]
1) Emulsion polymerization SBR: SBR # 1500, manufactured by JSR 2) Carbon black: N234, manufactured by Tokai Carbon Co., Ltd., trade name “SEAST 7HM”
3) Silica: Tosoh Silica Co., Ltd., trade name “Nipseal AQ”
4) Silane coupling agent: Degussa, trade name “Si69”
5) Thermoplastic resin A: C5 aliphatic hydrocarbon resin, manufactured by Tonen Chemical Co., Ltd., trade name “ESCOREZ1102” (softening point 100 ° C.)
6) Thermoplastic resin B: dicyclopentadiene resin, manufactured by Maruzen Petrochemical Co., Ltd., trade name “Marcaretz M M-890A” (softening point 105 ° C.)
7) Thermoplastic resin C: Terpene resin, manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Resin PX-1250” (softening point 125 ° C.)
8) Thermoplastic resin D: terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Polystar T145” (softening point 145 ° C.)
9) Low temperature softener: Octyl oleate, manufactured by Kao Corporation, trade name “Splendor R400”
10) Anti-aging agent 6PPD: “Noxeller 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
11) Vulcanization accelerator DPG: “Noxeller D” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
12) Vulcanization accelerator CZ: “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
13) Vulcanization accelerator DM: “Noxeller DM” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

As is clear from Table 1, the rubber compositions of Examples 1 to 7 are small in shrinkage of unvulcanized rubber and have good processability compared to the rubber compositions of Comparative Examples 1 to 6, The wet performance, ice and snow performance, low fuel consumption and wear resistance were well balanced.
Next, 17 kinds of rubber compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were respectively arranged on the tread of a pneumatic tire for all seasons (tire size 195 / 60R15), and 17 kinds of air for all seasons were used. Pneumatic tires are manufactured in accordance with ordinary methods, and each of the 17 types of tires has wet performance by running on a wet road test course, and snow and snow performance by running on a snow road surface and on an ice road, and a pneumatic tire in accordance with SAE J2452. In comparison with the pneumatic tires of Comparative Examples 1 to 6, the pneumatic tires of Examples 1 to 7 are all evaluated for low fuel consumption by rolling resistance measurement and abrasion resistance by running on a general road. The wet performance, ice and snow performance, low fuel consumption and wear resistance were good.

  The tire of the present invention has good snow and snow performance and wear resistance, and is excellent in handling stability on wet road surfaces. Therefore, pneumatic tires for passenger cars such as pneumatic tires for all seasons, winter pneumatic tires, etc. It is suitably used for pneumatic tires for automobiles, pneumatic tires for light trucks, pneumatic tires for trucks and buses, and the like.

Claims (21)

A rubber composition containing a rubber component, a thermoplastic resin and a filler,
The rubber component contains (A) a modified conjugated diene-aromatic vinyl copolymer in an amount of 10 to 20 % by mass, (B) a conjugated diene polymer in an amount of 90% by mass or less, and an emulsion-polymerized styrene-butadiene rubber.
The polymerization initiator of the component (A) is a lithium amide compound, or the modifier used at the active terminal of the component (A) is (C) a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom,
The hydrocarbyloxysilane compound of component (C), which is a denaturant used at the active terminal of component (A), has a primary amino group protected in the molecule, and one reactivity with one hydrocarbyloxy group. A rubber composition, which is a compound containing a bifunctional silicon atom bonded to the same silicon atom as the group, is used for the tread,
The thermoplastic resin is at least one selected from C5 aliphatic hydrocarbon resin, dicyclopentadiene resin, terpene resin, terpene phenol resin,
The tire characterized in that the conjugated diene polymer of the component (B) contains a modified polybutadiene rubber and natural rubber.   The conjugated diene compound used as one raw material monomer of the component (A) is 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, and The tire according to claim 1, wherein the tire is at least one selected from 2-phenyl-1,3-butadiene.   The tire according to claim 2, wherein the aromatic vinyl compound used as another raw material monomer of the component (A) is styrene.   The tire according to any one of claims 1 to 3, wherein a glass transition temperature Tg of the modified conjugated diene-aromatic vinyl copolymer of the component (A) is -60 to -20 ° C.   The tire according to claim 3 or 4, wherein the modified conjugated diene-aromatic vinyl copolymer of the component (A) is a modified styrene-butadiene rubber.   The tire according to any one of claims 1 to 5, wherein the rubber component contains 10 to 90 mass% of the component (B).   The tire according to any one of claims 1 to 6, wherein a glass transition temperature Tg of the conjugated diene polymer of the component (B) is -110 to -50 ° C.   The tire according to claim 7, wherein the conjugated diene polymer of the component (B) has a glass transition temperature Tg of -80 to -50 ° C.   The conjugated diene compound used as a raw material monomer for the component (B) is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethyl-1,3-butadiene. The tire according to any one of claims 1 to 8, which is at least one kind.   The tire according to claim 7 or 9, wherein the conjugated diene polymer of the component (B) has a glass transition temperature Tg of -110 ° C or higher and lower than -80 ° C.   The modified polybutadiene rubber as component (B) was obtained by coordination anionic polymerization of a conjugated diene compound alone or another conjugated diene compound in an organic solvent using a catalyst containing a lanthanum series rare earth element-containing compound. (C) component or (D) component which is a modifier at the active terminal of the conjugated diene polymer having an active terminal, wherein the cis-1,4 bond content in the conjugated diene moiety of the main chain is 90 mol% or more The tire according to claim 10, wherein the hydrocarbyloxysilane compound is reacted.   The tire according to any one of claims 1 to 11, wherein the rubber component contains 40% by mass or less of the component (B). The hydrocarbyloxysilane compound of the component (C), which is a modifier used for the active terminal of the component (B), has the following general formula (I)

[Wherein A ¹ is a monovalent group having at least one functional group selected from a cyclic tertiary amino group, an acyclic tertiary amino group, an isocyanate group, a thioisocyanate group, an imine residue, and a pyridine residue; ¹ is a single bond or a divalent inert hydrocarbon group, R ² and R ³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aliphatic group having 6 to 18 carbon atoms. an aromatic hydrocarbon group, n is an integer from 0 to 2, if the oR ³ there are a plurality, the plurality of oR ³ may be the same or different and active proton and onium salt in the molecule include I can't. ]
The tire according to claim 11 or 12, which is at least one selected from a hydrocarbyloxysilane compound represented by the formula (1) and a partial condensate thereof. The hydrocarbyloxysilane compound of the component (D), which is a modifier used for the active terminal of the component (B), has the following general formula (II)

[Wherein, R ⁴ and R ⁵ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; an integer 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ may be the same as or different from each other, also in the molecule does not include an active proton and an onium salt. And a partial condensate thereof, and the following general formula (III)

[In the formula, A ² represents an epoxy group, a thioepoxy group, a ketone group, a thioketone group, an aldehyde group, a thioaldehyde group, an isocyanuric acid trihydrocarbyl ester residue, a carboxylic acid ester residue, a thiocarboxylic acid ester residue, or a carboxylic acid anhydride. residues, monovalent group having at least one functional group selected from carboxylic acid halide residue and carbonate dihydrocarbyl ester residue, R ⁶ is a single bond or a divalent inactive hydrocarbon group, R ⁷ And R ⁸ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, m is an integer of 0 to 2, If oR ⁸ there are a plurality, the plurality of oR ⁸ may be the same or different, and in the molecule does not include an active proton and an onium salt. The tire according to claim 11 or 12, which is at least one selected from a hydrocarbyloxysilane compound represented by the above and a partial condensate thereof.   The hydrocarbyloxysilane compound of component (C), which is a modifying agent used at the active terminal of component (B), has a primary amino group protected in the molecule, and one reactivity with one hydrocarbyloxy group. The tire according to claim 11 or 12, wherein the tire is a compound containing a bifunctional silicon atom bonded to the same silicon atom. The compound containing a bifunctional silicon atom has the general formula (IV)

(In the formula, R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1. A silicon compound represented by formula (V): an alkylene group of -12, A is a reactive group, and f is an integer of 1-10.

(Wherein R ^{15 to} R ¹⁹ each independently represents a hydrocarbon group having 1 to ²⁰ carbon atoms, and R ²⁰ represents an alkylene group having 1 to 12 carbon atoms) and a general formula ( VI)

(In the formula, R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁴ is a carbon number 1. An alkylene group having ˜12, R ²¹ is an alkylene group having 1 to 12 carbon atoms, A is a reactive group, and f is an integer of 1 to 10). The tire according to claim 1 or 15.   The tire according to claim 1 or 16, wherein the reactive group A in the general formula (IV) or the general formula (VI) is a halogen atom or an alkoxy group having 1 to 20 carbon atoms.   The tire according to any one of claims 1 to 17, comprising 5 to 20 parts by mass of the thermoplastic resin and 50 to 100 parts by mass of the filler with respect to 100 parts by mass of the rubber component.   The tire according to any one of claims 1 to 18, wherein a softening point of the thermoplastic resin is 50 to 150 ° C.   The tire according to any one of claims 1 to 19, wherein the filler is carbon black and / or silica. The filler is carbon black and silica, and the content ratio of carbon black and silica is (10:90) to (50:50) in mass ratio. tire.